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                         Europäisches Patentamt
     (19)                European Patent Office
                         Office européen des brevets
                                                                                         dl)     EP 1294 799 B1
     (12)                              EUROPEAN PATENT SPECIFICATION

     (45) Date of publication and mention                              (51) intci7: C08K 5/00, C08L 27/06,
          of the grant of the patent:
                                                                                    C08K 5/1515
          04.08.2004 Bulletin 2004/32
                                                                       (86) International application number:
     (21) Application number: 01946592.1                                    PCT/US2001/019751

     (22) Date of filing: 20.06.2001                                   (87) International publication number:
                                                                            WO 2001/098404 (27.12.2001 Gazette 2001/52)

     (54) PLASTICIZERS DERIVED FROM VEGETABLE OILS
            AUS PFLANZENÖLEN STAMMENDE WEICHMACHER
            PLASTIFIANTS PRODUITS A PARTIR D'HUILES VEGETALES

     (84) Designated Contracting States:                                   • ELHARD, Joel, D.
          AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU                       Hilliard, OH 43026 (US)
          MCNLPTSETR                                                       • VIJAYENDRAN, Bhima, R.
                                                                             Dublin, OH 43017 (US)
     (30) Priority: 20.06.2000 US 596971
                    04.05.2001 US 849071                               (74) Representative:
                                                                            Bunke, Holger, Dr.rer.nat. Dipl.-Chem. etal
     (43) Date of publication of application:                               Prinz & Partner GbR
          26.03.2003 Bulletin 2003/13                                       Manzingerweg 7
                                                                            81241 München (DE)
     (73) Proprietor: BATTELLE MEMORIAL INSTITUTE
          Columbus Ohio 43201-2693 (US)                                (56) References cited:
                                                                            EP-A-0 358 181               EP-A-0 510 521
     (72) Inventors:                                                        US-A- 2 029 851              US-A- 5 643 501
        • BENECKE, Herman, P.
          Columbus, OH 43220 (US)




CD
O)


O)
     Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
     notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
     a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
Û_   99(1) European Patent Convention).
LU
                                                    Printed by Jouve, 75001 PARIS (FR)
                                                       EP 1 294 799 B1

     Description

     [0001] This application claims the benefit of pending U.S. Patent Application 09/849,071, filed May 4, 2001 ; and U.
     S. Patent Application No. 09/596,971, filed June 20, 2000, abandoned.
5
     FIELD OF THE INVENTION

     [0002] The present invention provides plasticizers for polyvinyl chloride based vinyl plastics that allow high loading
     of the plasticizer. The products of the invention are useful in applications where extended retention of plasticizer is
10   important (such as automobile products and other products subjected to heat), as well as in products where exposure
     to or contact by humans is a factor.

     BACKGROUND OF THE INVENTION

15   [0003] This invention relates to polyvinyl chloride plasticizers which have been derived from vegetable oil, their meth-
     od of making and their method of use.
     [0004] Polyvinyl chloride (PVC), the best known and most widely used of the vinyl plastics, is most often utilized in
     one or both of two general forms: substantially unplasticized PVC, and plasticized PVC. The substantially unplasticized
     form of PVC, commonly known as rigid PVC, is used for pipework, ducts, and similar applications in which high resist-
20   ance to chemical substances is required. The plasticized form of PVC is widely useful for numerous applications in-
     cluding films, sheeting, cable coverings, moldings, stationary products, conveyer belting, toys, and hose. Plasticized
     PVC is also used as a substitute for leather and may be used as a fabric for clothing and various furnishings.
     [0005] Among the most important physical characteristics of plasticized PVC are flexibility and pliability. These phys-
     ical characteristics are achieved by compounding PVC resin with one or more materials which serve as plasticizers
25   following their addition to the PVC resin. Broadly defined, plasticizers are high boiling point liquids which are used as
     ingredients in lacquers and certain plastics such as PVC. These liquids do not evaporate from the matrices they are
     added to, but rather preserve the flexibility and adhesive power of cellulose lacquer films or the flexibility of plastic
     sheeting and film. The majority of PVC plasticizers currently utilized in industrial processes are petroleum-derived
     phthalates and benzoate compounds. Dioctyl phthalate (DOP) and diallyl phthalate (DAP) are examples of petroleum-
30   derived compounds commonly used as primary plasticizers for PVC.
     [0006] While effective as primary plasticizers, petroleum-derived plasticizers are subject to several significant limi-
     tations. In addition to being processed from a nonrenewable source, petroleum-derived PVC plasticizers are often
     expensive to produce due to fluctuations in the price and availability of crude oil. Furthermore, petroleum-derived
     plasticizers such as DOP are suspected to disrupt human endocrine activity (see Modem Plastics, January 1998, p3S).
35   Therefore, it may be desirable or even necessary to limit the use of petroleum-derived plasticizers in certain situations,
     especially when the plasticized product comes into human contact at ambient temperature and especially at elevated
     temperature. Thus, there is a need for a low-cost, nontoxic, environmentally safe alternative to the petroleum-derived
     plasticizers that are currently incorporated into a great many consumer products. PVC plasticizers which are derived
     from vegetable oils provide such an alternative,
40   [0007] Unmodified vegetable oils are largely incompatible with polyvinyl chloride resin. However, certain modified
     derivatives of vegetable oils, such as epoxidized soybean oil, are compatible with PVC resin and provide an alternative
     to petroleum-based plasticizers. Furthermore, vegetable oils are derived from a renewable source, namely plants, and
     are not likely to create the potential for physiological disturbances or other injuries to persons coming into contact with
     products which require plasticizers in their composition.
45   [0008] Epoxidized soybean oil is currently used to a limited extent as a secondary plasticizer and co-thermal stabilizer
     in the processing and manufacturing of flexible, semi-rigid and rigid PVC products. Thermal stabilizers are needed in
     PVC formulations because at typical extrusion processing temperatures, PVC polymer undergoes slow elimination of
     hydrochloric acid because of labile beta hydrogen atoms. This leads to formation of isolated double bonds followed by
     fast allyl activated dehydohalogenation resulting in the formation of dark colored conjugated polyenes. This degrada-
50   tion, if not controlled, is auto-catalytic. Epoxidized soybean oil has been found useful in the prior art as a stabilizer in
     typical PVC formulations at a level of 2-3 %, but increased thermal stabilization has been determined at concentrations
     up to 27 pph PVC (pph = parts of plasticizer or additive per hundred parts of PVC resin). To further impart high tem-
     perature stability, metal soaps such as zinc and calcium stéarates are included as thermal stabilizers in combination
     with epoxidized soybean oil in PVC resins.
55   [0009] Despite the usefulness of epoxidized soybean oil as a thermal stabilizer, at use levels of about 5% (and in
     some cases up to 15%) in the compounded PVC resin, ESO tends to exude due to poor compatibility with the resin
     matrix at high levels. This incompatibility makes partially esterified and epoxidized soybean oil largely unsuitable as a
     primary plasticizer for use in PVC resins in high concentrations because primary plasticizers often represent up to 50%
                                                          EP 1 294 799 B1

     of the PVC matrix. The poor compatibility of partially esterified and epoxidized soybean oil with PVC resin is presumably
     due to factors such as the non-optimized match of the solubility parameter of partially epoxidized soybean oil polarity
     with that of PVC. Thus, for soybean oil or other vegetable oil derivatives to be useful as primary plasticizers, a useful
     oil must be modified to significantly improve its compatibility with PVC resins. Importantly, any chemical modifications
s    should not significantly diminish the thermal stabilizing properties of a preferred vegetable oil.
     [0010] Polyol esters have been used in PVC compositions as disclosed, for example, in U.S. Pat. No. 4,421,886
     issued to Worschech et al., which discloses PVC compositions wherein the partial ester of pentaerythritol and/or tri-
     methylol propane with a fatty acid of 8-22 carbon atoms is used in combination with a polybasic lead compound as a
     stabilizer/lubricant combination. The stabilizer lubricant is added in the amount of 0.5-10 % by weight. U.S. Pat. No.
10   4,605,694 issued to Walker discloses a plasticized PVC composition which includes a trimellitate ester, and a pen-
     traerythritol alkanoic acid ester. U.S. Pat. No. 5,886,072 issued to Linskey et al. discloses aflame retardant composition
     that includes a pentaerythritol ester plasticizer used with PVC resin along with other plasticizers. U.S. Pat. No. 5,430,108
     issued to Schlosberg et al. also discloses a plasticized PVC composition which includes a pentraerythritol alkanoic
     acid ester with mixed C5 , C7 and C9 alkanoic acids. J. T. Lutz, Jr. in Chapter/, Epoxy Plasticizers, of the "Handbook
15   of Polyvinyl Chloride Formulating" E. Wickson, Editor; Wiley & Sons, pp. 253-273 (1993) discloses examples of higher
     amounts of commercially available epoxidized soybean oil and commercially available epoxidized linseed oil than that
     used in the patent literature.
     [0011] The present invention provides unique combinations of plasticizers formed with substantially fully esterified
     and substantially fully epoxidized fatty acids from the fatty acids derived from commonly available vegetable oils.
20
     BRIEF SUMMARY OF THE INVENTION

     [0012] Accordingly, these and other disadvantages of the prior art are overcome by the present invention which
     provides plasticizers derived from vegetable oil which are highly compatible with polyvinyl chloride resin, and as such
25   are excellent for use as primary plasticizers in PVC resins. Typically, vegetable oil-based plasticizers have been real-
     istically used in PVC resins only at levels of 15% or less. Note that, unless otherwise specified herein, percent (%)
     refers to weight percent. The modified vegetable oil-based plasticizers of the present invention are significantly better
     than commercially available vegetable oil-based plasticizers, such as the commercially available ESO, and may be
     used at levels above 10%. Other embodiments provide for levels of plasticizers above about 15%, 20%, 40% and 50%.
30   A typical upper limit for plasticizer materials of the present invention is about 70%. It is expected that the higher con-
     centrations of plasticizers with high epoxy content will provide additional thermal stabilization. Thus, the materials of
     the invention provide for high and effective levels plasticizer for PVC formulations without evaporating or exuding from
     the PVC matrix. Furthermore, certain embodiments of the present invention exhibit both comparable plasticizing per-
     formance, and reduced migration tendencies as compared to the current industry standard, dioctyl phthalate (DOP),
35   which is derived from petroleum feed stock. The plasticizers of the present invention are also effective co-thermal
     stabilizers of PVC resins, and are particularly effective when combined with conventional metal soaps or other com-
     mercially available thermal stabilizers.
     [0013] In a broad embodiment, the improved vegetable oil-based plasticizers of the present invention are made by
     a preferred method which includes the basic steps of (i) creating ester linkages by attaching fatty acids derived from
40   vegetable oils (e.g., oleic, linoleic, linolenic acid, and palmitoleicacid, etc.) to monoalcohols (monools) orpolyalcohols
     (polyols) by means of direct esterification; and (ii) epoxidizing the esterified products (which contain saturated or un-
     saturated fatty acids) from step (i) to increase the polarity and increase the solubility parameter of these reaction
     products close to the solubility parameter of PVC. Presumably, increasing the polarity and solubility parameters in-
     creases the compatibility of the vegetable-oil based plasticizer with polyvinyl chloride resin. Alternatively, the first step
45   of this broad method (direct esterification) may be substituted with the step of transesterification, wherein a monool or
     polyol reacts directly with the vegetable oil to produce the desired product plus glycerin, and wherein a monool or polyol
     reacts with the lower alkyl ester of vegetable oil acid to produce the desired product plus the lower alcohol. Typically
     the saturated and unsaturated fatty acids are distributed randomly on each molecule of a polyol that is esterified with
     the fatty acids. This process also results in a random mix of esterified fatty acids.
50   [0014] An alternative broad embodiment includes the steps of (i) interesterification of one ester with another ester,
     or of a vegetable oil such as soybean oil with another vegetable oil such as linseed oil; and (ii) subsequent epoxidation
     of the product of the interesterification reaction. Interesterified oil may be further reacted with alcohols (monools and
     polyols) by transesterification of the interesterified product, followed by epoxidation of the transesterified, interesterified
     product. The immediately above mentioned alternative may also be used here.
55   [0015] The modified vegetable-oil based plasticizers of the present invention are derived from soybean oil, and in-
     clude: (i) epoxidized pentaerythritol tetrasoyate; (ii) epoxidized propylene glycol disoyate; (iii) epoxidized ethylene glycol
     disoyate; (iv) epoxidized methyl soyate; (v) epoxidized sucrose octasoyate; and (vi) the epoxidized product of soybean
     oil interesterified with linseed oil.
                                                          EP 1 294 799 B1

     [0016] A broad embodiment of the invention includes a plasticized vinyl chloride composition, having (a) 100 parts
     by weight of at least one vinyl chloride resin; (b) 10 to 230 parts by weight of a plasticizer compounded with the at least
     one vinyl chloride resin, wherein the plasticizer includes a fatty acid product derived from a vegetable oil having at
     least 80% by weight of unsaturated fatty acids, wherein the fatty acids are fully esterified with a monool or a polyol,
s    and the esterified unsaturated fatty acids have been fully epoxidized; (c) the vegetable oil derived plasticizers compo-
     sition including (1 ) the fatty acid product derived from direct esterification of fatty adds of the vegetable oil with a monool
     or a polyol; (2) the fatty acid product derived from transesterification of the vegetable oil with monools or polyols; (3)
     the fatty acid product derived from the vegetable oil interesterified with another vegetable oil having a higher degree
     of unsaturation; mixtures of the above; or (4) the fatty acid product derived from a fatty acids from the vegetable oil
10   esterified with a monool and interesterified with a polysaccharide carboxylic acid ester. The plasticized vinyl chloride
     composition is free of DOR Typically the alcohol is a polyol and the fatty acids derived from the vegetable oil are
     substantially randomly positioned on the hydroxyl sites of the polyol. Typical compositions contain one or more vege-
     table oils selected from the group consisting of, canolaoil (I.V. value 100-115), corn oil (I.V. value 118-128), linseed oil
     (IV. value 170-200), rapeseed oil (I.V. value 100-115), safflower oil (I.V. value 140-150), soybean oil (I.V. value 120-143),
'5   sunflower oil (I.V. value 125-140), tall oil (I.V. value 140-190), and tung oil (I.V. value about 180) (and mixtures of
     derivatives thereof) and mixtures thereof. Some typical embodiments have a plasticizer composition derived from a
     vegetable oil having an iodine value above 100. Some embodiments include a plasticizer composition of epoxidized
     pentaerythritol tetrasoyate having the formula:

20
                                                          CH2-0-R
                                                           I
                                                  R-O-CH2-C-CH2-O- R
                                                          CH2-0-R
25




     wherein R (each of the R's may be the same or different) is randomly selected from the group:

30       (i) epoxidized linoleoyl, oleoyl, linolenoyl, and palmitoleoyl; or
         (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl (the saturated fatty adds
         are present in minor amounts). In yet other embodiments the composition is epoxidized propylene glycol disoyate
         having the formula:

35

                                                               CH2-CH-CH3
                                                               I   I
                                                               0      o
40
                                                                1      I
                                                               R      R
     wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of:

         (i) epoxidized linoleoyl, oleoyl, linolenoyl, and palmitoleoyl; or
45       (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl (the saturated fatty acids
         are present in minor amounts). Other embodiments include a composition of epoxidized ethylene glycol disoyate
         having the formula:



50                                                             CH2-CH2
                                                               I   I
                                                               o           0
                                                                I          I
                                                               R       R
55
     wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of:

         (i) epoxidized linoleoyl, oleoyl, linolenoyl, and palmitoleoyl; or
                                                       EP 1 294 799 B1

         (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl (the saturated fatty acids
         are present in minor amounts). A yet further embodiment includes a plasticizer composition that is a mixture of
         epoxidized methyl soyate having the formula:


                                                               CH3-OR


     wherein R is randomly selected from the group consisting of:

10       (i) epoxidized linoleoyl. oleoyl, linolenoyl, and palmitoleoyl; or
         (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl(the saturated fatty acids are
         present in minor amounts). An additional embodiment of the invention includes a composition of epoxidized sucrose
         octasoyate having the formula:




20




25   wherein R (each of the R's may be the same or different) is selected from the group consisting of:

         (i) epoxidized linoleoyl. oleoyl, linolenoyl, and palmitoleoyl; or
         (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl (the saturated fatty acids
         are present in minor amounts). Typically each R is randomly selected from the above group. Another embodiment
30       includes a composition that is the epoxidized product of a first vegetable oil interesterified with a second vegetable
         oil, and having the formula:



                                                           CH2-CH-CH2
35                                                         I I     I
                                                           O O O
                                                           I   I   I
                                                           R   R R

40
     wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of:

         (i) epoxidized linoleoyl. oleoyl, linolenoyl, and palmitoleoyl; or
         (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl (the saturated fatty acids
45       are present in minor amounts). In some typical embodiments the first vegetable oil has an iodine value greater
         than 100 and the second vegetable oil has an iodine value greater than the first vegetable oil. Typically, first veg-
         etable oil is soybean oil, and the second vegetable oil is linseed oil.

     [0017]   A yet further embodiment of the invention includes epoxidized pentaetythritoltetrasoyate having the formula:
50


                                                            CH2-O-R
                                        R - O - C H 2 - C — CH2-O — R
55
                                                         CH2-O —R
                                                       EP 1 294 799 B1

     wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of:

         (i) substantially fully epoxidized unsaturated fatty acids derived from a vegetable oil; or
         (ii) non-epoxidized saturated fatty acids derived from a vegetable oil;

     wherein the vegetable oil has greater than about 80% unsaturated fatty acids and/or an iodine number above 100, and
     the saturated fatty acids are present in minor amounts.
     [0018] A further embodiment of the invention includes epoxidized propylene glycol disoyate having the formula:

10

                                                           CH2-CH-CH3
                                                           I   I
                                                           0      0
                                                            1      I
                                                           R      R

     wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of:

20       (i) epoxidized linoleoyl. oleoyl, linolenoyl, and palmitoleoyl; or
         (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl (the saturated fatty acids
         are present in minor amounts).

     [0019]   Another embodiment of the invention includes epoxidized ethylene glycol disoyate having the formula:
25



                                                            CH 2 -CH 2
                                                            I     i
30                                                         0       o
                                                           1       I
                                                           R       R
     wherein R (each of the R's may be the same or different) is randomly selected from the group:
35
         (i) epoxidized linoleoyl. oleoyl, linolenoyl, and palmitoleoyl; or
         (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl (the saturated fatty acids
         are present in minor amounts).

40   [0020]   A further embodiment of the invention includes an epoxidized methyl soyate mixture having the formula:


                                                             CH3-OR


45   wherein R represents a plurality of Rvalues in the mixture where each R is randomly selected from the following group:

         (i) epoxidized linoleoyl. oleoyl, linolenoyl, and palmitoleoyl; or
         (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl (the saturated fatty acids
         are present in minor amounts).
50
     [0021]   A yet further embodiment of the invention includes epoxidized sucrose octasoyate having the formula:




55
                                                         EP 1 294 799 B1




10
     wherein R (each of the R's may be the same or different) is selected from the group consisting of:

         (i) epoxidized linoleoyl. oleoyl, linolenoyl, and palmitoleoyl; or
         (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl (the saturated fatty acids
         are present in minor amounts). In some typical embodiments each R is randomly selected from the above group.

     [0022] A yet further embodiment of the invention includes epoxidized product of a first vegetable oil interesterified
     with a second vegetable oil having the formula:

20

                                                           CH2-CH-CH2
                                                            I   I         I
                                                           0        o     o
25
                                                            1       I      I
                                                           R        R     R

           wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of:

30       (i) epoxidized linoleoyl. oleoyl, linolenoyl, and palmitoleoyl; or
         (ii) non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, and margaroyl (the saturated fatty acids
         are present in minor amounts). In some typical embodiments the first vegetable oil is soybean oil other oil, and
         the second vegetable oil is linseed oil.

35   [0023] A yet further embodiment of the present invention includes a plasticized vinyl chloride composition, including
     (a) 100 parts by weight of at least one vinyl chloride resin; (b) 10 to 100 parts by weight of a plasticizer compounded
     with the at least one vinyl chloride resin, wherein the plasticizer is epoxidized pentaerythritol tetrasoyate; and (c) 1-3
     parts thermal stabilizer compounded with the at least one vinyl chloride resin and the plasticizer.
     [0024] An additional embodiment of the invention includes a plasticized vinyl chloride composition, including (a) 100
40   parts by weight of at least one vinyl chloride resin; (b) 10 to 100 parts by weight of a plasticizer compounded with the
     at least one vinyl chloride resin, wherein the plasticizer is epoxidized propylene glycol disoyate derived from randomized
     fatty acids; and (c) 1 -3 parts thermal stabilizer compounded with the at least one vinyl chloride resin and the plasticizer.
     [0025] A further embodiment of the invention includes a plasticized vinyl chloride composition, induding: (a) 100
     parts by weight of at least one vinyl chloride resin; (b) 10 to 100 parts by weight of a plasticizer compounded with the
45   at least one vinyl chloride resin, wherein the plasticizer is epoxidized ethylene glycol disoyate derived from randomized
     fatty acids; and (c) 1 -3 parts thermal stabilizer compounded with the at least one vinyl chloride resin and the plasticizer.
     [0026] A still further embodiment of the invention includes a plasticized vinyl chloride composition, including: (a) 100
     parts by weight of at least one vinyl chloride resin; (b) 10 to 100 parts by weight of a plasticizer compounded with the
     at least one vinyl chloride resin, wherein the plasticizer is epoxidized methyl soyate derived from randomized fatty
50   acids; and (c) 1 -3 parts thermal stabilizer compounded with the at least one vinyl chloride resin and the plasticizer.
     [0027] A further embodiment of the invention includes a plasticized vinyl chloride composition, including: (a) 100
     parts by weight of at least one vinyl chloride resin; (b) 10 to 100 parts by weight of a plasticizer compounded with the
     at least one vinyl chloride resin, wherein the plasticizer is epoxidized sucrose octasoyate; and (c) 1-3 parts thermal
     stabilizer. The epoxidized sucrose octasoyate may be derived from randomized fatty acids.
55   [0028] An additional embodiment includes a plasticized vinyl chloride composition, including: (a) 100 parts by weight
     of at least one vinyl chloride resin; and (b) 10 to 100 parts by weight of a plasticizer compounded with the at least one
     vinyl chloride resin, wherein the plasticizer is the epoxidized product of a first ester interesterified with a second ester;
     and 1 -3 parts thermal stabilizer compounded with the at least one vinyl chloride resin and the plasticizer.
                                                           EP 1 294 799 B1

     [0029] A yet further embodiment of the invention includes a plasticized vinyl chloride composition, including: (a) 100
     parts by weight of at least one vinyl chloride resin; and (b) 10 to 100 parts by weight of a plasticizer compounded with
     the at least one vinyl chloride resin, wherein the plasticizer is the epoxidized product of a first vegetable oil interesterif ied
     with a second vegetable oil; and 1 -3 parts thermal stabilizer compounded with the at least one vinyl chloride resin and
     the plasticizer. Typically the first vegetable oil is soybean oil or another vegetable oil. and the second vegetable oil is
     linseed oil.
     [0030] Therefore, it is an object of the present invention to provide vegetable oil-based plasticizers which are useful
     as primary plasticizers for vinyl plastics, and which can completely replace petroleum-based compounds, such as DOR
     as the primary plasticizers used with vinyl plastics.
10
     DETAILED DESCRIPTION OF THE INVENTION

     [0031] A preferred embodiment of the present invention modifies soybean oil for use as a primary plasticizer and
     co-thermal stabilizer in PVC resins. It should be noted, however, that soybean oil is not the only oil useful with this
     invention. Preferred oils include any vegetable or plant fatty acid gylceride that is significantly unsaturated. Significantly
     unsaturated means that the vegetable oil typically has more than about 80% unsaturated fatty acids. Most preferably
     the unsaturation should be about 84% or higher. Typically the oil has an iodine value (I.V.), which is a measurement
     of the amount of double bonds in the fatty acids of the oil, that is about 100 and higher. Examples of preferred oils as
     sources for fatty add dérivâtes include:
20
         canola oil (I.V. value 100-115),
         corn oil (I.V. value 118-128),
         linseed oil (IV. value 170-200),
         rapeseed oil (I.V. value 100-115),
25       safflower oil (I.V. value 140-150),
         soybean oil (I.V. value 120-143),
         sunflower oil (I.V. value 125-140),
         tall oil (I.V. value 140-190), and
         tung oil (I.V. value about 180) (and mixtures and derivatives thereof) all of which have an adequate number of
30       unsaturated fatty acids (e.g., oleic, linolenic, linoleic) which are suitable for epoxidation.

     [0032] Typically the unsaturated fatty acids useful in the invention are selected from a random mix of unsaturated
     fatty adds present in the vegetable oil, the saturated fatty acids are likewise selected from the random mix of saturated
     fatty adds present in the vegetable oil. The identifying portions of saturated fatty acids present are termed saturated
35   acyl groups that are derived from saturated fatty acids and are typified by palmitoyl, stearoyl, arachidoyl, behenoyl,
     myristoyl, and margaroyl.
     [0033] The term "polyvinyl chloride" (PVC) as used herein is intended to cover those homo- and copolymer resins
     of vinyl chloride known to persons of ordinary skill in the art. Generally speaking, copolymers of vinyl chloride (containing
     up to about 20% of such monomers as vinyl acetate, propylene, ethylene, diethyl maleate, dimethyl fumarate, and
40   other ethylenically unsaturated monomers) are intended to be covered.
     [0034] The compositions of the plasticized polyvinyl chloride resins of the present invention may be formulated, in
     addition to the above described plasticizers, with various kinds of additives according to need. For example, additives
     which contribute to improvement of properties such as heat stability, lubricity, weathering resistance, are exemplified
     by metal soaps such as calcium stéarate, zinc stéarate, lead stéarate, barium stéarate, cadmium stéarate, tribasic lead
45   sulfate, dibasic lead phosphite, organotin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, di-n-octyltin
     mercaptide, dimethyltin mercaptide as a stabilizer, and esters such as butyl stéarate, aliphatic acid amides such as
     ethylene bistearamide, higher fatty acids such as stearic acid and polyethylene waxes as a lubricant, fillers, anti-oxi-
     dants, ultraviolet absorbers, anti-static agents, anti-fogging agent, pigments, dye-stuffs, crosslinking aids.
     [0035] An important step in one embodiment of the present invention is to assure that the mixture of fatty adds
50   present in the triglyceride of the vegetable oils are removed from the triglycerides and the mixture of resulting saturated
     and unsaturated fatty acids, known as a vegetable acids, are used to esterify specified polyols or monools. Specifically
     mixtures of fatty acids derived from soybean oil are called soy add. Soy acid may then be reacted with apolyol having
     a plurality of sites available for esterification (such as pentaerythritol to produce a pentaerythritol tetrasoyate). The
     resulting product esterified polyol will then have fatty acids from the original vegetable oil randomly distributed on the
55   esterified polyol. This assures that each molecule of the esterified polyol will have a high plurality of unsaturated fatty
     acids to provide optimum compatibility with PVC after complete epoxidation. The resulting product will also contain a
     random mix of molecules esterified with the monool or the polyol.
     [0036] A preferred embodiment of the present invention provides a process for modifying soybean oil for use as a
                                                          EP 1 294 799 B1

     primary plasticizer in PVC. This process includes the general steps of reacting fatty acids derived from vegetable oil
     with an alcohol (monool or polyol) to create ester linkages between the fatty acids and the alcohol by means of ester-
     ification,transesterification, or interesterification reactions, followed by epoxidation of the product of these esterification,
     transesterification, or interesterification reactions. Presumably epoxidation increases the polarity and solubility param-
5    eter of the esterification, transesterification, or interesterification reaction products, resulting in increased compatibility
     of the vegetable-oil based plasticizer with polyvinyl chloride resin. Definitional descriptions of esterification reactions,
     transesterification reactions, interesterification reactions, and epoxidation reactions are provided below.
     [0037] Esterification is defined as the reaction of a fatty acid (e.g., carboxylic acid) with an alcohol to produce an
     ester and water. These reactions are equilibrium reactions and are generally driven to completion by removal of water.
10   typically by distillation if water is the lowest boiling component. This approach was used to create the ester linkages
     in the following preferred soybean oil-derived plasticizers: (i) epoxidized pentaerythritol tetrasoyate; (ii) epoxidized
     propylene glycol disoyate; and (iii) epoxidized ethylene glycol disoyate, discussed in greater detail below. The figure
     below illustrates atypical esterification reaction within the context of the present invention, wherein RCO2H is a mixture
     of fatty acids derived from soybean oil by hydrolysis of soybean oil, and R'OH represents alcohol functions in pentaer-
'5   ythritol, propylene glycol, or ethylene glycol.


                                                 RC02H + R'OH -> RCOgR' + H 2 0


20   [0038] Transesterification is defined as the reaction of an ester with an alcohol to produce a derived ester and the
     alcohol in the original ester. These reactions are equilibrium reactions and are generally driven to completion by removal
     of the product alcohol, typically by distillation if this alcohol is the lowest boiling component. This approach was used
     to create ester linkages in the following preferred soybean oil-derived plasticizers: (i) epoxidized methyl soyate. and
     (ii) propylene glycol disoyate, the former discussed in greater detail below.
25   [0039] The figure below illustrates a typical transesterification reaction within the context of the present invention,
     wherein RCOgR' typically represents triglycerides derived from soybean or other vegetable oils, and R"OH typically
     represents, propylene glycol, ethylene glycol, or methanol.


                                                RCOgR' + R"OH -> RC02R" + R'OH
30


     [0040] Interesterification involves reaction of two reactant esters to produce two product esters by interchange of
     original alcohol functions. Again, this reaction may be driven to completion by removal of one of the product esters,
     typically by distillation if one of the product ester is the lowest boiling component. Interesterification is used to prepare
35   the ester linkages in the plasticizer sucrose octasoyate by the reaction of sucrose octaacetate and methyl soyate which
     also produces methyl acetate that is removed by distillation. Soybean oil was also interesterified with linseed oil (with
     a higher IV value) to produce epoxidized, interesterified soybean oil. This interesterification process serves to increase
     the average number of double bonds in the modified triglyceride compared to those present in soybean oil. This sig-
     nificantly reduces the percentage of triglyceride molecules that have only zero, one, or two double bonds for subsequent
40   epoxidation. thus leading to reduced migration, exudation, volatilization.
     [0041] The figure below illustrates a typical interesterification reaction within the context of the present invention,
     wherein RCO2R' represents sucrose octaacetate and R"C02R"' represents methyl soyate, or alternatively wherein
     RCO2R' represents soybean oil and R"C02R"' represents linseed oil.

45
                                           RCOjR' + R"C02R"' -» RCO2R'" + R"C02R'


     [0042] Interesterification of soybean oil with other vegetable oils results in substantially complete randomization of
     fatty acid groups present in a mixture of preferred vegetable oils. Thus, interesterification of soybean oil with a vegetable
so   oil such as linseed oil or safflower oil, which have a higher percentage of highly unsaturated fatty acids (e.g., linolenic
     acid) than soybean oil, followed by epoxidation, decreases the percentage of non-epoxidized or minimally epoxidized
     ESO molecules. Presumably, it is these non-epoxidized or minimally epoxidized ESO molecules which are primarily
     responsible for exudation from PVC due their low solubility in or incompatibility with PVC.
     [0043] In an alternative embodiment, interesterified oil is further reacted with alcohols (monools and polyols) by
55   transesterification of the interesterified product, followed by epoxidation of the transesterified product.
     [0044] Epoxidation is defined as the addition of an oxygen atom across a carbon-carbon double bond to create
     epoxide (or oxirane) functionality. Epoxidation reactions are typically performed with percarboxylic acids or other peroxy
     compounds. The figure below illustrates a typical epoxidation reaction within
                                                         EP 1 294 799 B1



                                                                             O
                    R2C=CR'2         +     R"C03H                   ^     RzC7—CR':          +     RXC^H



     the context of the present invention, wherein Rand R'are alkyl, substituted alkyl or hydrogen, and R" isaryl, substituted
     aryl, alkyl, or hydrogen.
10   [0045] The vegetable oil derivatives of the present invention are epoxidized for several reasons. Firstly, the fatty acid
     esters of pentaerythritol, sucrose, propylene glycol and ethylene glycol are minimally compatible (i.e., minimally soluble)
     with PVC resin. However, these compounds become compatible with PVC when their long chain fatty acid groups are
     epoxidized. In the present invention, increasing compatibility of soybean oil with PVC resin by means of randomization
     of fatty acids, substantially complete esterification, and substantially full epoxidation resulting in low migration and
'5   exudation rates of this material in PVC resins or matrices.
     [0046] An additional reason for epoxidizing preferred vegetable-oil based plasticizers is that epoxide functionality
     significantly contributes to the thermal stability of the PVC matrix. Commercially available epoxidized soybean oil is
     typically used in concentrations of about 2 to 5% in PVC resins, and is used as a secondary thermal stabilizer in
     combination with certain metal salts, which are considered the primary thermal stabilizers in PVC matrices. In current
20   industrial formulations. DOP serves as the primary plasticizers, but does not contribute to thermal stability, whereas
     typical epoxidized soybean oil is included only for its marginal thermal stabilization functionality.
     [0047] The present invention provides vegetable oil-derivatives which are typically useful alone as a primary plasti-
     cizer, and also fulfill a dual role as both the primary plasticizer and the thermal stabilizer. In alternate embodiments,
     metal salts may be added to further enhance thermal stability. When the soybean oil-derived plasticizers of the present
25   invention are compounded with PVC resins at concentrations of above 15%, preferably above 20% and most preferably
     above about 40% or 50% of the matrix weight, these materials are effective primary plasticizers and thermal stabilizers.
     The upper limit of the plasticizer materials of the present invention is about 70% of the matrix weight. When the vegetable
     oil or soybean oil-derived plasticizers of the present invention are compounded with PVC resins at concentrations of
     above 15%, preferably above 20% and most preferably above about 40% or above about 50% of the matrix weight,
30   these materials are effective primary plasticizers and thermal stabilizers. The upper limit of the soybean derived plas-
     ticizers is about 70% of the matrix weight. When the vegetable oil or soybean oil-derived fatty acids are randomly
     reacted with materials having multiple attachment sites such as sucrose (e.g. to obtain sucrose octasoyate that is
     substantially fully epoxidized), pentaerythritol (e.g. to obtain pentaerythritol tetrasoyatethat is substantially fully epox-
     idized) effective primary plasticizers that allow high plasticizer content in PVC resins can be obtained. These materials,
35   in combination with metal soaps, are highly effective as thermal stabilizers due to the high epoxide concentrations
     contributed by these materials. Typically the materials may be used without combination with the metal salts and are
     still effective thermal stabilizers. DOP, which is currently the most widely used industrial plasticizer. can function only
     as a plasticizer and has no significant thermal stabilization properties.
     [0048] Typical and preferred embodiments of the present invention include the following soybean oil-derived plasti-
40   cizers which are useful as primary plasticizers in vinyl plastics:

         (i) epoxidized pentaerythritol tetrasoyate;
         (ii) epoxidized propylene glycol disoyate;
         (iii) epoxidized ethylene glycol disoyate;
45       (iv) epoxidized methyl soyate;
         (v) epoxidized sucrose octasoyate; and
         (vi) the epoxidized product of soybean oil interesterified with linseed oil (epoxidized interesterified soybean oil).

     [0049] Typically other embodiments of the present invention include hydrolysis products of the equivalent vegetable
50   oil-derived plasticizers, equivalent to those listed immediately above, that are derived from vegetable oils having about
     the same or higher amounts of unsaturated double bonds. These equivalent vegetable oils include oils having iodine
     values above 100. Typically oils can vary greatly in iodine number, even within the same type of vegetable oil depending
     on the growing site of the oil. Typically oils harvested from plants grown in cooler sites will have more double bonds
     and thus higher iodine values than those grown in warmer regions such as the tropics or subtropics. Accordingly
55   vegetable oils having iodine values above 100 and/or chosen from the group of vegetable oils listed herein are useful
     in the invention. For purposes of comparison, derivatives of vegetable oils such as palm oil (I.V. 50-55), coconut oil (I.
     V. 7-12), as well as any other varieties of vegetable oil where the I.V. value is below 100, are outside the scope of the
     invention.




                                                                  10
                                                       EP 1 294 799 B1

     [0050] The following examples provide detailed methods for making each of the immediately above listed soybean
     oil-derived plasticizers and are not meant to limit the broad disclosure and teachings of the invention in any way.

     EXAMPLE 1
5
     Epoxidized Pentaerythritol Tetrasoyate

     [0051] Epoxidized pentaerythritol tetrasoyate is a plasticizer typically having four epoxidized C18 soy acid-derived
     chains attached by means of ester linkages to a central molecule, pentaerythritol. Epoxidized pentaerythritol tetrasoyate
10   has a lower exudation rate when compounded with PVC resin than does epoxidized soybean oil, which has three
     epoxidized C18 soy acid-derived chains attached via ester linkages to a central glycerin molecule. More highly branched
     and higher molecular weight polymer additives typically have lower diffusion rates compared to those additives which
     are less highly branched and which have lower molecular weights. Additionally, epoxidized pentaerythritol tetrasoyate
     has a lower exudation rate than DOP, since it is known that ESO has a lower exudation rate than DOP in PVC.
'5   [0052] According to a preferred method, epoxidized pentaerythritol tetrasoyate was prepared in two steps. The first
     step required the direct esterification, without catalyst, of pentaerythritol with 1.10 to 1.12 equivalents of soy acid (4.4
     to 4.5 moles of soy acid for every 1.0 mole of pentaerythritol) to form pentaerythritol tetrasoyate (see A.A. Blagonravova
     and A.M. Lazarev, 13 J. Applied Chem. U.S.S.R., 879-882 (1940); H. Burrel, 37 Ind. Eng. Cham., 86-89 (1945); and
     U.S. Pat. No. 2,029,851 to Arvin). This approach leads to substantially full rather than partial esterification. Soy acids,
20   as used herein, is the mixture of carboxylic adds obtained from hydrolysis of soybean oil. Substantially complete hy-
     drolysis of soybean oil results in a mixture of acids termed soy acids and glycerin.
     [0053] The reaction mixture was placed in typical distillation apparatus and heated to about 170oC (at which tem-
     perature water started to evolve), and subsequently heated to about 235°C and held at this, temperature until approx-
     imately 100% of the expected water was collected. Obtaining the theoretical amount of water during this esterification
25   indicated that all four hydroxyl groups of pentaerythritol had been esterified with soy acid. In case of the present in-
     vention, the proton NMR spectra of these materials obtained after removal of fatty acids was also in good agreement
     with the expected structure of the materials.
     [0054] Excess fatty acids remaining after esterification can be removed by column chromatography, deodorization,
     or treatment with MagnesoKB). Materials obtained by these processes typically result in pentaerythritol tetrasoyate with
30   acid values of about 1.0 or lower. Acid values are defined as the milligrams of potassium hydroxide required to neutralize
     the alkali-reactive groups in 1 gram of material. Column chromatography is typically used for small-scale reactions,
     while deodorization and Magnesol®treatment is used for large-scale reactions. Atypical large-scale reaction uses
     about 1400 grams of pentaerythritol (Aldrich; 10.3 mole) and 12,741grams of soy acid (Emersol 315; 46.3 mole). The
     reaction was held at approximately 2350C for about 12 hours (until water collection had ceased) with a slow nitrogen
35   purge to obtain 12,070 grams of product with an acid value of about 1.0 after deodorization.
     [0055] Deodorization is a technique wherein water vapor from an external source is allowed to pass through the
     pentaerythritol layer, which has been heated at high temperature to remove impurities such as soy acids. Typically,
     the apparatus used to perform deodorization includes a vacuum distillation system that also has a water-containing
     flask attached to the pentaerythritol-containing flask via an open tube that passes through a safety trap to prevent
40   backflow of the pentaerythritol into the water-containing flask. This tube is open to the water vapor in the water-con-
     taining flask and is directed to the bottom of the pentaerythritol-containing flask so that the tube opening is significantly
     below the upper surface of the pentaerythritol. A vacuum is applied to a receiver flask that is attached to a condenser,
     that is attached to the pentaerythritol-containing flask. The pentaerythritol-containing flask is typically heated to 235°C
     to 260°C, whereas the water-containing flask is mildly heated at a temperature not quite high enough to cause water
45   condensation in the trap between the water-containing flask and the pentaerythritol-containing flask.
     [0056] The second step involves epoxidation of the double bonds in pentaerythritol tetrasoyate to prepare epoxidized
     pentaerythritol tetrasoyate with any of a number of percarboxylic acids such as m-chloroperbenzoic acid, peracetic
     acid, or performic acid. Preferred peracids used for epoxidation are m-chloroperbenzoic acid and peracetic acid using
     standard approaches well known in the art (See D. Swern, Organic Peroxides, Volume 2, 355-533, Interscience Pub-
50   lishers, 1971). Epoxidized pentaerythritol tetrasoyate prepared by this method was characterized by epoxide numbers
     of approximately 7.8 (this represents about 100% epoxidation). Epoxide numbers are defined as the grams of epoxide
     oxygen atoms per 100g of material.
     [0057] Epoxidized pentaerythritol tetrasoyate has the basic formula:

55




                                                                11
                                                        EP 1 294 799 B1


                                                                      CH2-0-R
                                                                      l
                                              R—O—CHz-C—CHz-O-R
                                                                    CH2-O — R


           wherein R (each of the R's may be the same or different) isepoxidizedlinoleoyl, oleoyl, linolenoyl, orpalmytoleoyl
     (in decreasing concentrations); or non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, or margaroyl
10   (the saturated fatty acids being present in minor concentrations). The material is substantially fully epoxidized and a
     substantially random mixture of fatty acids.

     EXAMPLES 2 - 3

15   [0058] Although epoxidized pentaerythritol tetrasoyate and epoxidized sucrose octasoyate (see below) have signif-
     icantly reduced exudation rates in PVC compared to ESO (or DOP), these plasticizers also have viscosities which are
     greater than the viscosities of ESO or DOP. Increased viscosity may contribute to increases in both the mechanical
     torque and the time required for compounding a plasticizer with a PVC resin. Epoxidized propylene glycol disoyate
     and epoxidized ethylene glycol disoyate are plasticizers of the present invention which have lower viscosities than
20   epoxidized pentaerythritol tetrasoyate and epoxidized sucrose octasoyate, and may therefore be compounded with
     PVC resin with less difficulty than higher viscosity materials.
     [0059] Direct esterification was used to attach soy fatty acid to each of the two hydroxyl groups in both propylene
     glycol and ethylene glycol to yield propylene glycol disoyate and ethylene glycol disoyate, respectively. Instrumental
     analysis showed substantially complete esterification of both hydroxyl groups. Subsequent epoxidation of these inter-
ns   mediates by means of employing performic acid yields plasticizers with preferred viscosity characteristics because the
     epoxidized products have lower molecular weights and a lower number of epoxide groups per molecule compared to
     ESO.
     These will allow easier processing.

so   EXAMPLE 2: Epoxidized Propylene Disoyate

     [0060] According to a preferred method, epoxidized propylene glycol disoyate was prepared in two steps. The first
     step involved the direct esterification, without catalyst, of a 2 to 1 molar mixture of soy acid (10,000g, acid value 200.4,
     35.72 moles) and propylene glycol (1359.1 g, 17.86 mole) to form propylene glycol disoyate.
35   [0061] A reaction flask was equipped with two connected distilling bulbs topped with a distillation head equipped
     with a heating mantle, mechanical stirring, thermometer and a gas inlet tube. The reaction vessel was sparged with a
     slow argon flow which exited into the receiver vessel and was maintained throughout the distillation. While maintaining
     vigorous stirring, the temperature of the reaction mixture was increased slowly such that the head temperature was
     maintained very close to 100oC, while maintaining distillation rates of about 0.9 to 0.3 ml/minute and presumably
40   distilling mainly water.
     [0062] When the distillation rate decreased to 0.3 ml/minute, the head temperature began to increase from 100°C.
     at which time the reaction mixture temperature was raised to approximately 194°C. The reaction mixture will be com-
     posed of approximately 19 percent soy acid (based on an acid value of 39.0). One of the distillation bulbs was removed
     and the argon flow increased through the reaction vessel. The reaction mixture temperature was increased slowly to
45   approximately 240oC while increasing the head temperature to 160oC, at which point a total of approximately 604 ml
     distillate was collected (94 percent of the theoretical water if the distillate is exclusively water) and the reaction termi-
     nated. Another 18 ml of a water insoluble oil may also be collected. The soy acid content of the reaction mixture was
     about 8.0 percent, based on an acid value of 15.9 at this stage of the distillation.
     [0063] The majority of excess soy acid in the reaction mixture was removed by treatment with neat granular sodium
50   carbonate (2456 g) while heating up to 90-100oC and holding at approximately this temperature for a 24 hour period.
     A moderate mechanical stirring rate was maintained during this time while continually flushing the flask with argon.
     Significant foaming may occur initially due to the formation of carbon dioxide and water. Propylene glycol disoyate was
     isolated from this mixture by decanting and filtering the liquid phase. Much of the propylene glycol disoyate in the
     remaining solid was removed by high speed centrifugation at 8500 RPM (or higher) followed by decanting and filtering
55   the resulting oil. Finally, the solid remaining from this step was extracted with methylene chloride and centrifugation
     used to help separate this mixture. Methylene chloride layers were stripped on a rotary evaporator with aspirator pres-
     sure and then with high vacuum while heating at 50°C to remove traces of solvent. A total of about 8.33 kg propylene
     glycol disoyate was obtained by this process wherein fractions obtained by the purification methods described above




                                                                 12
                                                           EP 1 294 799 B1

     have acid values of 0.58 or lower.
     [0064] In the second step, epoxidized propylene glycol disoyate was prepared by epoxidation with performic acid
     prepared in-situ by the reaction of formic acid and hydrogen peroxide, see European Patent EP 0295534 A3 to Wor-
     schech. etal. (in German), filed June?, 1988, published Jan. 2,1991; or its equivalent South African Patent Application
     ZA 8804250A (in English) filed June 14, 1988, published Dec. 15, 1988.
     [0065] Epoxidized propylene glycol disoyate has the following formula:



in                                                    CH2-CH-CH 3
10                                                     ,    *   ,
                                                      O         O
                                                       I        I
                                                      R         R


            wherein R (each of the R's may be the same or different on a random basis) is epoxidized linoleoyl, oleoyl,
     linolenoyl, or palmitoleoyl (in decreasing concentrations); or non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl,
     myristoyl, or margaroyl (the saturated fatty acids being present in minor concentrations). The material is substantially
20   fully epoxidized and has a substantially random mixture of attached fatty adds.

     EXAMPLE 3: Epoxidized Ethylene Glycol Disoyate

     [0066] A preferred method for producing epoxidized ethylene glycol disoyate consists of two steps. In the first step
25   ethylene glycol disoyate was prepared at relatively small scale in two stages by reaction of an excess of soy acid and
     ethylene glycol in benzene by the azeotropic distillation of water while using a mineral acid as a catalyst. The amount
     of water obtained and thin layer chromatography evidence will indicated that the primary product obtained in this step
     was ethylene glycol monosoyate. This product was then subjected to moderately high temperature heating under rapid
     gas flow to promote acylation of the remaining hydroxyl group in ethylene glycol monosoyate by selective removal of
30   water. In the second step epoxidized ethylene glycol disoyate was prepared in relatively small scale by epoxidizing
     ethylene glycol disoyate with meta-chloroperbenzoic acid in methylene chloride.
     [0067] Epoxidized ethylene glycol disoyate has the following formula:


35
                                                            C H ? - CH?
                                                            I            I
                                                           o         o
                                                            I            I
                                                           R         R
40


           wherein R(each of the R's may be the same or different) is epoxidized linoleoyl, oleoyl, linolenoyl, or palmitoleoyl
     (in decreasing concentrations); or non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, or margaroyl
     (the saturated fatty acids being present in minor concentrations). The material is substantially fully epoxidized and has
45   a substantially random mixture of attached fatty acids.

     EXAMPLE 4

     Epoxidized Methyl Soyate
50
     [0068] Epoxidized methyl soyate was prepared by epoxidation of commercially available methyl soyate with performic
     add prepared in-situ by the reaction of formic acid and hydrogen peroxide (see European Patent EP 0 295534 A3 to
     Worschech, et al. and its English language counterpart cited above).
     [0069] Epoxidized methyl soyate has the following formula:
55

                                                                CH3-OR




                                                                    13
                                                         EP 1 294 799 B1

           wherein R is randomly selected from epoxidized linoleoyl, oleoyl, linolenoyl, or palmitoleoyl (in decreasing con-
     centrations); or non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, or margaroyl (the saturated fatty
     acids being present in minor concentrations). The mixed material is substantially fully esterified and epoxidized. The
     typical product contains attached fatty acids from a random mixture of fatty acids astound in the parent vegetable oil.
5
     EXAMPLE 5

     Epoxidized Sucrose Octasoyate

10   [0070] This example illustrates interesterification of a polysaccharide carboxylic acid ester with a fatty add ester of
     a monool.
     [0071] Epoxidized sucrose octasoyate was prepared to obtain a plasticizer with eight lengthy C 18 chains attached
     to a central molecule having eight hydroxyl groups (sucrose). This material has even lower exudation rates in PVC
     than epoxidized pentaerythritol tetrasoyate, which has four lengthy C 18 chains attached to a central molecule (pen-
's   taerythritol). Interesterification involved the reaction of sucrose octaacetate and methyl soyate which led to the efficient
     synthesis of sucrose octasoyate. Subsequent epoxidation of this intermediate resulted in the desired plasticizer.
     [0072] Sucrose is a disaccharide with eight hydroxyl groups, thereby allowing the attachment of eight fatty acids per
     molecule in preparing sucrose octa(fatty acid), and epoxidation will lead to epoxidized sucrose octa(fatty acid). When
     sucrose was interesterified with soy fatty acids the resulting compound was sucrose octasoyate and subsequent epox-
20   idation resulted in epoxidized sucrose octasoyate. Given the normal distribution of individual fatty acids, epoxidized
     sucrose octasoyate presumably contained about 11.5 to 12.3 epoxide groups per molecule which is predicted to lead
     to high retention (i.e., low exudation) in PVC.
     [0073] Epoxidized sucrose octasoyate was prepared by the interesterification of sucrose octaacetate and methyl
     soyate (see C.C. Akoh and B.G. Swanson, J. Food Science, 55:1, 236-243 (1990). Epoxidation was performed with
25   peracetic add to obtain epoxidized sucrose octasoyate. According to a preferred method, the interesterified sucrose
     octaacetate and methyl soyate were epoxidized to obtain an oil which may be characterized as having an iodine value
     of about 2.75, an acid value of about 3.00, and an oxirane percentage of about 6.63%.
     [0074] Epoxidized sucrose octasoyate has the following formula:

30




35




           wherein R(each of the R's may be the same or different) is epoxidized linoleoyl, oleoyl, linolenoyl, or palmitoleoyl
40   (in decreasing concentrations); or non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, or margaroyl
     (the saturated fatty acids being present in minor concentrations). In some typical embodiments the material is sub-
     stantially fully esterified and epoxidized and has a substantially random mixture of attached fatty adds.

     EXAMPLE 6
45
     Epoxidized Product of Soybean Oil Interesterified with Linseed Oil

     [0075] In one embodiment of the present invention, interesterification reactions of SBO with linseed oil were per-
     formed using 90:10 mixtures of SBO and linseed oil. In another embodiment of the present invention, interesterification
50   reactions of SBO with linseed oil were performed using 70:30 mixtures of SBO and linseed oil. In still another embod-
     iment, any acceptable ratio of SBO to linseed oil may be utilized.
     [0076] Interesterification of soybean oil with linseed oil (70:30 mixture) may be accomplished by the following pre-
     ferred method:

55       (i) transfer 175.Og of refined, bleached and deodorized soybean oil and 75.00g linseed oil (7:3 mixture) to a three
         neck 500 ml round bottom flask equipped with a gas inlet, mechanical stirrer, and thermometer;
         (ii) after flushing the flask with argon, heat the flask in an oil bath while stirring the mixture at a moderate rate and
         maintaining a positive argon pressure within the flask by using a gas bubbler;




                                                                 14
                                                         EP 1 294 799 B1

         (iii) when the temperature of the contents has reached 70oC, 0.526g, slowly add 95% sodium methoxide (weighed
         in a glove bag under argon) while gently purging the sodium methoxide vial with argon;
         (iv) maintain reaction mixture at 70oC for two hours after addition of sodium methoxide is complete (during this
         time, the reaction mixture will undergo a characteristic color change from yellow to light brown);
s        (v) after the reaction mixture cools to ambient temperature, transferred the mixture to a 2 liter separatory funnel
         using 300 ml diethyl ether to rinse the flask;
         (vi) wash the mixture three times with 300 ml water while obtaining a nearly neutral final pH;
         (vii) add 350 microliters of concentrated phosphoric acid and the stir the mixture;
         (viii) extract with four 300ml water washes, to obtain final wash pH of 5;
10       (ix) add 150 ml of ether and filter this solution through cotton, dry over sodium sulfate and then dry overnight over
         sodium sulfate; (x) evaporate this solution with a rotary evaporator using aspirator pressure and then vacuum
         pump pressure to obtain 222.2 yellow clear oil which is purified by column chromatography on silica gel to remove
         residual fatty acids and monoglycerides.

'5   [0077]   Epoxidized interesterified soybean oil has the following formula:



                                                           CH 2 -CH-CH2i
                                                            I   f         I
20                                                         O        O    O
                                                            I        I    I
                                                           R        R     R


25
     wherein R (each of the R's may be the same or different) is epoxidized linoleoyl, oleoyl, linolenoyl, or palmitoleoyl (in
     decreasing concentrations); or non-epoxidized palmitoyl, stearoyl, arachidoyl, behenoyl, myristoyl, or margaroyl (the
     saturated fatty acids being present in minor concentrations). The material is substantially fully esterified and epoxidized
     and has a substantially random mixture of attached fatty acids.
30
     Comparison of Plasticizer Performance

     [0078] The present invention provides six improved vegetable (soybean) oil-based materials that are useful in vinyl
     chloride resins as primary plasticizers and as thermal stabilizers. Each of these compounds is intended to replace
35   petroleum-based plasticizers such as DOP as the primary plasticizer in PVC formulations. The tables below present
     test data in a comparative format that indicates that the vegetable oil-based plasticizers of the present invention out-
     perform, or are at least as good as DOP in a number of critical test categories.
     [0079] The data in the tables below were derived from tests on plasticized PVC films made by the following process:
     PVC resin (either a single resin, or combinations of resins) is dry blended with plasticizer and T-763 thermal stabilizer
40   and extruded in a laboratory Brabender unit according to the procedure given in ASTM 2538-94. The resultant material
     is then pressed into a film using a Carver Press at 191°C, 69,000 kPa (3750F, 10,000 PSI) for 1 minute. Mechanical
     properties of plasticized films are determined by pulling the film clamped between the jaws of an Instron device at a
     cross-head speed of about twenty inches per minute. By constructing a stress-strain curve, modulus (a measure of
     stiffness), elongation (a measure of flexibility), and breaking strength (a measure of ultimate strength) can be calculated.
45   Volatile loss is measured gravimetrically by determining the weight loss of plasticized film upon exposure to 70oC for
     periods of 24 and 120 hours.
     [0080] Typical preferred formulations of PVC include 100 parts per weight of a vinyl chloride resin, 10-230 parts per
     weight of a preferred plasticizer, and optionally 1-3 parts of a preferred thermal stabilizer such as Witco T-763.
     [0081] The viscosity of SBO derived plasticizers may be modified by esterification with mono, di or multi hydroxyl
50   containing compounds. As the hydroxyl functionality increases, structure and higher molecular weight of the resultant
     ester leads to higher viscosity. The viscosity of plasticizer has a significant effect on rate of plasticizing and volatility
     of the plasticizer from PVC resin matrix. Higher plasticizer viscosity typically leads to slower up-take of plasticizer and
     reduced volatility and migration from the PVC resin matrix. Table 1 illustrates comparative viscosities for DOP and the
     plasticizers of the present invention.
55   [0082] Tables 2 and 3 present comparative data for modulus, elongation, break strength at room temperature and
     70°C respectively. Table 4 presents comparative data for volatile loss at three different loading levels. The data pre-
     sented in Table 4 illustrate that the soybean oil-derived plasticizers of the present invention demonstrate significantly
     reduced exudation from PVC compared to phthalate plasticizers (DOP). Specifically at all loading levels the epoxidized




                                                                    15
                                                               EP 1 294 799 B1

     pentaerythritol tetrasoyate and epoxidized product of soybean oil interesterified with linseed oil were significantly better
     than the DOP. For higher loadings (150 to 230 pph) at about 120 hours the epoxidized product of soybean oil interes-
     terified with linseed oil was an order of magnitude better than DOP at all loading levels. The epoxidized pentaerythritol
     tetrasoyate appeared to perform better overall than the epoxidized soybean oil. The epoxidized product of soybean oil
s    interesterified with linseed oil performed about the same as ESO at low loading, but significantly outperformed ESO
     at the higher loading.
     [0083] Table 5 shows the results of placing the samples in hexane and extracting for about four hours. The epoxidized
     pentaerythritol tetrasoyate performed best in these tests with consistently the lowest weight loss at all loading levels.
     This is consistent with the teachings of the invention where the four sites for attachment of the various soya acids
10   increase the eventual epoxy content of the molecule and decrease the probability of having one or two fully saturated
     fatty acids on the same molecule, thereby leading to decreased exudation. The epoxidized product of soybean oil
     interesterified with linseed oil appeared to perform about the same as the epoxidized soybean oil except at the highest
     loading where it performed best. The interesterified product of the present invention has a higher average epoxy content
     and a lower saturated fatty acid content per molecule. The introduced randomness at the molecular level from the
'5   teachings of the present invention will provide a plasticizerthat is more compatible with PVC. In addition, having four
     or more sites available on a polyol compared to three for glycerol reduces the probability of having a low unsaturation
     number or a saturated fatty acid which leads to lower exudation and migration. These results show that the best results
     will be obtained from with polysaccharides represented by sucrose or with pentaerythritol because of their great number
     of attachment sites. As mentioned earlier, the random attachment of various unsaturated fatty acids together with
20   increased attachment sites significantly reduces the percentage of molecules that have only zero, one, or two double
     bonds for subsequent epoxidation, thus leading to reduced migration, exudation, volatilization, and the like. Thus,
     molecules with increased amounts of unsaturation and thus higher levels of epoxidation are favored over those with
     very little or no unsaturation.

25                                                                    Table 1.
      Viscosity*

                       Plasticizer                                  Viscosity (cP)                              Temperature °C

         Dioctyl Phthalate (DOP) [control]                                135                                           24
30
                     Soybean Oil                                          70                                            23

          Epoxidized Soybean Oil (ESO)                                    440                                           23

      Epoxidized Pentaerythritol Tetrasoyate                             1380                                           23

35        Epoxidized Sucrose Octasoyate                                  3830                                           24

      Epoxidized Propylene Glycol Disoyate                                180                                           23



       Epoxidized Ethylene Glycol Disoyate                          solid at 23°C                                       23
40
             Epoxidized Methyl Soyate                                     15.1                                          24

        Epoxidized Product of Soybean Oil                                 435                                           24
          interesterified with Linseed Oil
      * - Data measured with Rheometric Scientific rheometer. A 50 mm cone and plate geometry (cone angle 0.0402 radians) was used for the me
45    urements. The steady shear rate was varied from 10 to 100 radians/sec with data collected in five equally spaced intervals per decade.




50




55




                                                                         16
                                                  EP 1 294 799 B1


      Table 2. Mechanical Properties at Room Temperature.

                                                               Mechanical Properties at Room Temperature 1
            Primary Plastidzer           Plasticizer          100%         300%          Break   Elongation
                                          Loading3          Modulus     Modulus        Strength
                                           (pph)           kPa/PSI) kPa(PSI)        kPa (PSI)       m
        Dioctyl Phthatate (DOP)             100              (532)      (1210)          (1470)      283
                fcontroll                                     3671        8349          10143
10     Epoxid/zed Pentaerythritol           100              (630)       (1556)         (2027)      317
              Tetrasoyate                                     4347        10736         13986
          Epoxidized Sucrose                100             (1039)       (1429)        (2114)       237
              Octasoyate                                     7169         9860         14587
         Epoxidized Product of              100              (551)      (1214)         (1558)       436
       Soybean Oil interesterified                           3802
           with Unseed Oil                                              8377         10750

        Dioctyl Phthalate (DOP)             60            (1156)     (2469)        (2482)        240
                                                           7976       17036         17126
20    Epoxidized Propylene Glycol             60         (1109)      (2316)        (2615)        257
                Disoyate                                   7652       15980         18044
     - Epoxidized Ethylene Glycol             60         (1186)      (2533)        (2436)        247
                Disoyate                                  8183        17478         16808
       Epoxidized Methyl Soyate               60          (784)       (1779)       (2139)        317
25
                                                           5410       12275         14759
     a- loading levels of plastidzer in parts per hundred by weight öf PVC resin (Geon Resin); 3
     pph of a thermal stabilizer from Witco T-763 was used in all formulations


30   Table 3. Mechanical Properties at 700C / 120 hours.

                                                                Mechanical Properties at 700C / 120 hours
           Primary Plasticizer          Plastidzer           100%        300%           Break      Elongation
                                        Loading*            Modulus     Modulus       Strength
35                                                         kPafPSI) kPa (PSI) kPa(PSI)
       Dioctyl Phthalate (DOP)              100              (632)      (1223)         (1557)
               fcontrol]                                     4361        8439           10743
      Epoxidized Pentaerythritol            100              (885)      (2030)         (2437)         330
            Tetrasoyate                                      6107        14007         16815
40       Epoxidized Sucrose                 100             (1185)      (1391)         (2179)         240
             Octasoyate                                      8177        9598           15035
        Epoxidized Product of              100               (545)      (1043)         (1584)         380
      Soybean Oil interesterified
          with Unseed Oil                                     3671       7197          10930
45
        Dioctyl Phthalate (DOP)             60            (1173)       (2401)       (2374)           240
                                                           8094         16567       16381
      Epoxidized Propylene Glycol              60         (1156)       (2469)       (2482)          240
                Disoyate                                   7976         17036        17126
50     Epoxidized Ethylene Glycol              60         (1176)       (2526)       (2446)          247
                Disoyate                                   8114        17429        16877
       Epoxidized Methyl Soyate                60         (1066)       (2254)       (2375)          290
                                                       I   7355         15553        16388
     a- loading levels of plasticizer in parts per hundred by weight of PVC resin (Geon Resin); 3
55
     pph of a thermal stabilizer from Witco T-763 was used in all formulation




                                                           17
                                                                                            EP 1 294 799 B1




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55




                                                                                                  18
                                                                  EP 1 294 799 B1

                                                                         Table 5.
                              3
      HexaneExtraction .

                            Primary Plasticizer                               Sample No.       Plasticizer Loading 3 (pph)   % Loss b

                        Dioctyl Phthalate (DOP)                                   39-1                    100                 42.2

      Epoxidized Product of Soybean Oil interesterified with                      52-1                    100                   9.4
                          Linseed Oil

               Epoxidized Pentaerythritol Tetrasoyate                             52-2                    100                   2.6
10
                        Epoxidized Soybean Oil                                    52-3                    100                   8.3



                        Dioctyl Phthalate (DOP)                                   58-1                    150                 51.0

      Epoxidized Product of Soybean Oil interesterified with                      58-2                    150                  19.6
                          Linseed Oil

               Epoxidized Pentaerythritol Tetrasoyate                             58-3                    150                   8.6

                        Epoxidized Soybean Oil                                    58-4                    150                  17.0
20


                        Dioctyl Phthalate (DOP)                                   56-1                    233                 62.7

      Epoxidized Product of Soybean Oil interesterified with                      56-2                    233                 36.1
                          Linseed Oil
25
               Epoxidized Pentaerythritol Tetrasoyate                             56-3                    233                  19.2

                        Epoxidized Soybean Oil                                    56-4                    233                 43.7
      a - 4 hour exposure/24 hour dry
      b - starting samples weighed approximately 0.5 g +/- about 0.1 g.
30    c - film thickness about (0.022 inch +/- about 0.007 inch) 0.056 cm +/- about 0.018 cm


     [0084] Table 1 illustrates that the polyols such as sucrose pentaerythritol and provide the highest viscosities. This in
     combination with the random distribution of the fatty acids in the plasticizer should provide the best retention of plas-
     ticizer. Tables 2 and 3 illustrate that the polyols exhibit excellent mechanical properties at high loadings relative to DOP
35
     The epoxidized glycols and epoxidized methyl soyate having randomly distributed fatty acids likewise exhibit good
     properties at lower loadings versus DOP. Table 4 illustrates volatile loss in percent and shows that the products of the
     present invention are superior to DOP at all loadings. The data from Table 4 illustrate that the products of the present
     invention definitely show their advantages at higher loadings over epoxidized soybean oil (e.g. about 150 pph and
     higher). This corresponds to a loading of about 60%. Thus, it is expected that better volatility results will be obtained
40
     at loadings above 50%. Table 5 illustrates the results of hexane extraction. It is noted that all of the materials of the
     present invention have better loss characteristics than DOP for all loading levels. Epoxidized pentaerythritol was better
     than epoxidized soybean oil at all levels, while the epoxidized product of soybean oil interesterified with linseed oil was
     better than epoxidized soybean oil at the highest level (233 pph).
     [0085] While the above description contains many specificities, these should not be construed as limitations on the
45
     scope of the invention, but rather as exemplification of preferred embodiments. Numerous other variations of the
     present invention are possible, and it is not intended herein to mention all of the possible equivalent forms or ramifi-
     cations of this invention. Various changes may be made to the present invention without departing from the scope of
     the invention.
50

     Claims

     1.   A plasticized vinyl chloride composition, comprising:

55
               (a) 100 parts by weight of at least one vinyl chloride resin;

               (b) 10 to 230 parts by weight of a primary plasticizer compounded with said at least one vinyl chloride resin,




                                                                             19
                                                         EP 1 294 799 B1

              wherein said plasticizer comprises a fatty acid product derived from a vegetable oil having at least 80% by
              weight of unsaturated fatty acids, wherein said fatty acids are fully esterified with a monool or a polyol, and
              said esterified unsaturated fatty acids have been fully epoxidized;

s         wherein, in said vegetable oil derived plasticizers,

              (1) said fatty acid product is derived from direct esterification of fatty acids of said vegetable oil with a monool
              or a polyol;

10            (2) said fatty acid product is derived from transesterification of said vegetable oil with monools or polyols;

              (3) said fatty acid product is derived from said vegetable oil interesterified with another vegetable oil having a
              higher degree of unsaturation; and/or

'5            (4) said fatty acid product is derived from a fatty acids from said vegetable oil esterified with a monool and
              interesterified with a polysaccharide carboxylic acid ester.

     2.   The composition of claim 1, wherein said plasticized vinyl chloride composition is free of dioctyl phthalate (DOP).

20   3.   The composition of claim 1, wherein when said alcohol is a polyol and said fatty acids derived from said vegetable
          oil are randomly positioned on the hydroxyl sites of said polyol.

     4.   The composition of claim 1, wherein said vegetable oil is selected from the group consisting of:

25            canola oil (iodine value 100-115)

              linseed oil (iodine value 118-128)

              rapeseed oil (iodine value 100-115)
30

              safflower oil (iodine value 140-150)

              soybean oil (iodine value 120-143)

35            tall oil (iodine value 140-190), and

              tung oil (iodine value about 180) (and mixtures of derivatives thereof)

          and mixtures thereof.
40
     5.   The composition of claim 1, wherein said plasticizer composition is derived from a vegetable oil having an iodine
          value above 100.

     6.   The composition of claim 1, wherein said plasticizer composition is epoxidized pentaerythritol tetrasoyate having
45        the formula:




                                                                   CH,—O          R

50                                                                 I
                                           R         o—CHa—C—CHa                      O     R

                                                                   CHs—O          R

55


          wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of epox-
          idized linoleoyl, epoxidized oleoyl, epoxidized linolenoyl, epoxidized palmitoleoyl, non-epoxidized palmitoyl, non-




                                                                  20
                                                      EP 1 294 799 B1

         epoxidized stearoyl, non-epoxidized arachidoyl, non-epoxidized behenoyl, non-epoxidized myristoyl, and non-
         epoxidized margaroyl, provided that at least one of said groups R is an epoxidized unsaturated fatty acid.

     7. The composition of claim 1, wherein said plasticizer is epoxidized propylene glycol disoyate having the formula:



                                                          CHo-"Cn-"CHj

                                                           I         I
10                                                        O          0
                                                           I         I
                                                          R          R

'5       wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of epox-
         idized linoleoyl, epoxidized oleoyl, epoxidized linolenoyl, epoxidized palmitoleoyl, non-epoxidized palmitoyl, non-
         epoxidized stearoyl, non-epoxidized arachidoyl, non-epoxidized behenoyl, non-epoxidized myristoyl, and non-
         epoxidized margaroyl, provided that at least one of said groups R is an epoxidized unsaturated fatty acid.

20   8. The composition of claim 1, wherein said plasticizer is epoxidized ethylene glycol disoyate having the formula:



                                                               CHo^CHo

25                                                             I         I
                                                               o         o


30
         wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of epox-
         idized linoleoyl, epoxidized oleoyl, epoxidized linolenoyl, epoxidized palmitoleoyl, non-epoxidized palmitoyl, non-
         epoxidized stearoyl, non-epoxidized arachidoyl, non-epoxidized behenoyl, non-epoxidized myristoyl, and non-
         epoxidized margaroyl, provided that at least one of said groups R is an epoxidized unsaturated fatty acid.
35
         The composition of claim 1, wherein said plasticizer composition is a mixture of epoxidized methyl soyate having
         the formula:


                                                               H3C—OR
40


         wherein R is randomly selected from the group consisting of epoxidized linoleoyl, epoxidized oleoyl. epoxidized
         linolenoyl, epoxidized palmitoleoyl.

45   10. The composition of claim 1, wherein said plasticizer is epoxidized sucrose octasoyate having the formula:




50




55
                                                                             OR         \
                                                                                         OR




                                                                21
                                                        EP 1 294 799 B1

         wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of epox-
         idized linoleoyl, epoxidized oleoyl, epoxidized linolenoyl, epoxidized palmitoleoyl, non-epoxidized palmitoyl, non-
         epoxidized stearoyl, non-epoxidized arachidoyl, non-epoxidized behenoyl, non-epoxidized myristoyl, and non-
         epoxidized margaroyl, provided that at least one of said groups R is an epoxidized unsaturated fatty acid.

     11. The composition of claim 1, wherein said plasticizer is the epoxidized product of a first vegetable oil interesterified
         with a second vegetable oil, and having the formula:



10
                                                        CHo^CH                 CH9

                                                        I
                                                        O     O
                                                                  I. I O

                                                        I         I I
                                                        R         R            R


         wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of epox-
         idized linoleoyl, epoxidized oleoyl, epoxidized linolenoyl, epoxidized palmitoleoyl, non-epoxidized palmitoyl, non-
20       epoxidized stearoyl, non-epoxidized arachidoyl, non-epoxidized behenoyl, non-epoxidized myristoyl, and non-
         epoxidized margaroyl, provided that at least one of said groups R is an epoxidized unsaturated fatty acid.

     12. The composition according to claim 11, wherein said first vegetable oil has an iodine value greater than 100 and
         the second vegetable oil has an iodine value greater than the first vegetable oil.
25
     13. The composition of claim 11, wherein said first vegetable oil is soybean oil, and said second vegetable oil is linseed
         oil.

     14. Epoxidized pentaerithritol tetrasoyate having the formula:
30


                                                                      C H      _ 0        R

                                                                      I
35                                         R       O—CHa—C—CH2                                O   R

                                                                      CH2—O               R



40       wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of:

              (i) fully epoxidized unsaturated fatty acids derived from a vegetable oil; and
              (ii) non-epoxidized saturated fatty acids derived from a vegetable oil;

45       wherein said vegetable oil has greater than about 80% unsaturated fatty acids and/or an iodine number above
         100 and provided that at least one of said groups R is an epoxidized unsaturated fatty acid.

     15. Epoxidized propylene glycol disoyate having the formula:

50

                                                              C H j - - C H " " ~ " CH3

                                                              I            I
                                                              o           o
55
                                                              I            I
                                                              R            R




                                                                  22
                                                       EP 1 294 799 B1

         wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of epox-
         idized linoleoyl, epoxidized oleoyl, epoxidized linolenoyl, epoxidized palmitoleoyl, non-epoxidized palmitoyl, non-
         epoxidized stearoyl, non-epoxidized arachidoyl, non-epoxidized behenoyl, non-epoxidized myristoyl, and non-
         epoxidized margaroyl, provided that at least one of said groups R is an epoxidized unsaturated fatty acid.

     16. Epoxidized ethylene glycol disoyate having the formula:




                                                             CHj—CH2
10


                                                             o      o



         wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of epox-
         idized linoleoyl, epoxidized oleoyl, epoxidized linolenoyl, epoxidized palmitoleoyl, non-epoxidized palmitoyl, non-
         epoxidized stearoyl, non-epoxidized arachidoyl, non-epoxidized behenoyl, non-epoxidized myristoyl, and non-
20       epoxidized margaroyl, provided that at least one of said groups R is an epoxidized unsaturated fatty acid.

     17. Epoxidized methyl soyate having the formula:


                                                             H3C—OR
25


         wherein R is randomly selected from the group consisting of epoxidized linoleoyl, epoxidized oleoyl. epoxidized
         linolenoyl, epoxidized palmitoleoyl.

30   18. Epoxidized sucrose octasoyate having the formula:




35




40




45       wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of epox-
         idized linoleoyl, epoxidized oleoyl, epoxidized linolenoyl, epoxidized palmitoleoyl, non-epoxidized palmitoyl, non-
         epoxidized stearoyl, non-epoxidized arachidoyl, non-epoxidized behenoyl, non-epoxidized myristoyl, and non-
         epoxidized margaroyl, provided that at least one of said groups R is an epoxidized unsaturated fatty acid.

so   19. The epoxidized product of a first vegetable oil interesterified with a second vegetable oil having the formula:




55




                                                               23
                                                        EP 1 294 799 B1




                                                            C H-?   CH-~~ CHo

                                                            i         i i
                                                            o         o       o
                                                            I         I I
                                                            R         R       R

10
         wherein R (each of the R's may be the same or different) is randomly selected from the group consisting of epox-
         idized linoleoyl, epoxidized oleoyl, epoxidized linolenoyl, epoxidized palmitoleoyl, non-epoxidized palmitoyl, non-
         epoxidized stearoyl, non-epoxidized arachidoyl, non-epoxidized behenoyl, non-epoxidized myristoyl, and non-
         epoxidized margaroyl, provided that at least one of said groups R is an epoxidized unsaturated fatty acid.

     20. The composition of claim 19, wherein said first vegetable oil is soybean oil, and said second vegetable oil is linseed
         oil.

     21. A plasticized vinyl chloride composition according to claim 6, comprising:
20
              (a) 100 parts by weight of at least one vinyl chloride resin;

             (b) 10 to 100 parts by weight of a plasticizer compounded with said at least one vinyl chloride resin, wherein
             said plasticizer is epoxidized pentaerythritol tetrasoyate; and
25
              (c) 1-3 parts thermal stabilizer compounded with said at least one vinyl chloride resin and said plasticizer.

     22. A plasticized vinyl chloride composition according to claim 7, comprising:

30            (a) 100 parts by weight of at least one vinyl chloride resin;

             (b) 10 to 100 parts by weight of a plasticizer compounded with said at least one vinyl chloride resin, wherein
             said plasticizer is epoxidized propylene glycol disoyate; and

35            (c) 1 -3 parts thermal stabilizer compounded with said at least one vinyl chloride resin and said plasticizer.

     23. A plasticized vinyl chloride composition according to claim 8, comprising:

              (a) 100 parts by weight of at least one vinyl chloride resin;
40
             (b) 10 to 100 parts by weight of a plasticizer compounded with said at least one vinyl chloride resin, wherein
             said plasticizer is epoxidized ethylene glycol disoyate; and

              (c) 1-3 parts thermal stabilizer compounded with said at least one vinyl chloride resin and said plasticizer.
45

     24. A plasticized vinyl chloride composition according to claim 9, comprising:

              (a) 100 parts by weight of at least one vinyl chloride resin;

50            (b) 10 to 100 parts by weight of a plasticizer compounded with said at least one vinyl chloride resin, wherein

             said plasticizer is epoxidized methyl soyate; and

              (c) 1 -3 parts thermal stabilizer compounded with said at least one vinyl chloride resin and said plasticizer.

55   25. A plasticized vinyl chloride composition according to claim 10, comprising:

              (a) 100 parts by weight of at least one vinyl chloride resin;




                                                                 24
                                                        EP 1 294 799 B1

             (b) 10 to 100 parts by weight of a plasticizer compounded with said at least one vinyl chloride resin, wherein
             said plasticizer is epoxidized sucrose octasoyate; and

              (c) 1-3 parts thermal stabilizer compounded with said at least one vinyl chloride resin and said plasticizer.
5

     26. A plasticized vinyl chloride composition according to claim 1, comprising:

              (a) 100 parts by weight of at least one vinyl chloride resin;

10            (b) 10 to 100 parts by weight of a plasticizer compounded with said at least one vinyl chloride resin, wherein

             said plasticizer is the epoxidized product of a first ester interesterified with a second ester; and

              (c) 1-3 parts thermal stabilizer compounded with said at least one vinyl chloride resin and said plasticizer.

'5   27. A plasticized vinyl chloride composition according to claim 1, comprising:

              (a) 100 parts by weight of at least one vinyl chloride resin;
             (b) 10 to 100 parts by weight of a plasticizer compounded with said at least one vinyl chloride resin, wherein
20           said plasticizer is the epoxidized product of a first vegetable oil interesterified with a second vegetable oil; and
              (c) 1-3 parts thermal stabilizer compounded with said at least one vinyl chloride resin and said plasticizer.

     28. The composition of claim 27, wherein said first vegetable oil is soybean oil, and said second vegetable oil is linseed
25       oil.



     Patentansprüche

30   1.   Weichmacherhaltige Vinylchlorid-Zusammensetzung, umfassend:

              (a) 100 Gewichtsteile mindestens eines Vinylchloridharzes;

             (b) 10 bis 230 Gewichtsteile eines mit dem mindestens einen Vinylchloridharz vermischten Primärweichma-
35           chers, bei dem der Weichmacher ein Fettsäureprodukt umfaßt, das aus einem Pflanzenöl mit mindestens 80
             Gew.-% ungesättigter Fettsäuren gewonnen wurde, bei dem die Fettsäuren vollständig mit einem Monool oder
             einem Polyol verestert sind, und die veresterten ungesättigten Fettsäuren vollständig epoxidiert worden sind;

          bei der in dem aus dem Pflanzenöl gewonnenen Weichmacher
40
              (1) das Fettsäureprodukt aus der direkten Veresterung der Fettsäuren des Pflanzenöls mit einem Monool oder
              mit einem Polyol gewonnen ist;

              (2) das Fettsäureprodukt aus der Umesterung des Pflanzenöls mit Monoolen oder Polyolen gewonnen ist;
45
              (3) das Fettsäureprodukt aus dem Pflanzenöl gewonnen wird, das mit einem anderen Pflanzenöl mit einem
              höheren Unsättigungsgrad umgeestert ist; und/oder

              (4) das Fettsäureprodukt aus einer Fettsäure aus dem Pflanzenöl gewonnen ist, die mit einem Monool verestert
50            und mit einem Polysaccharidcarbonsäureester umgeestert ist.

     2.   Zusammensetzung nach Anspruch 1. bei der die weichmacherhaltige Polyvinylchlorid-Zusammensetzung frei von
          Dioctylphthalat (DOP) ist.

55   3.   Zusammensetzung nach Anspruch 1, bei der der Alkohol ein Polyol ist, und die aus dem Pflanzenöl gewonnenen
          Fettsäuren statistisch an den Hydroxyfunktionalitäten des Polyols positioniert sind.

     4.   Zusammensetzung nach Anspruch 1, bei der das Pflanzenöl aus der aus:




                                                                 25
                                                       EP 1 294 799 B1

              Canolaöl(lodzahl 100-115)

              Leinöl (lodzahl 118-128)

              Rapsöl (lodzahl 100-115)

              Safloröl (lodzahl 140-150)

              Sojaöl (lodzahl 120-143)
10
              Tallöl (lodzahl 140-190) und

              Tungöl (lodzahl etwa 180) (und Gemische aus dessen Derivaten)

'5        bestehenden Gruppe und deren Gemischen ausgewählt ist.

     5.   Zusammensetzung nach Anspruch 1, bei der die Weichmacher-Zusammensetzung aus einem Pflanzenöl mit einer
          lodzahl über 100 gewonnen ist.

20   6.   Zusammensetzung nach Anspruch 1, bei der die Weichmacher-Zusammensetzung epoxidiertes Pentaerythritol-
          tetrasoyat mit der folgenden Formel ist:




25
                                                                      CHj—O—R

                                                  R      O—CHj-C—CH2—O—R

                                                                      CH2—O—R
30


                worin R (jeder R kann gleich oder verschieden sein) statistisch aus der Gruppe ausgewählt ist, die aus
          epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl, epoxidiertem Palmitoleoyl, nicht-epoxidier-
          tem Palmitoyl. nicht-epoxidiertem Stearoyl, nicht-epoxidiertem Arachidoyl, nicht-epoxidiertem Behenoyl, nicht-ep-
35        oxidiertem Myristoyl und nicht-epoxidiertem Margaroyl besteht, vorausgesetzt, daß mindestens eine der Gruppen
          R eine epoxidierte ungesättigte Fettsäure ist.

     7.   Zusammensetzung nach Anspruch 1. bei der der Weichmacher epoxidiertes Propylenglycoldisoyat mit der folgen-
          den Formel ist:
40


                                                             CHj-CH       CH3
                                                             I
                                                             0
                                                                      I
                                                                      0
                                                             I        I
                                                             R        R


                worin R (jeder R kann gleich oder verschieden sein) statistisch aus der Gruppe ausgewählt ist, die aus
50        epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl, epoxidiertem Palmitoleoyl, nicht-epoxidier-
          tem Palmitoyl, nicht-epoxidiertem Stearoyl, nicht-epoxidiertem Arachidoyl, nicht-epoxidiertem Behenoyl, nicht-ep-
          oxidiertem Myristoyl und nicht-epoxidiertem Margaroyl besteht, vorausgesetzt, daß mindestens eine der Gruppen
          R eine epoxidierte ungesättigte Fettsäure ist.

55   8.   Zusammensetzung nach Anspruch 1, bei der der Weichmacher epoxidiertes Ethylenglycoldisoyat mit der folgen-
          den Formel ist:




                                                                 26
                                                       EP 1 294 799 B1



                                                                  CH2-CH 2

                                                                  II
                                                                  0        0
                                                                  I        I
                                                                  R        R

                worin R (jeder R kann gleich oder verschieden sein) statistisch aus der Gruppe ausgewählt ist, die aus
10        epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl, epoxidiertem Palmitoleoyl, nicht-epoxidier-
          tem Palmitoyl. nicht-epoxidiertem Stearoyl, nicht-epoxidiertem Arachidoyl, nicht-epoxidiertem Behenoyl, nicht-ep-
          oxidiertem Myristoyl und nicht-epoxidiertem Margaroyl besteht, vorausgesetzt, daß mindestens eine der Gruppen
          R eine epoxidierte ungesättigte Fettsäure ist.

'5   9.   Zusammensetzung nach Anspruch 1, bei der die Weichmacher-Zusammensetzung ein Gemisch aus epoxidiertem
          Methylsoyat mit der folgenden Formel ist:


                                                                       O—R
20
               worin R statistisch aus der aus epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl und
          epoxidiertem Palmitoleoyl bestehenden Gruppe ausgewählt ist.

     10. Zusammensetzung nach Anspruch 1, bei der der Weichmacher epoxidiertes Saccharoseoctasoyatmit derfolgen-
25       den Formel ist:



                                                       .OR
                                                                                   OR
30
                                                   J     O.                             OR



                                              OR
                                                                               OR        \
35                                                       OR                                  OR


                worin R (jeder R kann gleich oder verschieden sein) statistisch aus der Gruppe ausgewählt ist, die aus
          epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl, epoxidiertem Palmitoleoyl, nicht-epoxidier-
40        tem Palmitoyl, nicht-epoxidiertem Stearoyl, nicht-epoxidiertem Arachidoyl, nicht-epoxidiertem Behenoyl, nicht-ep-
          oxidiertem Myristoyl und nicht-epoxidiertem Margaroyl besteht, vorausgesetzt, daß mindestens eine der Gruppen
          R eine epoxidierte ungesättigte Fettsäure ist.

     11. Zusammensetzung nach Anspruch 1, bei der der Weichmacher das epoxidierte Produkt eines ersten Pflanzenöls
45       ist, das mit einem zweiten Pflanzenöl umgeestert wurde, und die folgende Formel aufweist:



                                                              CH? - CH         CH2

50
                                                              1 1
                                                              O O          O
                                                                               I
                                                              R        R       R



55              worin R (jeder R kann gleich oder verschieden sein) statistisch aus der Gruppe ausgewählt ist, die aus
          epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl, epoxidiertem Palmitoleoyl, nicht-epoxidier-
          tem Palmitoyl, nicht-epoxidiertem Stearoyl, nicht-epoxidiertem Arachidoyl, nicht-epoxidiertem Behenoyl, nicht-ep-
          oxidiertem Myristoyl und nicht-epoxidiertem Margaroyl besteht, vorausgesetzt, daß mindestens eine der Gruppen




                                                                  27
                                                      EP 1 294 799 B1

         R eine epoxidierte ungesättigte Fettsäure ist.

     12. Zusammensetzung nach Anspruch 11, bei der das erste Pflanzenöl eine lodzahl aufweist, die größer als 100 ist,
         und das zweite Pflanzenöl eine lodzahl aufweist, die größer als die des ersten Pflanzenöl ist.

     13. Zusammensetzung nach Anspruch 11, bei der das erste Pflanzenöl Sojaöl und das zweite Pflanzenöl Leinöl ist.

     14. Exoxidiertes Pentaerythritoltetrasoyat mit der folgenden Formel:

10

                                                               CH2—0—R

                                              R—0—CH2-C—CH2—0—R
                                                               I
                                                      |
15
                                                               CHj—O—R



              worin R (jeder R kann gleich oder verschieden sein) statistisch aus der Gruppe ausgewählt ist, die aus:

20           (i) vollständig epoxidierten, ungesättigten, aus einem Pflanzenöl gewonnenen Fettsäuren; und

             (ii) nicht-epoxidierten, gesättigten, aus einem Pflanzenöl gewonnenen Fettsäuren besteht,

               worin das Pflanzenöl mehr als 80% ungesättigte Fettsäuren und/oder eine lodzahl über 100 aufweist, und
25       vorrausgesetzt, daß mindestens eine der Gruppen R eine epoxidierte ungesättigte Fettsäure ist.

     15. Epoxidiertes Propylenglycoldisoyat mit der folgenden Formel:



30
                                                           CHÎ-CH           CH3

                                                           I
                                                           0
                                                                    I
                                                                    0
                                                           I        I
                                                           R       R
35


               worin R (jeder R kann gleich oder verschieden sein) statistisch aus der Gruppe ausgewählt ist, die aus
         epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl, epoxidiertem Palmitoleoyl, nicht-epoxidier-
         tem Palmitoyl. nicht-epoxidiertem Stearoyl, nicht-epoxidiertem Arachidoyl, nicht-epoxidiertem Behenoyl, nicht-ep-
40       oxidiertem Myristoyl und nicht-epoxidiertem Margaroyl besteht, vorausgesetzt, daß mindestens eine der Gruppen
         R eine epoxidierte ungesättigte Fettsäure ist.

     16. Epoxidiertes Ethylenglycoldisoyat mit der folgenden Formel:

45



                                                               II
                                                               00
                                                               I        I
so                                                             RR

               worin R (jeder R kann gleich oder verschieden sein) statistisch aus der Gruppe ausgewählt ist, die aus
         epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl, epoxidiertem Palmitoleoyl, nicht-epoxidier-
55       tem Palmitoyl. nicht-epoxidiertem Stearoyl, nicht-epoxidiertem Arachidoyl, nicht-epoxidiertem Behenoyl, nicht-ep-
         oxidiertem Myristoyl und nicht-epoxidiertem Margaroyl besteht, vorausgesetzt, daß mindestens eine der Gruppen
         R eine epoxidierte ungesättigte Fettsäure ist.




                                                               28
                                                      EP 1 294 799 B1

     17. Epoxidiertes Methylsoyat mit der folgenden Formel:


                                                           H3C— O- R


              worin R statistisch aus der aus epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl und
         epoxidiertem Palmitoleoyl bestehenden Gruppe ausgewählt ist.

     18. Epoxidiertes Saccharoseoctasoyat mit der folgenden Formel:
10


                                                         ,OR
                                                                            ,OR
                                                                                  OR
                                                    OR

                                               OR
                                                                          OR       \
                                                          OR                           OR
20


               worin R (jeder R kann gleich oder verschieden sein) statistisch aus der Gruppe ausgewählt ist, die aus
         epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl, epoxidiertem Palmitoleoyl, nicht-epoxidier-
         tem Palmitoyl. nicht-epoxidiertem Stearoyl, nicht-epoxidiertem Arachidoyl, nicht-epoxidiertem Behenoyl, nicht-ep-
25       oxidiertem Myristoyl und nicht-epoxidiertem Margaroyl besteht, vorausgesetzt, daß mindestens eine der Gruppen
         R eine epoxidierte ungesättigte Fettsäure ist.

     19. Epoxidiertes Produkt eines ersten Pflanzenöls, das mit einem zweiten Pflanzenöl umgeestert wurde, mit der fol-
         genden Formel:
30

                                                               CHo-CH—CH»
                                                               I
                                                               0
                                                                    I I
                                                                    0 0
35                                                             I    I I
                                                               R    R   R

               worin R (jeder R kann gleich oder verschieden sein) statistisch aus der Gruppe ausgewählt ist, die aus
         epoxidiertem Linoleoyl, epoxidiertem Oleoyl, epoxidiertem Linolenoyl, epoxidiertem Palmitoleoyl, nicht-epoxidier-
40       tem Palmitoyl. nicht-epoxidiertem Stearoyl, nicht-epoxidiertem Arachidoyl, nicht-epoxidiertem Behenoyl, nicht-ep-
         oxidiertem Myristoyl und nicht-epoxidiertem Margaroyl besteht, vorausgesetzt, daß mindestens eine der Gruppen
         R eine epoxidierte ungesättigte Fettsäure ist.

     20. Zusammensetzung nach Anspruch 19, bei der das erste Pflanzenöl Sojaöl und das zweite Pflanzenöl Leinöl ist.
45
     21. Weichmacherhaltige Vinylchlorid-Zusammensetzung nach Anspruch 6, umfassend:

             (a) 100 Gewichtsteile mindestens eines Vinylchloridharzes;

50           (b) 10 bis 100 Gewichtseile eines mit dem mindestens einen Vinylchloridharz vermischten Weichmachers, bei
             dem der Weichmacher ein epoxidiertes Pentaerythritoltetrasoyat ist; und

             (c) 1 bis 3 Teile eines mit dem mindestens einen Vinylchloridharz und dem Weichmacher vermischten Wär-
             mestabilisators.
55
     22. Weichmacherhaltige Vinylchlorid-Zusammensetzung nach Anspruch 7, umfassend:

             (a) 100 Gewichtsteile mindestens eines Vinylchloridharzes;




                                                               29
                                                    EP 1 294 799 B1

            (b) 10 bis 100 Gewichtseile eines mit dem mindestens einen Vinylchloridharz vermischten Weichmachers, bei
            dem der Weichmacher ein epoxidiertes Propylenglycoldisoyat ist; und

            (c) 1 bis 3 Teile eines mit dem mindestens einen Vinylchloridharz und dem Weichmacher vermischten Wär-
            mestabilisators.

     23. Weichmacherhaltige Vinylchlorid-Zusammensetzung nach Anspruch 8, umfassend:

            (a) 100 Gewichtsteile mindestens eines Vinylchloridharzes;
10
            (b) 10 bis 100 Gewichtseile eines mit dem mindestens einen Vinylchloridharz vermischten Weichmachers, bei
            dem der Weichmacher ein epoxidiertes Ethylenglycoldisoyat ist; und

            (c) 1 bis 3 Teile eines mit dem mindestens einen Vinylchloridharz und dem Weichmacher vermischten Wär-
            mestabilisators.

     24. Weichmacherhaltige Vinylchlorid-Zusammensetzung nach Anspruch 9, umfassend:

            (a) 100 Gewichtsteile mindestens eines Vinylchloridharzes;
20
            (b) 10 bis 100 Gewichtseile eines mit dem mindestens einen Vinylchloridharz vermischten Weichmachers, bei
            dem der Weichmacher ein epoxidiertes Methylsoyat ist; und

            (c) 1 bis 3 Teile eines mit dem mindestens einen Vinylchloridharz und dem Weichmacher vermischten Wär-
25          mestabilisators.

     25. Weichmacherhaltige Vinylchlorid-Zusammensetzung nach Anspruch 10, umfassend:

            (a) 100 Gewichtsteile mindestens eines Vinylchloridharzes;
30
            (b) 10 bis 100 Gewichtseile eines mit dem mindestens einen Vinylchloridharz vermischten Weichmachers, bei
            dem der Weichmacher ein epoxidiertes Saccharoseoctasoyat ist; und

            (c) 1 bis 3 Teile eines mit dem mindestens einen Vinylchloridharz und dem Weichmacher vermischten Wär-
35          mestabilisators.

     26. Weichmacherhaltige Vinylchlorid-Zusammensetzung nach Anspruch 1, umfassend:

            (a) 100 Gewichtsteile mindestens eines Vinylchloridharzes;
40
            (b) 10 bis 100 Gewichtseile eines mit dem mindestens einen Vinylchloridharz vermischten Weichmachers, bei
            dem der Weichmacher das epoxidierte Produkt eines ersten Esters ist, der mit einem zweiten Ester umgeestert
            wurde; und

45          (c) 1 bis 3 Teile eines mit dem mindestens einen Vinylchloridharz und dem Weichmacher vermischten Wär-

            mestabilisators.

     27. Weichmacherhaltige Vinylchlorid-Zusammensetzung nach Anspruch 1, umfassend:

50          (a) 100 Gewichtsteile mindestens eines Vinylchloridharzes;
            (b) 10 bis 100 Gewichtseile eines mit dem mindestens einen Vinylchloridharz vermischten Weichmachers, bei
            dem der Weichmacher das epoxidierte Produkteines ersten Pflanzenöls ist, das mit einem zweiten Pflanzenöl
            umgeestert wurde; und
55
            (c) 1 bis 3 Teile eines mit dem mindestens einen Vinylchloridharz und dem Weichmacher vermischten Wär-
            mestabilisators.




                                                            30
                                                          EP 1 294 799 B1

     28. Zusammensetzung nach Anspruch 27, bei der das erste Pflanzenöl Sojaöl und das zweite Pflanzenöl Leinöl ist.



     Revendications
5
     1.   Composition de chlorure de vinyle plastifiée, comprenant :

              (a) 100 parties en poids d'au moins une résine de chlorure de vinyle ;
              (b) 10 à 230 parties en poids d'un plastifiant primaire mélangé à ladite au moins une résine de chlorure de
10            vinyle, ledit plastifiant comprenant un produit acide gras dérivé d'une huile végétale comprenant au moins
              80% en poids d'acides gras insaturés, lesdits acides gras étant totalement estérifiés avec un monool ou un
              polyol, et lesdits acides gras insaturés estérifiés ayant été totalement époxydés ;

          dans laquelle, dans lesdits plastifiants dérivés de l'huile végétale,
15
              (1) ledit produit acide gras est dérivé de l'estérification directe des acides gras de ladite huile végétale avec
              un monool ou un polyol ;
              (2) ledit produit acide gras est dérivé de la transestérification de ladite huile végétale avec des monools ou
              polyols ;
20            (3) ledit produit acide gras est dérivé de ladite huile végétale interestérifiée avec une autre huile végétale
              ayant un plus haut degré d'insaturation ; et/ou
              (4) ledit produit acide gras est dérivé d'un acide gras provenant de ladite huile végétale estérifiée avec un
              monool et interestérifiée avec un ester d'acide carboxylique de polysaccharide.

25   2.   Composition suivant la revendication 1. dans laquelle ladite composition de chlorure de vinyle plastifiée est dé-
          pourvue de phtalate de dioctyle (DOP).

     3.   Composition suivant la revendication 1, dans laquelle ledit alcool est un polyol et lesdits acides gras dérivés de
          ladite huile végétale sont à des positions aléatoires sur les sites hydroxyle dudit polyol.
30
     4.   Composition suivant la revendication 1, dans laquelle ladite huile végétale est choisie dans le groupe consistant en :

              huile    decanola (indice d'iode de 100 à 115)
              huile    de graines de lin (indice d'iode de 118 à 128)
35            huile    de colza (indice d'iode de 100 à 115)
              huile    de carthame (indice d'iode de 140 à 150)
              huile    de soja (indice d'iode de 120 à 143)
              tallöl   (indice d'iode de 140 à 190), et
              huile    d'abrasin (indice d'iode d'environ 180) (et des mélanges de ses dérivés)
40
          et leurs mélanges.

     5.   Composition suivant la revendication 1, dans laquelle ladite composition de plastifiant est dérivée d'une huile
          végétale ayant un indice d'iode supérieur à 100.
45
     6.   Composition suivant la revendication 1, dans laquelle ladite composition de plastifiant est un tétrasojate de pen-
          taérythritol époxydé répondant à la formule :



50
                                                   <;Ha—o—R


                                I—-O—CHi—à—CMa
                                                    1               O—R

55
                                                    I
          dans laquelle R (les groupes R peuvent être identiques ou différents) est choisi de manière aléatoire dans le groupe
          consistant en des groupes linoléoyle époxydé. oléoyle époxydé, linolénoyle époxydé, palmitoléoyle époxydé, pal-




                                                                  31
                                                        EP 1 294 799 B1

          mitoyle non époxydé, stéaroyle non époxydé, arachidoyle non époxydé, béhénoyle non époxydé, myristoyle non
          époxydé et margaroyle non époxydé, sous réserve qu'au moins un desdits groupes R soit un acide gras insaturé
          époxydé.

     7.   Composition suivant la revendication 1, dans laquelle ledit plastifiant est le disojate de propylèneglycol époxydé
          répondante la formule :




                                                          i*-\ïH,""*CHj

                                                      P
10




                                                       1
          dans laquelle R (les groupes R peuvent être identiques ou différents) est choisi de manière aléatoire dans le groupe
          consistant en des groupes linoléoyle époxydé. oléoyle époxydé, linolénoyle époxydé, palmitoléoyle époxydé, pal-
          mitoyle non époxydé, stéaroyle non époxydé, arachidoyle non époxydé, béhénoyle non époxydé, myristoyle non
20        époxydé et margaroyle non époxydé, sous réserve qu'au moins un desdits groupes R soit un acide gras insaturé
          époxydé.

     8.   Composition suivant la revendication 1, dans laquelle ledit plastifiant est le disojate d'éthylèneglycol époxydé ré-
          pondant à la formule :
25




30




35        dans laquelle R (les groupes R peuvent être identiques ou différents) est choisi de manière aléatoire dans le groupe
          consistant en des groupes linoléoyle époxydé. oléoyle époxydé, linolénoyle époxydé, palmitoléoyle époxydé, pal-
          mitoyle non époxydé, stéaroyle non époxydé, arachidoyle non époxydé, béhénoyle non époxydé, myristoyle non
          époxydé et margaroyle non époxydé, sous réserve qu'au moins un desdits groupes R soit un acide gras insaturé
          époxydé.
40
     9.   Composition suivant la revendication 1, dans laquelle ladite composition de plastifiant est un mélange de sojate
          de méthyle époxydé répondant à la formule :


                                                              H3C—OR
45


          dans laquelle R est choisi de manière aléatoire dans le groupe consistant en des groupes linoléoyle époxydé,
          oléoyle époxydé, linolénoyle époxydé et palmitoléoyle époxydé.

so   10. Composition suivant la revendication 1, dans laquelle ledit plastifiant est l'octasojate de saccharose époxydé ré-
         pondant à la formule :




55




                                                                32
                                                       EP 1 294 799 B1




10




         dans laquelle R (les groupes R peuvent être identiques ou différents) est choisi de manière aléatoire dans le groupe
'5       consistant en des groupes linoléoyle époxydé. oléoyle époxydé, linolénoyle époxydé, palmitoléoyle époxydé, pal-
         mitoyle non époxydé, stéaroyle non époxydé, arachidoyle non époxydé, béhénoyle non époxydé, myristoyle non
         époxydé et margaroyle non époxydé, sous réserve qu'au moins un desdits groupes R soit un acide gras insaturé
         époxydé.

20   1 1 . Composition suivant la revendication 1, dans laquelle ledit plastifiant est le produit époxydé d'une première huile
           végétale interestérifiée avec une seconde huile végétale, et répondant à la formule :



                                    ;H,—CH
                                        CH—CH,
25
                                          l T
                                          i
                                          o

30
                                          I      i
         dans laquelle R (les groupes R peuvent être identiques ou différents) est choisi de manière aléatoire dans le groupe
         consistant en des groupes linoléoyle époxydé. oléoyle époxydé, linolénoyle époxydé, palmitoléoyle époxydé, pal-
         mitoyle non époxydé, stéaroyle non époxydé, arachidoyle non époxydé, béhénoyle non époxydé, myristoyle non
         époxydé et margaroyle non époxydé, sous réserve qu'au moins un desdits groupes R soit un acide gras insaturé
35       époxydé.

     12. Composition suivant la revendication 11, dans laquelle ladite première huile végétale a un indice d'iode supérieur
         à 100 et ladite seconde huile végétale a un indice d'iode supérieur à celui de la première huile végétale.

40   13. Composition suivant la revendication 11, dans laquelle ladite première huile végétale est l'huile de soja et ladite
         seconde huile végétale est l'huile de graines de lin.

     14. Tétrasojate de pentaérythritol époxydé répondant à la formule :

45

                                                        CHz-<

                                   R      O—-CHz—6—CMg                 O      R
50
                                                        CHΗO         R




         dans laquelle R (les groupes R peuvent identiques ou différents) est choisi de manière aléatoire dans le groupe
55       consistant en :

             (i) des acides gras insaturés totalement époxydés dérivés d'une huile végétale ; et
             (il) des acides gras saturés non époxydés dérivés d'une huile végétale ;




                                                                33
                                                       EP 1 294 799 B1

         dans lequel ladite huile végétale comprend plus d'environ 80% d'acides gras insaturés et/ou a un indice d'iode
         supérieur à 100, sous réserve en outre qu'au moins un desdits groupes R soit un acide gras insaturé époxydé.

     15. Disojate de proprylèheglycol époxydé répondant à la formule :




10




         dans laquelle R (les groupes R peuvent être identiques ou différents) est choisi de manière aléatoire dans le groupe
'5       consistant en des groupes linoléoyle époxydé. oléoyle époxydé, linolénoyle époxydé, palmitoléoyle époxydé, pal-
         mitoyle non époxydé, stéaroyle non époxydé, arachidoyle non époxydé, béhénoyle non époxydé, myristoyle non
         époxydé et margaroyle non époxydé, sous réserve qu'au moins un desdits groupes R soit un acide gras insaturé
         époxydé.

20   16. Disojate d'éthylèneglycol époxydé répondant à la formule :




25




30       dans laquelle R (les groupes R peuvent être identiques ou différents) est choisi de manière aléatoire dans le groupe
         consistant en des groupes linoléoyle époxydé. oléoyle époxydé, linolénoyle époxydé, palmitoléoyle époxydé, pal-
         mitoyle non époxydé, stéaroyle non époxydé, arachidoyle non époxydé, béhénoyle non époxydé, myristoyle non
         époxydé et margaroyle non époxydé, sous réserve qu'au moins un desdits groupes R soit un acide gras insaturé
         époxydé.
35
     17. Disojate de méthyle époxydé répondant à la formule :


                                                             H3C—OR

40
         dans laquelle R est choisi de manière aléatoire dans le groupe consistant en des groupes linoléoyle époxydé,
         oléoyle époxydé, linolénoyle époxydé et palmitoléoyle époxydé.

     18. Octasojate de saccharose époxydé répondant à la formule :
45




50




55


         dans laquelle R (les groupes R peuvent être identiques ou différents) est choisi de manière aléatoire dans le groupe
         consistant en des groupes linoléoyle époxydé. oléoyle époxydé, linolénoyle époxydé, palmitoléoyle époxydé, pal-




                                                               34
                                                       EP 1 294 799 B1

         mitoyle non époxydé, stéaroyle non époxydé, arachidoyle non époxydé, béhénoyle non époxydé, myristoyle non
         époxydé et margaroyle non époxydé, sous réserve qu'au moins un desdits groupes R soit un acide gras insaturé
         époxydé.

s    19. Produit époxydé d'une première huile végétale interestérifiée avec une seconde huile végétale répondant à la
         formule :




10
                                rI I  —CH—Ç
                                     ;— C H — Ç H j




                                 II
         dans laquelle R (les groupes R peuvent être identiques ou différents) est choisi de manière aléatoire dans le groupe
         consistant en des groupes linoléoyle époxydé. oléoyle époxydé, linolénoyle époxydé, palmitoléoyle époxydé, pal-
20       mitoyle non époxydé, stéaroyle non époxydé, arachidoyle non époxydé, béhénoyle non époxydé, myristoyle non
         époxydé et margaroyle non époxydé, sous réserve qu'au moins un desdits groupes R soit un acide gras insaturé
         époxydé.

     20. Composition suivant la revendication 19, dans laquelle ladite première huile végétale est l'huile de soja et ladite
25       seconde huile végétale est l'huile de graines de lin.

     21. Composition de chlorure de vinyle plastifiée suivant la revendication 6. comprenant :

             (a) 100 parties en poids d'au moins une résine de chlorure de vinyle ;
30           (b) 10 à 100 parties en poids d'un plastifiant mélangé à ladite au moins une résine de chlorure de vinyle, ledit
             plastifiant étant le tétrasojate de pentaérythritol époxydé ; et
             (c) 1 à 3 parties d'un stabilisant thermique mélangé à ladite au moins une résine de chlorure de vinyle et audit
             plastifiant.

35   22. Composition de chlorure de vinyle plastifiée suivant la revendication 7. comprenant :

             (a) 100 parties en poids d'au moins une résine de chlorure de vinyle ;
             (b) 10 à 100 parties en poids d'un plastifiant mélangé à ladite au moins une résine de chlorure de vinyle, ledit
             plastifiant étant le disojate de propylèneglycol époxydé ; et
40           (c) 1 à 3 parties d'un stabilisant thermique mélangé à ladite au moins une résine de chlorure de vinyle et audit
             plastifiant.

     23. Composition de chlorure de vinyle plastifiée suivant la revendication 8. comprenant :

45           (a) 100 parties en poids d'au moins une résine de chlorure de vinyle ;
             (b) 10 à 100 parties en poids d'un plastifiant mélangé à ladite au moins une résine de chlorure de vinyle, ledit
             plastifiant étant le disojate d'éthylèneglycol époxydé ; et
             (c) 1 à 3 parties d'un stabilisant thermique mélangé à ladite au moins une résine de chlorure de vinyle et audit
             plastifiant.
50
     24. Composition de chlorure de vinyle plastifiée suivant la revendication 9. comprenant :

             (a) 100 parties en poids d'au moins une résine de chlorure de vinyle ;
             (b) 10 à 100 parties en poids d'un plastifiant mélangé à ladite au moins une résine de chlorure de vinyle, ledit
55           plastifiant étant le sojate de méthyle époxydé ; et
             (c) 1 à 3 parties d'un stabilisant thermique mélangé à ladite au moins une résine de chlorure de vinyle et audit
             plastifiant.




                                                               35
                                                      EP 1 294 799 B1

     25. Composition de chlorure de vinyle plastifiée suivant la revendication 10, comprenant :

             (a) 100 parties en poids d'au moins une résine de chlorure de vinyle ;
             (b) 10 à 100 parties en poids d'un plastifiant mélangé à ladite au moins une résine de chlorure de vinyle, ledit
s            plastifiant étant l'octasojate de saccharose époxydé ; et
             (c) 1 à 3 parties d'un stabilisant thermique mélangé à ladite au moins une résine de chlorure de vinyle et audit
             plastifiant.

     26. Composition de chlorure de vinyle plastifiée suivant la revendication 1. comprenant :
10
             (a) 100 parties en poids d'au moins une résine de chlorure de vinyle ;
             (b) 10 à 100 parties en poids d'un plastifiant mélangé à ladite au moins une résine de chlorure de vinyle, ledit
             plastifiant étant le produit époxydé d'un premier ester interestérifié avec un second ester ; et
             (c) 1 à 3 parties d'un stabilisant thermique mélangé à ladite au moins une résine de chlorure de vinyle et audit
'5           plastifiant.

     27. Composition de chlorure de vinyle plastifiée suivant la revendication 1, comprenant :

             (a) 100 parties en poids d'au moins une résine de chlorure de vinyle ;
20           (b) 10 à 100 parties en poids d'un plastifiant mélangé à ladite au moins une résine de chlorure de vinyle, ledit
             plastifiant étant le produit époxydé d'une première huile végétale interestérifiée avec une seconde huile
             végétale ; et
             (c) 1 à 3 parties d'un stabilisant thermique mélangé à ladite au moins une résine de chlorure de vinyle et audit
             plastifiant.
25
     28. Composition suivant la revendication 27, dans laquelle ladite première huile végétale est l'huile de soja et ladite
         seconde huile végétale est l'huile de graines de lin.


30




35




40




45




50




55




                                                               36

				
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