GB2239251A - Polymers from diene hydrocarbons and vinyl acetate - Google Patents

Polymers from diene hydrocarbons and vinyl acetate Download PDF

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Publication number
GB2239251A
GB2239251A GB9025746A GB9025746A GB2239251A GB 2239251 A GB2239251 A GB 2239251A GB 9025746 A GB9025746 A GB 9025746A GB 9025746 A GB9025746 A GB 9025746A GB 2239251 A GB2239251 A GB 2239251A
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Prior art keywords
copolymer
set forth
mole percent
composition
matter
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GB9025746A
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GB9025746D0 (en
Inventor
Eric Lind
Pauls Davis
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BASF Corp
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BASF Corp
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Publication of GB9025746D0 publication Critical patent/GB9025746D0/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

A polymer based on diene hydrocarbons (e.g. butadiene or isoprene) and vinyl acetate has the general formula <IMAGE> wherein R<1> and R<2> are each end groups, and x is equal or greater than y and R<3> is CH3 or H. The polymers may be used to react with isocyanates to form urethanes or for copolymerisation with vinyl monomers or for graft polymerisation.

Description

POLYMERS FROM DIENE HYDROCARBONS AND VINYL ACETATE This invention relates to polymers based on diene hydrocarbons and vinyl acetate.
Vinyl acetate is a relatively inexpensive material from which polymers may be produced. Heretofor, polymerization of vinyl acetate produced molecules of relatively high viscosity, and having low hydroxyl functionality. Such characteristics of polyvinyl acetate make it undesirable as a polyol, and more particularly undesirable for use in the production of urethanes. Vinyl acetate is a monomer with relatively low reactivity and thus the polymerization of such a monomer requires a great deal of heat or excess quantities of initiator. Further, vinyl acetate polymers do not contain a double bond suitable for graft polymerization.
Thus, polymers of vinyl acetate which have relatively low viscosity, have acceptable functionality, and require relatively low heat or acceptable amounts of initiator to produce would be advantageous as polyols, are used in the production of urethanes and are suitable for use in graft polymerization.
The present invention provides vinyl acetate based copolymers prepared from the free radical copolymerization of diene hydrocarbons and vinyl acetate. The copolymers, prepared in a single stage continuous flow tubular reactor system, have low molecular weight and viscosity, have functional groups and unsaturation, are suitable for reaction with isocyanates, are miscible in polyethers and polyesters, and are suitable for peroxide initiated copolymerization with vinyl monomers such as styrene.
The vinyl acetate based copolymers of the present invention have relatively low viscosity, have sufficient functionality for use as a polyol, are suitable for use in the production of urethanes, are soluble in polyethers and are suitable for use in graft polymerization.
In one embodiment, the invention provides, a modified polyvinyl acetate from the free radical copolymerization of a diene hydrocarbon and vinyl acetate.
By way of example, suitable diene hydrocarbons included isoprene, butadiene and the like. The formulas which follow are illustrative only, and the copolymers may include 1,4 addition and 1,2 addition products. Copolymers based on vinyl acetate and isoprene preferably have the general formula I:
wherein R1 and R2 are each end group preferably hydroxyl or isopropoxyl groups, and x is equal to or greater than y.
In another embodiment, the copolymer based on vinyl acetate and isoprene may include a vinyl alcohol group. The vinyl alcohol group may be present in an amount ranging from trace quantities to about 5 mole percent. Such a copolymer, preferably has the general formula II:
wherein R1, R2, x and y are as defined above and x' ranges from trace quantities to about 5 mole percent.
Copolymers based on vinyl acetate and butadiene preferably have the general formula III:
wherein R1, R2, x and y are as defined above.
In another embodiment, the copolymer based on vinyl acetate and butadiene may also include a vinyl alcohol group as defined above. Such a copolymer preferably has the general formula IV:
wherein R1, R2, x, x' and y are as defined above.
In more preferred embodiments, formulas I-IV are such that, R1 and R2 are each end groups, preferably beinq selected from the group consisting of hydroxyl and isopropoxyl, and wherein x is 50-99.999 mole percent and y is 0.001-50 mole percent; preferably x is 75-99.995 mole percent and y is 0.005-25 mole percent; and most preferably x is 85-99.995 mole percent and y is 0.005-15 mole percent, and wherein x' ranges from trace quantities to about five mole percent.
The above formulas I-IV are representative only and the invention is contemplated as incluing the 1, 2addition products of isoprene and butadiene.
The copolymer has a number average molecular weight (GPC MWn) ranging from about 500 to about 5000, and more preferably, from about 500 to about 2000. The copolymers have a viscosity ranging frcm about 500 to about 20,000 cP, and preferably from about 500-10,000 cP e 250C.
By way of example, suitable diene hydrocarbons include isoprene, butadiene and the like. The copolymer produced from the diene hydrocarbons has a double bond which is suitable for producing graft polymers therefrom.
By way of example, suitable initiators for the random copolymerization include isopropyl alcohol, hydrogen peroxide and solketal.
The copolymers may be blended with hydroxyl-groupcontaining compounds for use in preparing urethane foams.
Suitable hydroxyl-group-containing compounds include aliphatic glycols, dihydroxy aromatics, bisphenols, hydroxyl terminated polyethers, polyesters and polyacetals. The copolymer may comprise from about 2 to about 99, preferably about 2 to about 20, and most preferably 5 to about 20 weight percent of the blend.
Preferably, the vinyl acetate based copolymer is prepared by the free radical process using a continuous process tubular reactor system. U.S. Patent No. 3,673,168 discloses a tubular reactor and continuous process for producing polymeric materials which are suitable for use in producing the vinyl acetate based copolymer of the present invention. U.S. Patent No. 3,673,168 is hereby incorporated by reference. Vinyl acetate monomer and a diene hydrocarbon are continuously fed into a tubular reactor in the presence of a solvent and an initiator. The vinyl acetate monomer is randomly polymerised with the diene hydrocarbon to yield the polyol in the tubular reactor. The polyol crude products so produced are continuously withdrawn from the tubular reactor mixture.
The following examples illustrate the nature of the invention; Example I Copolymers of the present invention were prepared in a single stage continuous flow tubular reactor. Monomer mix consisting of vinyl acetate (675 g), isoprene (225 g), isopropanol (510 g) and 50% hydrogen peroxide (90 g) were combined and added to the stirred water cooled feeder vessel of the tubular reactor. The monomer mix was gravity fed into the high pressure diaphragm pump which in turn pumped the monomer mix at 450 psig and a rate of approximately 1000 mL/hr into the heated (155 C) stainless steel coil. The colorless reaction mixture exited from the tubular reactor into a collecting vessel. The reaction mixture was stripped under vacuum to remove volatiles to give 14.4% yield. The GPC MWn = 1057 g/m, OH i = 147 mg KOH/g polyol, acid 1 = 3.78 mg KOH/g polyol, viscosity = 6120 Cps at 25 C. % H2O 0.04T, saponification I = 106 mg KOH/g polyol, unsaturation = 8.17 meq KOH/g polyol, IR cm 1 3460, 2940, 1740, 1650, 1250.
The vinyl acetate based copolymers prepared in Example I was soluble in polyethers, had low molecular weight with functional groups, was suitable for use in preparing polyurethanes, and contained double bonds suitable for preparing graft polymers therefrom.

Claims (55)

Claims
1. A vinyl acetate based copolymer having the general formula:
wherein R1 and R2 are each end groups, and x is equal to or greater than y.
2. A copolymer as set forth in claim 1 wherein x is 50 - 99.999 mole percent and y is 0.001 - 50 mole percent of x + y.
3. A copolymer as set forth in claim 1 wherein R1 and R2 are each OH.
4. A copolymer as set forth in claim 1 wherein R1 and R2 are each an isopropoxyl group.
5. A copolymer as set forth in claim 1 wherein R1 is OH and R2 is an isopropoxyl group.
6. A copolymer as set forth in claim 1 wherein R1 and R2 are each selected from the group consisting of OH and an isopropoxyl group.
7. A copolymer as set forth in claim 1 wherein x is 75-99.995 mole percent and y is 0.005-25 mole percent.
8. A copolymer as set forth in claim 1 wherein x is 85-99.995 mole percent and y is 0.005-15 mole percent.
9. A copolymer as set forth in claim 1 further comprising a vinyl alcohol group present in an amount ranging from trace quantities to about five mole percent.
10. A copolymer as set forth in claim 1 having a viscosity ranging from about 500 to about 20,000 cP.
11. A copolymer as set forth in claim 1 having a viscosity ranging from about 500 to about 10,000 cP.
12. A composition of matter comprising: a) a copolymer comprising the reaction product of vinyl acetate and a diene hydrocarbon, and b) a component comprising a nydroxyl-group containing compound, wherein said copolymer is uniformly dispersed in said component.
13. A composition of matter as set forth in claim 12 wherein said diene hydrocarbon comprises isoprene.
14. A composition of matter as set forth in claim 12 wherein said diene hydrocarbon comprises butadiene.
15. A composition of matter as set forth in claim 12 wherein said hydroxyl-group-containing compound comprises at least one selected from the group consisting of aliphatic glycols, dihydroxyl aromatics, bisphenols, hydroxyl terminated polyethers, polyesters, and polyacetals.
16. A composition of matter as set forth in claim 12 wherein said copolymer comprises from about 2 to about 99 weight percent of said composition.
17. A composition of matter as set forth in claim 12 wherein said copolymer comprises from about 2 to about 20 weight percent of said composition.
18. A composition of matter as set forth in claim 12 wherein said copolymer comprises from about 5 to about 20 weight percent of said composition.
19. A composition of matter as set forth in claim 12 whetein said diene hydrocarbon comprises from about 0.001 to about 50 mole percent of said copolymer.
20. A composition of matter as set forth in claim 12 wherein said diene hydrocarbon comprises from about 0.005 to about 25 mole percent of said copolymer.
21. A composition of matter as set forth in claim 12 wherein said diene hydrocarbon comprises from about 0.005 to about 15 mole percent of said copolymer.
22. A copolymer as set forth in claim 1 having an average molecular weight ranging from about 500 to about 5000.
23. A copolymer as set forth in claim 1 having an average molecular weight ranging from about 500 to about 2000.
24. A composition of matter as set forth in claim 12 wherein said copolymer has an average molecular weight ranging from about 500 to about 5000.
25. A composition of matter as set forth in claim 12 wherein said copolymer has an average molecular weight ranging from about 500 to about 2000.
26. A vinyl acetate based copolymer having the general formula:
wherein R1 and R2 are each end groups, and x is equal to or greater than y.
27. A copolymer as set forth in claim 26 wherein x is 50-99.999 mole percent and y is 0.001-50 mole percent.
28. A copolymer as set forth in claim 26 wherein R1 and R2 are each OH.
29. A copolymer as set forth in claim 26 wherein R1 and R2 are each an isopropoxyl group.
30. A copolymer as set forth in claim 26 wherein R1 is OH and R2 is an isopropoxyl group.
31. A copolymer as set forth in claim 26 wherein R1 and R2 are each selected from the group consisting of OH and an isopropoxyl group.
32. A copolymer as set forth in claim 26 wherein x is 75-99.995 mole percent and y is 0.005-25 mole percent.
33. A copolymer as set forth in claim 26 wherein x is 85-99.995 mole percent and y is 0.005-15 mole percent.
34. A copolymer as set forth in claim 26 further comprising a vinyl alcohol group present in an amount ranging from trace quantities to about five mole percent.
35. A copolymer as set forth in claim 26 having a viscosity ranging from about 500 to about 10,000 cP.
36. A copolymer as set forth in claim 26 having a viscosity ranging from about 500 to about 20,000 cP.
37. A copolymer comprising the reaction product of vinyl acetate and a diene hydrocarbon.
38. A copolymer as set forth in claim 37 wherein said diene hydrocarbon comprises isoprene.
39. A copolymer as set forth in claim 37 wherein said diene hydrocarbon comprises butadiene.
40. A copolymer as set forth in claim 37 which is initiated from a material selected from the group consisting of isopropyl alcohol, hydrogen peroxide and solketal.
41. A copolymer as set forth in claim 37 further comprising a cap selected from the group consisting of hydroxyl and isopropoxyl groups.
42. A copolymer as set forth in claim 37 comprising vinyl acetate groups ranging from about 50 to about 99.999 mole percent.
43. A copolymer as set forth in claim 37 comprising vinyl acetate groups ranging from about 75 to about 99.995 mole percent.
44. A copolymer as set forth in claim 37 comprising vinyl acetate groups ranging from about 85 to about 99.995 mole percent
45. A copolymer as set forth in claim 37 comprising vinyl alcohol groups present in an amount ranging from trace quantities to about five mole percent.
46. A copolymer as set forth in claim 37 having an average molecular weight ranging from about 500 to about 5000.
47. A copolymer as set forth in claim 37 having an average molecular weight ranging from about 500 to about 2000.
48. A copolymer as set forth in claim 37 having a viscosity ranging from about 500 to about 10,000 cP.
49. A copolymer as set forth in claim 37 having a viscosity ranging from about 500 to about 20,000 cP.
50. A composition of matter as set forth in claim 12 wherein said copolymer has a viscosity ranging from about 500 to about 20,000 cP.
51. A composition of matter as set forth in claim 12 wherein said copolymer has a viscosity ranging from about 500 to about 20,000 cP.
52. A copolymer as claimed in claim 1 or 26 or 37 and substantially as hereinbefore described or exemplified.
53. A composition of matter as claimed in claim 12 and substantially as hereinbefore described or exemplified.
54. Polyurethanes obtained from copolymers or compositions of matter as claimed in any of claims 1 to 53.
55. Copolymers and graft polymers from vinyl monomers and copolymers or compositions of matter as claimed in any of claims 1 to 53.
GB9025746A 1989-12-22 1990-11-27 Polymers from diene hydrocarbons and vinyl acetate Withdrawn GB2239251A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114195938A (en) * 2021-12-22 2022-03-18 天元航材(营口)科技股份有限公司 Preparation method of high-functionality hydroxyl-terminated liquid rubber

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57204783A (en) * 1981-06-10 1982-12-15 Denki Kagaku Kogyo Kk Inner box for electric refrigerator
JPS62275154A (en) * 1986-05-22 1987-11-30 Hitachi Chem Co Ltd Fiber-reinforced unsaturated polyester resin composition
JPS63151445A (en) * 1986-12-15 1988-06-24 西田　成夫 Winterizing or waterproof clothing fabric
EP0287140A1 (en) * 1987-03-13 1988-10-19 van der Groep, Lambertus Adrianus Polymer composition, a process for producing a polymer composition, and the use of such a polymer composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57204783A (en) * 1981-06-10 1982-12-15 Denki Kagaku Kogyo Kk Inner box for electric refrigerator
JPS62275154A (en) * 1986-05-22 1987-11-30 Hitachi Chem Co Ltd Fiber-reinforced unsaturated polyester resin composition
JPS63151445A (en) * 1986-12-15 1988-06-24 西田　成夫 Winterizing or waterproof clothing fabric
EP0287140A1 (en) * 1987-03-13 1988-10-19 van der Groep, Lambertus Adrianus Polymer composition, a process for producing a polymer composition, and the use of such a polymer composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114195938A (en) * 2021-12-22 2022-03-18 天元航材(营口)科技股份有限公司 Preparation method of high-functionality hydroxyl-terminated liquid rubber
CN114195938B (en) * 2021-12-22 2024-04-05 天元航材(营口)科技股份有限公司 Preparation method of high-functionality hydroxyl-terminated liquid rubber

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MX23802A (en) 1994-01-31
CA2032997A1 (en) 1991-06-23
GB9025746D0 (en) 1991-01-09

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