GB2239250A - Copolymers from polyalkylene oxides containing a maleate reactive double bond and vinyl acetate - Google Patents

Copolymers from polyalkylene oxides containing a maleate reactive double bond and vinyl acetate Download PDF

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Publication number
GB2239250A
GB2239250A GB9025745A GB9025745A GB2239250A GB 2239250 A GB2239250 A GB 2239250A GB 9025745 A GB9025745 A GB 9025745A GB 9025745 A GB9025745 A GB 9025745A GB 2239250 A GB2239250 A GB 2239250A
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Prior art keywords
copolymer
set forth
oxide
composition
polyol
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GB9025745A
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GB9025745D0 (en
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Pauls Davis
Steven D Gagnon
Eric Lind
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BASF Corp
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BASF Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • 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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Graft Or Block Polymers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A copolymer based on vinyl acetate and polyalkylene oxide(s) containing a maleate reactive double bond has the general formula <IMAGE> wherein R is a polyalkylene oxide, R<3> is an oxide cap, R<1> and R<2> are each end groups, and x is equal to or greater than y. The copolymers and compositions of matter comprising the copolymer uniformly dispersed in a hydroxyl group-containing compound may be used for produced of urethanes.

Description

COPOLYMERS FROM POLYALKYLENE OXIDES CONTAINING A MALEATE REACTIVE DOUBLE BOND AND VINYL ACETATE This invention relates to copolymers based on vinyl acetate and a polyalkylene oxide containing a maleate reactive double bond.
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.
Further, 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.
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, and more particularly for use in the production of urethanes.
The present invention provides vinyl acetate based copolymers prepared from the free radical copolymerization of vinyl acetate and polyalkylene oxide(s) having a maleate unit. Preferably, the vinyl acetate based copolymers have the general formula I:
wherein R is a polyalkylene oxide, R1 and R2 are each end groups, preferably hydroxyl or isopropoxyl groups, and x is equal to or greater than y.
The polyalkylene oxide having a maleate unit has the general formula II,
wherein R is a polyalkylene oxide and R3 is an oxide cap.
The vinyl acetate based copolymers of the present invention have relatively low viscosity, have sufficient functionality for use as a polyol and for use in the production of urethanes, and are soluble in polyethers.
In one embodiment, the invention provides, a modified polyvinyl acetate from the free radical copolymerization of vinyl acetate and polyalkylene oxide(s) having a maleate unit of the general formula II
wherein R is a polyalkylene oxide; preferably polyethylene oxide, polypropylene oxide, polybutylene oxide or polytetrahydrofuran, and R3 is an oxide cap, preferably polyethylene oxide or polypropylene oxide and having from about 0 to about 5 oxide units. The molecular weight of the polyalkylene oxide may vary but is preferably in the range of about 200 to about 2000 grams per vole. 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 from about 5000 to about 100,000 cP, and preferably from about 40,000 to about 100,000 cP e 25it. The polyalkylene oxide may be synthesized with a variety of initiators which are discussed in greater detail hereafter.
The polyalkylene oxide having a maleate unit is polymerized with vinyl acetate to produce a copolymer of the general formula I:
wherein R is a polyalkylene oxide as described above, R1 and R2 are end groups, preferably each being selected from the group consisting of hydroxyl and/or isopropoxyl, and wherein xis 50 - 99.999 mole percent andy is 0.001 - 50 mole percent; preferably x is 75 - 99.995 mole percent and y is 0.005 - 25 mole percent, and ost preferably x is 85 99.995 mole percent and y is 0.005 - 15 mole percent, and R3 is an oxide cap, preferably polyethylene oxide or polypropylene oxide having from about 0 to 5 oxide units.
In another embodiment, the vinyl acetate based copolymer, prepared from the free radical copolymerization of vinyl acetate and polyalkylene oxide(s) having a maleate, includes a vinyl alcohol group. The vinyl alcohol group may be present in an amount ranging from trace quantities to about five mole percent.Such copolymers preferably have the formula:
wherein R is a polyalkylene oxide as described above, R1 and R2 are end groups, preferably each being 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 and xl ranges from trace quantities to about 5 mole percent, preferably x is 75-99.999 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 R3 is an oxide cap, preferably polyethylene oxide or polypropylene oxide having from about 0 to 5 oxide units.
The polyalkylene oxide in the above formulas are generally prepared by well-known methods, for example by the base catalyzed addition of alkylene oxide, preferably ethylene oxide, propylene oxide or butylene oxide to initiator molecule containing on an average two or more active hydrogens. Also acid catalyzed polymerization of tetrahydrofuran is suitable. Preferably such initiators include methanol and solketal.Examples of other suitable initiator molecules include dihydric initiators such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, hydroquinone, resorcinol, the bisphenols, aniline and other aromatic monoamines, aliphatic monoamines, and monoesters of glycerine; trihydric initiators such as glycerine, trimethylolpropane, trimethylolethane, N-alkylphenylenediamines, mono-, di, and trialkanolamines; tetrahydric initiators such as ethylene diamine, propylenediamine, 2,4'-, 2,2'-, and 4,4 '- methylenedianiline, toluenediamine, and pentaerythritol; pentahydric initiators such as diethylenetriamine; and hexahydric and octahydric initiators such as sorbitol and sucrose.
Addition of alkylene oxide to the initiator molecules may take place simultaneously or sequentially when more than one alkylene oxide is used, resulting in block, heteric, and block-heteric polyoxyalkylene polyethers. The number of hydroxyl groups will generally equal the number of active hydrogens in the initiator molecule. Processes for preparing such polyethers are described both in the Polyurethane Handbook and Polyurethanes: Chemistry and Technology as well as in many patents, for example U.S.
Patents 1,922, 451; 2,674,619; 1,922,459; 3,190,927; and 3,346,557 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 the polyalkylene oxide containing either an allyl glycidyl ether or maleate unit are continuously fed into a tubular reactor in the presence of a solvent and an initiator. The vinyl acetate monomer is randomly polymerized with the polyalkylene oxide containing a maleate unit 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 In the following examples the materials used, were vinyl acetate (99t pure), butanol, ethyl alcohol, ethyl acetate from Aldrich Chemical Company; hydrogen peroxide from Dupont Chemical Company under the name Albone 50; and 2-propanol (purity of 99t) from American Scientific Products under the above name.
Example 1 The reactants shown in Table I were charged to a feeder vessel in the polymerization system described above.
Table I VAc 500 g Solketal initiated polypropylene oxide (PPO) (1500g/m)/maleate-PPO cap 100 g 50% H2 2 30 g IPA 340 g The reactants were added in no special order to a 2000 mL flask then poured into a stirred, water cooled feeder vessel. Nitrogen was bubbled through the reaction mixture. The contents were gravity fed into a diaphragm high pressure pump. The diaphragm pumps fed the reaction mixture at 450 psig and at a rate of 300 mL/hour into a heated (1550C) stainless steel coil. The slightly viscous liquid reaction product was collected at the end of the tubular reactor in a collector vessel. The volatiles were stripped off using a rotary evaporator. The resulting viscous oil was dissolved in ethyl acetate and neutralized to pH 8 with aqueous sodium bicarbonate. The organic layer was extracted, then washed with brine. The organic layer was collected and dried over sodium sulfate to give a 31 percent yield of product, OBI 41.5, % H2O = 0.159.
The vinyl acetate based copolymer prepared in Example I was soluble in polyethers and was suitable for use in preparing polyurethanes.

Claims (47)

Claims
1. A vinyl acetate based copolymer having the general formula:
wherein R is a polyalkylene oxide, R3 is an oxide cap, 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 R is selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetrahydrofuran.
4. A copolymer as set forth in claim 1 wherein R1 and R2 are each OH.
5. A copolymer as set forth in claim 1 wherein R1 and R2 are each an isopropoxyl group.
6. A copolymer as set forth in claim 1 wherein Rl is 0E and R2 is an isopropoxyl group.
7. 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.
8. A copolymer as set forth in claim 1 wherein x is 75 - 99.995 mole percent and y is 0.005-25 mole percent.
9. A copolymer as set forth in claim 1 wherein x is 85 - 99.995 mole percent and y is 0.005-15 mole percent.
10. A copolymer as set forth in claim 1 wherein R3 has from about 0 to about 5 oxide units.
11. A copolymer as set forth in claim 1 wherein R3 is selected from the group consisting of polyethylene oxide and polypropylene oxide.
12. A polyol comprising the free radical polymerization product of vinyl acetate and a polyalkylene oxide/maleate compound.
13. A polyol as set forth in claim 12 wherein the polyalkylene oxide/maleate compound comprises:
wherein R is selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetrahydrofuran; and R3 is an oxide cap.
14. A polyol as set forth in claim 13 wherein R3 is selected from the group consisting of polyethylene oxide and polypropylene oxide.
15. A polyol as set forth in claim 13 wherein R3 is selected from the group consisting of ethylene oxide and propylene oxide cap having from about 0 to about 5 repeating oxide units.
16. A copolymer as set forth in claim 1 wherein R has a molecular weight ranging from about 200 to about 2000 grams per mole.
17. A polyol as set forth in claim 13 wherein R has a molecular weight ranging from about 200 to about 2000 grams per mole.
18. A copolymer comprising the reaction product of vinyl acetate and maleate.
19. A copolymer as set forth in claim 18 having a viscosity ranging from about 5000 to about 100,000 cP.
20. A copolymer as set forth in claim 18 having a viscosity ranging from about 40,000 to about 100,000 cP.
21. A composition of matter comprising: a) a copolymer comprising the reaction product of vinyl acetate and maleate, and b) a component comprising a hydroxyl-group containing compound, wherein said copolymer is uniformly dispersed in said component.
22. A composition of matter as set forth in claim 21 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.
23. A composition of matter as set forth in claim 21 wherein said copolymer comprises from about 2 to about 99 weight percent of said composition.
24. A composition of matter as set forth in claim 21 wherein said copolymer comprises from about 2 to about 20 weight percent of said composition.
25. A composition of matter as set forth in claim 21 wherein said copolymer comprises from about 5 to about 20 weight percent of said composition.
26. A composition of matter as set forth in claim 21 wherein said maleate comprises from about 0.001 to about 50 mole percent of said copolymer.
27. A composition of matter as set forth in claim 21 wherein said maleate comprises from about 0.005 to about 25 mole percent of said copolymer.
28. A composition of matter as set forth in claim 21 wherein said maleate comprises from about 0.005 to about 15 mole percent of said copolymer.
29. A copolymer as set forth in claim 1 wherein said copolymer has an average molecular weight ranging from about 500 to about 5000.
30. A copolymer as set forth in claim 1 wherein said copolymer has an average molecular weight ranging from about 500 to about 2000.
31. A polyol as set forth in claim 12 wherein said polyol has an average molecular weight ranging from about 500 to about 5000.
32. A polyol as set forth in claim 12 wherein said polyol has an average molecular weight ranging from about 500 to about 2000.
33. A copolymer as set forth in claim 18 wherein said copolymer has an average molecular weight ranging from about 500 to about 5000.
34. A copolymer as set forth in claim 18 wherein said copolymer has an average molecular weight ranging from about 500 to about 2000.
1
35. A composition of matter as set forth in claim 21 wherein said copolymer has an average molecular weight ranging from about 500 to about 5000.
36. A composition as set forth in claim 21 wherein said copolymer has an average molecular weight ranging from about 500 to about 2000.
37. A copolymer as set forth in claim 1 wherein said copolymer has a viscosity ranging from about 5000 to about 100,000 cP.
38. A copolymer as set forth in claim 1 wherein said copolymer has a viscosity ranging from about 40,000 to about 100,000 cP.
39. A polyol as set forth in claim 12 wherein said polyol has a viscosity ranging from about 5000 to about 100,000 cP.
40. A polyol as set forth in claim 12 wherein said polyol has a viscosity ranging from about 40,000 to about 100,000 cP.
41. A composition of matter as set forth in claim 21 wherein said copolymer has a viscosity ranging from about 5000 to about 100,000.
42. A composition of matter as set forth in claim 21 wherein said copolymer has a viscosity ranging from about 40,000 to about 100,000 cP.
43. 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.
44. A copolymer as claimed in claim 1 or 18 and substantially as hereinbefore described or exemplified.
45. A polyol as claimed in claim 12 and substantially as hereinbefore described or exemplified.
46. A composition of matter as claimed in claim 21 and substantially as hereinbefore described or exemplified.
47. Polyurethanes obtained from copolymers or polyols or compositions of matter as claimed in any of claims 1 to 46.
GB9025745A 1989-12-22 1990-11-27 Copolymers from polyalkylene oxides containing a maleate reactive double bond and vinyl acetate Withdrawn GB2239250A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5880239A (en) * 1995-06-08 1999-03-09 Wacker-Chemie Gmbh Fusible chlorine-free vinyl acetate copolymer fibres
WO2001007496A2 (en) * 1999-07-22 2001-02-01 Bp Chemicals Limited Polymers, their precursors and processes for preparation thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1133277A (en) * 1963-01-28 1968-11-13 Air Reduction Vinyl acetate-alkoxy polyalkylene glycol half ester copolymers, and their use in remoistenable adhesives
JPS60151382A (en) * 1984-01-17 1985-08-09 工業技術院長 Curing treatment
JPS62236789A (en) * 1986-04-08 1987-10-16 Idemitsu Petrochem Co Ltd Binder for thermal recording paper

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1133277A (en) * 1963-01-28 1968-11-13 Air Reduction Vinyl acetate-alkoxy polyalkylene glycol half ester copolymers, and their use in remoistenable adhesives
JPS60151382A (en) * 1984-01-17 1985-08-09 工業技術院長 Curing treatment
JPS62236789A (en) * 1986-04-08 1987-10-16 Idemitsu Petrochem Co Ltd Binder for thermal recording paper

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5880239A (en) * 1995-06-08 1999-03-09 Wacker-Chemie Gmbh Fusible chlorine-free vinyl acetate copolymer fibres
WO2001007496A2 (en) * 1999-07-22 2001-02-01 Bp Chemicals Limited Polymers, their precursors and processes for preparation thereof
WO2001007496A3 (en) * 1999-07-22 2002-09-26 Bp Chem Int Ltd Polymers, their precursors and processes for preparation thereof

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MX23878A (en) 1994-02-28
CA2032979A1 (en) 1991-06-23
GB9025745D0 (en) 1991-01-09

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