Novel Polyvinyl Ester and Novel Polyvinylalcohol Copolymers

Abstract

The present invention relates to new polyvinyl polymers, to initiator systems for preparing them, to a process for preparing the polymers, and also to their use as an adhesive component, emulsifier, detergent, lubricant, coating component, for electrically insulating magnetic wires, for producing laminated glass sheets, as an adhesive primer, for textile coatings, as an additive for motor fuels, engine oils, concrete, and in papermaking, for producing water-soluble films and for preparing biodegradable and water-soluble polymers.

Description

EXAMPLE 1

ω-methoxypolyethylene glycol 2-iodo-2-methyl propionate

A 500 ml round-bottomed flask is charged with 21.5 g (4.3 mmol) of polyethylene is glycol monomethyl ether (M=5000 g/mol) in 100 ml of dichloromethane. At 0° C. 0.435 g (4.3 mmol) of triethylamine and then 1 g of 2-iodo-2-methylpropionyl chloride (D. N. Harpp et al., J. Org. Chem. 1975, 40, 3420-3427) are added dropwise. The solution is stirred at room temperature overnight and then washed with 100 ml of water and 50 ml of 2 M NaOH. The solvent is removed by drying over magnesium sulphate under reduced pressure, and the residue is dried under an oil pump vacuum, giving the product as a white solid. Yield: 19.34 g (3.7 mmol, 87%). ¹H-NMR (500 MHz, CDCl₃): δ=3.62 (m, about 520 H, PEG), 3.36 (s, 3H, PEG-OMe), 2.15 (s, 6H, C(CH₃)₂I) ppm.

EXAMPLE 2

Polymerization of a Vinyl Acetate with the Initiator of Example 1

A 100 ml round-bottomed flask is charged in succession and under argon with the following reagents: 85 mg (0.24 mmol) of cyclopentadienyldicarbonyliron(I) dimer, 2.0 ml of anisol, 4.42 ml (48 mmol) of vinyl acetate, 2.5 g (0.48 mmol) of ω-methoxypolyethylene glycol 2-iodo-2-methyl-propionate and 0.96 ml (0.24 mmol, c=0.25 mol/l in anisol) of aluminium triisopropoxide. The solution is stirred at 70° C. for 18 hours. Then the solvent and residual monomer are removed at 70° C. under reduced pressure. The product is dissolved in 30 ml of methanol and filtered over Alox 90 N. It is washed in portions with a further 100 ml of methanol. The solvent is removed under reduced pressure, giving the product as a pale powder. Yield: 3.0 g. ¹H-NMR (500 MHz, CDCl₃): δ=4.85 (PVAc), 3.62 (PEG), 3.35 (PEG-OCH₃), 2.05-1.95 (PVAc), 1.90-1.63 (PVAc & OC(O)C(CH₃)₂PVAc) ppm. GPC: M₂=11.000 g/mol, M_n=8700 g/mol, M_w/M_n=1.27. DSC: T_m=54° C.

EXAMPLE 3

Tetrakis-p-iodomethylphenylmethyl-4-Star-PEG[10]

11.1 g (80 mmol) of potassium carbonate are cautiously baked in a 250 ml round-bottomed flask. Following the addition of 150 ml of dimethylformamide, 20 g (10 mmol) of Tetrakis-hydroxy-4-Star-PEG[10] (M_w=2000 Da, Nektar Therapeutics, # 0J000D04), and 28.6 g (80 mmol) of 1,4-bisiodomethylbenzene, the mixture is stirred at 120° C. for 72 hours. The solvent is distilled off under reduced pressure and the residue is taken up in 200 ml of dichloromethane and 100 ml 2 M hydrochloric acid. The aqueous phase is extracted with twice 100 ml of dichloromethane. The combined organic phases are dried over magnesium sulphate and the solvent is removed under reduced pressure. The product is purified by column chromatography (silica gel, mobile solvent 1:1 dichloromethane/methanol) and obtained as a white amorphous solid. Yield: 19.3 g (6.6 mmol, 66%). ¹H-NMR (500 MHz, CDCl₃); δ=7.07, 6.99 (2×d, aromatic H), 4.63 (s, CH₂O) 4.36 (s, CH₂l) 3.71-3.53 (m, PEG) ppm.

EXAMPLE 4

Polymerization of Vinyl Acetate with the Initiator of Example 3 and Purification of the Polymer to Tetrakis-PVAc-methylphenylmethyl-4-Star-PEG[10]

A 250 ml round-bottomed flask is charged in succession and under argon with the following reagents: 0.71 mg (2.0 mmol) of cyclopentadienyidicarbonyliron(I) dimer, 20 ml of anisol, 88.8 ml (960 mmol) of vinyl acetate, 2.92 g (1.00 mmol) of Tetrakis-p-iodomethylphenylmethyl-4-Star-PEG[10] and 8 ml (2 mmol, c=0.25 mol/l in anisol) of aluminium triisopropoxide. The solution is stirred at 70° C. for four hours. Thereafter the solvent and residual monomer are removed at 70° C. under reduced pressure. The reaction mixture is dissolved in 800 ml of acetone and added to 1.25 l of n-heptane.

The system is allowed to settle for an hour and then the supernatant n-heptane is decanted off. The dark brown polymer thus obtained is dried under reduced pressure for two hours and taken up again in 800 ml of acetone. The dark polymer solution is added dropwise, with vigorous stirring using a KPG stirrer, to 2 l of an ice/2 M hydrochloric acid mixture (1 kg ice/1 l 2 M HCl). The polymer powder obtained in this way is isolated by filtration, washed to neutrality with twice 250 ml of water and freeze-dried under reduced pressure. The polymer thus obtained is colourless and no longer contains anisol. Yield: 37 g. ¹H-NMR (500 MHz, CDCl₃): δ=4.93-4.81 (PVAc), 3.67-3.51 (PEG), 2.05-1.95 (PVAc), 1.93-1.68 (PVAc) ppm. GPC: M_w=37.000 g/mol, M_n=32.000 g/mol, M_w/M_n=1.16. DSC: T_m=36° C.

EXAMPLE 5

Preparation of Tetrakis-PVOH-methylphenylmethyl-4-Star-PEG[10]

In a 250 ml round-bottomed flask 50 ml of a 1% strength methanolic sodium hydroxide solution are heated to 50° C. in a waterbath. Added dropwise to this solution over a period of 30 minutes is a solution of 5 g of Tetrakis-PVAc-methylphenylmethyl-4-Star-PEG[10] (Example 4) in 100 ml of methanol. After the end of the addition the system is stirred for 30 minutes. The white precipitate is isolated by filtration, washed alkali-free with methanol and dried under reduced pressure. Yield: 2.6 g. ¹H-NMR (500 MHz, [D₆]-DMSO): δ=6.83, 6.65 (2×s, aromatic H), 3.55-3.41 (PEG), 4.65, 4.46, 3.89, 3.84, 3.31, 1.44-1.33 (4×s, 1×m, PVOH) ppm. DSC: T_g=45° C., T_m=154° C.

EXAMPLE 6

Preparation of Tetrakis-PVB-methylphenylmethyl-4-Star-PEG[10]

A 100 ml round-bottomed flask is charged with 1.7 g of n-butyraldehyde, and added dropwise to this is a solution, heated at 65° C., of 2.5 g of Tetrakis-PVOH-methylphenylmethyl-4-Star-PEG[10] (Example 5) in 25 ml of water/0.15 g of concentrated sulphuric acid, the dropwise addition being carried out over the course of 2 minutes. Following complete addition a further 0.5 g of concentrated sulphuric acid is added and the mixture is stirred at 55° C. for an hour. After cooling to room temperature, the precipitate is isolated by filtration and washed to neutrality with water. The polymer is dissolved in 25 ml of hot methanol and the solution is added to 100 ml of water. The polymer is isolated by filtration. Yield: 4.2 g. ¹H-NMR (500 MHz, [D₆]-DSMO): δ=6.87, 6.69 (2×s, aromatic H), 3.59-3.40 (PEG), 4.69 (m, CH), 4.63, 4.41, 3.81, 3.55, 3.31, 1.44-1.21 (PVOH & alkyl groups) ppm.

Claims

1-9. (canceled)

10. Polyvinyl polymer based on formulae IV, IVa and IVb

11. The polymer as claimed in claim 10 wherein R6 is identical or different and is hydrogen or methyl,Z is carbon, silicon, nitrogen, phosphorus, oxygen or sulphur, or is an aromatic parent structure with at least four carbon atoms, in which one or more carbon atoms is optionally replaced by boron, nitrogen or phosphorus, wherein said aromatic or heteroaromatic parent structures are derived from benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, benzopyrrole, benzotriazole, benzopyridine, benzopyrazidine, benzopyrimidine, benzopyrazine, benzotriazine, indolizine, quinolizine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, which optionally are substituted, or is a cyclic non-aromatic parent structure with at least three carbon atoms, which optionally contains as nitrogen, boron, phosphorus, oxygen or sulphur, and said cyclic non-aromatic parent structure is derivable from the cycloalkyl group, cycloheteroalkyl group, or from the saccharides group,X1 is identical or different at each occurrence and is fluorine, chlorine, bromine or iodine andPol is polyvinyl butyral.

12. The polymer as claimed in claim 11, wherein Z is a cyclic non-aromatic parent structure with at least three carbon atoms, which optionally contains as nitrogen, boron, phosphorus, oxygen or sulphur, and said cyclic non-aromatic parent structure is derivable cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, azididine, azetidine, pyrrolidine, piperidine, azepane, azocane, 1,3,5-triazinane, 1,3,5-trioxane, oxetane, furan, dihydrofuran, tetrahydrofuran, pyran, dihydropyran, tetrahydropyran, oxepane, oxocane, alpha-glucose or beta-glucose, and X1 is identical or different at each occurrence and is chlorine, bromine or iodine.

13. The polymer according to claim 10, wherein Pol is a polymer based on polyvinyl acetate or polyvinyl butyral.

14. The polymer according to claim 10, wherein Pol is a copolymer based on a polyvinyl ester with 1 or more 1-olefins having 4 to 20 carbon atoms.

15. The polymer according to claim 10, wherein Pol is a homopolymer based on polyvinyl acetate.

16. The polymer according to claim 10, wherein Pol is a copolymer based on a polyvinyl acetate with 1 or more 1-olefins having 4 to 20 carbon atoms.

17. A component which comprises the polymer as claimed in claim 10, wherein the component is an adhesive component, emulsifier, detergent, lubricant, coating component for electrically insulating magnetic wires, coating component for producing laminated glass sheets, an additive for motor fuels, an additive for engine oils, concrete, and additive in papermaking, an additive for producing water-soluble films and additive for preparing biodegradable and water-soluble polymers.

18. The component as claimed in claim 17, wherein the component is an adhesive primer or a textile coating.

19. An initiator system which comprises at least one initiator of formula I, Ia or Ib, at least one metal compound of formula II and optionally at least one additive of the formula III:

20. The initiator system as claimed in claim 19, wherein R6 is identical or different and is hydrogen or methyl,Z is carbon, silicon, nitrogen, phosphorus, oxygen or sulphur, or is an aromatic parent structure with at least four carbon atoms, in which one or more carbon atoms is optionally replaced by boron, nitrogen or phosphorus, wherein said aromatic or heteroaromatic parent structures are derived from benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, benzopyrrole, benzotriazole, benzopyridine, benzopyrazidine, benzopyrimidine, benzopyrazine, benzotriazine, indolizine, quinolizine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, which optionally are substituted, or is a cyclic non-aromatic parent structure with at least three carbon atoms, which optionally contains as nitrogen, boron, phosphorus, oxygen or sulphur, and said cyclic non-aromatic parent structure is derivable from the cycloalkyl group, cycloheteroalkyl group, or from the saccharides group,X1 is identical or different at each occurrence and is fluorine, chlorine, bromine or iodine,M1 is identical or different at each occurrence and is chromium, molybdenum, ruthenium, iron, rhodium, nickel, palladium or copper,X2 is identical or different at each occurrence and is oxygen, fluorine, chlorine, bromine or iodine,L is identical or different at each occurrence and is a a carbon-containing ligand or a phosphorus-containing ligand,M2 is identical or different and is Li, Mg, Ti, B, Al, P or N, andR7 is identical or different and is methoxy, ethoxy, n-propoxy or isopropoxy.

21. The initiator system as claimed in claim 20, wherein Z is a cyclic non-aromatic parent structure with at least three carbon atoms, which optionally contains as nitrogen, boron, phosphorus, oxygen or sulphur, and said cyclic non-aromatic parent structure is derivable cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, aziridine, azetidine, pyrrolidine, piperidine, azepane, azocane, 1,3,5-triazinane, 1,3,5-trioxane, oxetane, furan, dihydrofuran, tetrahydrofuran, pyran, dihydropyran, tetrahydropyran, oxepane, oxocane, alpha-glucose or beta-glucose, X1 is identical or different at each occurrence and is chlorine, bromine or iodine andX2 is identical or different at each occurrence and is oxygen, fluorine, chlorine, bromine or iodine,L is identical or different at each occurrence and is methyl, phenyl, cymene, cumene, tolyl, mesityl, xylyl, indenyl, benzylidene, cyclopentadienyl or carbonyl, a nitrogen-containing ligand, such as triethylamine, tetramethylethylenediamine, pyridine, 2,2′-bipyridyl, substituted 2,2′-bipyridyl, 1,10-phenanthroline, phenylpyridin-2-yl-methylenamine, acetonitrile, substituted imidazolidine, terpyridyl, triphenylphosphine, tricyclohexylphosphine, bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane or BINAP, andM1 is identical or different at each occurrence and is iron or ruthenium.

22. A process to produce the initiator system as claimed in claim 19 which comprises reacting the compound of the formula I, Ia or Ib with a metal compound of the formula II.

23. A process for preparing a polymer which comprises polymerizing vinyl esters with one or more initiator systems according to claim 20.

24. A process for purifying the polymer as claimed in claim 10, which comprises the following steps: (A) reacting at least one compound of the formula I, Ia or Ib with at least one metal compound of the formula II, optionally in the presence of at least one additive of the formula III;(B) concentrating the reaction mixture from step A) to remove residual monomer and solvents,(C) dissolving the reaction mixture from step B) in one or more organic solvents;(D) optionally oxidizing the catalyst present in the mixture, by stirring in the presence of atmospheric oxygen or addition of oxidizing agents;(E) optionally separating off reaction products formed during the oxidization in step D);(F) precipitating the polymer by adding the polymer solution to one or more apolar aprotic solvents, separating the supernatant solvent, and optionally drying the polymer obtained;(G) optionally, redissolving the polymer obtained from step F) in one or more organic solvents,(H) precipitating the polymer by adding the solution from step G) to water or to an aqueous solution of an acid or to an aqueous solution of a base, where appropriate with stirring and cooling,(I) isolating the precipitated polymer, preferably by filtration or phase separation, optionally washing the polymer with water or with one of the liquids specified in step H),(J) optionally repeating steps G), H) and I), and(K) drying the polymer.