Plasticizers derived from vegetable oils

• US 20020013396A1
• Filed: 05/04/2001
• Published: 01/31/2002
• Est. Priority Date: 06/20/2000
• Status: Active Grant

• Current Assignee: Battelle Memorial Institute
• Original Assignee: Battelle Memorial Institute
• Inventors: Vijaydendran, Bhima R., Elhard, Joel D., Benecke, Herman P.
• Granted Patent: US 6,797,753 B2
• Time in Patent Office: Days
• US Class Current: 524/315
• CPC Class Codes: C08K 5/0016 Plasticisers
• CPC Class Codes: C08K 5/1515 Three-membered rings
• CPC Class Codes: C08L 27/06 Homopolymers or copolymers of vinyl chloride

Abstract

Compositions and methods for plasticizing polyvinyl chloride polymers where the plasticizers contain fatty acids derived from vegetable oils and the fatty acids are substantially fully esterified with an alcohol (monool or polyol), the fatty acids having unsaturated bonds that are substantially fully epoxidized, and wherein the fatty acids are added substantially randomly to one or more hydroxyl sites on the alcohol. The plasticizers may be added in amounts between about 10 to 230 pph of PVC resin.

Claims

1. A plasticized vinyl chloride composition, comprising:

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

(b) about 10 to 230 parts by weight of a plasticizer compounded with said at least one vinyl chloride resin, 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 substantially fully esterified with a monool or a polyol, and said esterified unsaturated fatty acids have been substantially fully epoxidized;

(c) said vegetable oil derived plasticizers composition comprising,

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

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

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

mixtures of the above;

or

(4) said fatty acid product 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 essentially free of DOP.

3. The composition of claim 1, wherein when said alcohol is a polyol and said fatty acids derived from said vegetable oil are substantially 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,

canola oil (I.V. value about 100-115),

corn oil (I.V. value about 118-128),

linseed oil (IV. value about 170-200),

rapeseed oil (I.V. value about 100-115),

safflower oil (I.V. value about 140-150),

soybean oil (I.V. value about 120-143),

sunflower oil (I.V. value about 125-140),

tall oil (I.V. value about 140-190), and

tung oil (I.V. value about 180) (and mixtures of derivatives thereof) and mixtures thereof.

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

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

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

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

9. The composition of claim 1, wherein said plasticizer composition is a mixture of epoxidized methyl soyate having the formula:

CH₃—

OR

wherein R 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.

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

11. The composition of claim 1, wherein each R is randomly selected from said group.

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

13. The composition according to claim 12, 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.

14. The composition of claim 12, wherein said first vegetable oil is soybean oil, and said second vegetable oil is linseed oil.

20. The composition of claim 1, wherein each R is randomly selected from said group.

15. Epoxidized pentaerythritol tetrasoyate having the formula:

16. Epoxidized propylene glycol disoyate having the formula:

17. Epoxidized ethylene glycol disoyate having the formula:

18. Epoxidized methyl soyate having the formula:

CH₃—

OR

wherein R 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.

19. Epoxidized sucrose octasoyate having the formula:

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

22. The composition of claim 21, wherein said first vegetable oil is soybean oil, and said second vegetable oil is linseed oil.

23. A plasticized vinyl chloride composition, comprising:

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

(b) about 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

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

24. A plasticized vinyl chloride composition, comprising:

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

(b) about 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

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

25. A plasticized vinyl chloride composition, comprising:

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

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

26. A plasticized vinyl chloride composition, comprising:

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

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

27. A plasticized vinyl chloride composition, comprising:

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

(b) about 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) about 1-3 parts thermal stabilizer.

28. A plasticized vinyl chloride composition, comprising

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

and

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

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

29. A plasticized vinyl chloride composition, comprising

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

and

(b) about 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 vegetable oil interesterified with a second vegetable oil; and

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