COPOLYMERISATION OF ALDEHYDES AND VINYL ETHERS

Abstract

A process for the manufacturing of copoly mers of aldehydes, vinyl ethers, and certain copolymers of aldehydes and vinyl ethers can be performed. The copolymerisation is carried out in the presence of at least one reactive boron trihalide complex, and optionally, in the presence of at least one Bronsted Acid and/or Lewis Base.

Claims

1. A process, comprising: copolymerising at least one vinyl ether (V) and at least one aldehyde (A), optionally in the presence of at least one solvent, wherein the copolymerisation is carried out in the presence of at least one reactive boron trihalide complex of the formula
BX.sub.3x ROH wherein X is a halide, ROH is an alcohol or water, and x is a positive number of more than 0(zero), optionally in the presence of at least one Brnsted Acid (BA) and/or Lewis Base (LB), wherein a molar ratio of the at least one vinyl ether (V):the at least one aldehyde (A) is from 10:1 to 1:1.

2. The process according to claim 1, wherein the alcohol ROH is at least one selected from the group consisting of methanol, ethanol, n-propanol, iso-propanol, n-butanol, and tert.butanol.

3. The process according to claim 1, wherein the Bronsted Acid (BA) is at least one selected from the group consisting of organic sulfonic acids and sulfuric acid.

4. The process according to claim 1, wherein the Lewis Base (LB) is at least one selected from the group consisting of ethers and esters.

5. The process according to claim 1, wherein the vinyl ethers (V) are C.sub.1- to C.sub.20-alkyl vinyl ethers, C.sub.3- to C.sub.20-alkenyl vinyl ethers, C.sub.5- to C.sub.12-cycloalkyl vinyl ethers, cyclic vinylethers, vinyl ethers comprising alkylene glycol side chains, vinyl ethers comprising ester groups in the side chain, and C.sub.6- to C.sub.12-aryl vinyl ethers.

6. The process according to claim 1, wherein the at least one vinyl ether (V) bears two or more vinyl ether groups.

7. The process according to claim 1, wherein the at least one aldehyde (A) is at least one selected from the group consisting of optionally substituted C.sub.6- to C.sub.12-aromatic aldehydes, C.sub.1- to C.sub.100-aliphatic aldehydes, one- or multifold unsaturated C.sub.3- to C.sub.20-aliphatic aldehydes, and C.sub.5- to C.sub.12-cycloaliphatic aldehydes.

8. The process according to claim 1, wherein the copolymerisation is carried out at a temperature of from 90 to 0 C.

9. The process according to claim 1, wherein the copolymerisation is carried out for 0.5 to 24 hours.

10. The process according to claim 1, wherein the copolymerisation is stopped by quenching with at least one selected from the group consisting of alcohols, water, ammonia, amines, hydroxides, carbonates, and hydrogen carbonates.

11. A copolymer, comprising: a polymerised form of at least one vinyl ether (V) and at least one aldehyde (A), wherein the at least one aldehyde (A) is an aliphatic aldehyde, wherein a molar incorporation ratio of the at least one vinyl ether (V):the at least one aldehyde (A) is from 10:1 to 1:1.

12. A copolymer, comprising: a polymerised form of at least one vinyl ether (V) and at least one aldehyde (A), wherein the at least one vinyl ether (V) is a C.sub.5- to C.sub.12-cycloalkyl vinyl ether, wherein a molar incorporation ratio of the at least one vinyl ether (V):the at least one aldehyde (A) is from 10:1 to 1:1.

13. A copolymer, comprising: a polymerised form of at least one vinyl ether (V) and at least one aldehyde (A), wherein the at least one vinyl ether (V) is at least one selected from the group consisting of C.sub.10- to C.sub.20-alkyl vinyl ethers and C.sub.10- to C.sub.20-alkenyl vinyl ethers, wherein a molar incorporation ratio of the at least one vinyl ether (V):the at least one aldehyde (A) is from 10:1 to 1:1.

14. The copolymer according to claim 11, wherein a polydispersity is from 1 to 5.

15. The copolymer according to claim 11, wherein a weight average molecular weight M.sub.w is from 1000 to 40000.

16. A process for hydrolysis of a copolymer according to claim 11, the process comprising: reacting the the copolymer, optionally dissolved in at least one solvent, with water in the presence of at least one Brnsted Acid with a pK.sub.a-value of not more than 3.0.

17. The process according to claim 1, wherein X is fluorine.

18. The process according to claim 1, wherein ROH is a linear or branched C.sub.1-C.sub.4-alkanol.

19. The process according to claim 1, wherein the molar ratio of the at least one vinyl ether (V):the at least one aldehyde (A) is from 2:1.2 to 1:1.2.

20. The process according to claim 1, wherein the Brnsted Acid (BA) is at least one selected from the group consisting of methane sulfonic acid and ethane sulfonic acid.

Description

EXAMPLES

Preparation of BF.SUB.3..Math.MeOH

[0119] 10 g of dry methanol were placed in a stirred vessel and purged with gaseous BF.sub.3 under inert conditions at 20 C. The determination of BF.sub.3 to methanol ratio was performed via elemental analysis.

Typical Polymerisation Procedure

[0120] Reagents were not distilled or dried before use, but used as obtained. Polymerisation was carried out under a dry nitrogen atmosphere in a 500 mL baked glass tube equipped with a four-way stopcock. The pre-chilled Brnsted acid was added to a stirred pre-chilled mixture of the monomers, the Lewis Base (optional) and 200 mL toluene at 0 C. The temperature was subsequently lowered to 78 C. and the reaction was started by the addition via dry medical syringe of pre-chilled Lewis acid. The reaction mixture was magnetically stirred throughout the polymerization. After a reaction time of 2-6 hours, the polymerization was quenched with pre-chilled methanol containing a small amount of ammonia solution. The quenched reaction mixture was diluted with dichloromethane and then washed with water to remove the initiator residues. After filtration, the solvent and other volatiles were evaporated under reduced pressure (50 C., 5 mbar), and the residue was vacuum-dried for at least 6 h at 50 C. The monomer conversion was determined by .sup.1H NMR, molecular weight and molecular weight distribution by GPC in THF against polystyrene standards.

Typical Extraction Procedure (Optional)

[0121] The obtained copolymer was washed two times with methanol. Each time, the upper methanol phase was discarded. The obtained viscous or solid residue was subsequently dried under reduced pressure (50 C., 5 mbar). The copolymer was dissolved in few dichloromethane and placed on a foil. Solvent was allowed to evaporate and the obtained film was dried at 50 C., 10 mbar overnight. In some cases, a white powder was obtained by milling of the film in a milling apparatus.

Typical Hydrolysis Procedure

[0122] The copolymer was dissolved in few THF under magnetic stirring. A 1.0 M acid solution was added and the mixture was stirred for 4 days at room temperature. Then, aqueous NaOH was added. The mixture was diluted with dichloromethane and the two phases were separated by extraction. The organic phase was washed three times with water after which the solvents were evaporated at 25-50 C., 5 mbar to (typically) obtain a transparent, oily or solid product.

TABLE-US-00001 TABLE 1 Overview of examples. Residual Brnsted Lewis M.sub.w Aldehyde # VE Aldehyde Lewis Acid Acid Base (g/mol) PDI (%) 1 (C) 0.15 0.15 mol 1 mmol 1 mmol 0.25 15700 2.0 14 mol Anisaldehyde GaCl.sub.3 EtSO.sub.3H mol IBVE dioxane 2 (C) 0.15 0.15 mol 1 mmol 1 mmol 0.25 No polymer 78 mol Anisaldehyde BF.sub.3(OEt).sub.2 MeSO.sub.3H mol IBVE dioxane 3 (C) 0.15 0.15 mol 1.5 mmol 1 mmol 0.25 No polymer 83 mol Anisaldehyde BF.sub.3(OEt).sub.2 MeSO.sub.3H mol IBVE dioxane 4 0.15 0.15 mol 1 mmol 1 mmol 0.25 14700 2.2 20 mol Anisaldehyde BF.sub.3(0.92 MeOH) MeSO.sub.3H mol IBVE dioxane 5 0.15 0.15 mol 1 mmol 0.83 0.25 17400 2.3 20 mol Anisaldehyde BF.sub.3(0.92 MeOH mmol mol IBVE MeSO.sub.3H dioxane 6 0.15 0.15 mol 1 mmol 1 mmol 0.125 18800 2.7 17 mol Anisaldehyde BF.sub.3(0.92MeOH) MeSO.sub.3H mol IBVE dioxane 7 0.15 0.15 mol 1.5 mmol 1 mmol 0.25 13200 2.1 22 mol Anisaldehyde BF.sub.3(0.92MeOH) MeSO.sub.3H mol IBVE dioxane 8 0.15 0.15 mol 0.5 mmol 1 mmol 0.25 18000 2.5 16 mol Anisaldehyde BF.sub.3(0.92MeOH) MeSO.sub.3H mol IBVE dioxane 9 0.15 0.15 mol 1 mmol 1 mmol 0.25 20900 2.8 n.d. mol Benzaldehyde BF.sub.3(0.92MeOH) MeSO.sub.3H mol IBVE dioxane 10 0.15 0.15 mol Cis- 1 mmol 1 mmol 0.25 14600 (RI) 4.3 <1 mol 4-heptene-1-al BF.sub.3(0.92MeOH) MeSO.sub.3H mol IBVE dioxane 11 0.15 0.15 mol 1 mmol 1 mmol 0.25 10700 2.1 26 mol Anisaldehyde BF.sub.3(0.92MeOH) MeSO.sub.3H mol EVE dioxane 12 0.15 0.15 mol 1 mmol 1 mmol 0.25 8800 (RI) 1.6 <1 mol Trans-2- BF.sub.3(0.92MeOH) MeSO.sub.3H mol IBVE decenal dioxane 13 0.15 0.15 mol 1 mmol 1 mmol none 15000 2.2 23 mol Anisaldehyde BF.sub.3(0.92MeOH) MeSO.sub.3H IBVE 14 0.15 0.15 mol 1 mmol 1 mmol 0.25 9700 1.7 4 mol Furfural BF.sub.3(0.92MeOH) MeSO.sub.3H mol IBVE dioxane 15 0.15 0.15 mol 1 mmol 1 mmol 0.25 26000 1.4 15 mol Anisaldehyde BF.sub.3(0.92MeOH) MeSO.sub.3H mol IBVE + dioxane 7.5 mmol TEG- DVE 16 0.15 0.15 mol 1 mmol 1 mmol 0.25 59000 2.9 11 mol Anisaldehyde BF.sub.3(0.92MeOH) MeSO.sub.3H mol IBVE + dioxane 15 mmol TEG- DVE VE: vinyl ether IBVE: iso-butyl vinyl ether EVE: ethyl vinyl ether TEG-DVE = triethylene glycol divinyl ether MeOH: methanol EtSO.sub.3H/MeSO.sub.3H: ethane/methane sulfonic acid n.d. = not determined Mw measured using UV-detection of crude polymer unless explicitly stated to be determined using RI-detection (C): Comparative Example Residual aldehyde: as determined in the crude polymer by .sup.1H-NMR spectroscopy. After extraction, the residual aldehyde levels after typically <1%.

[0123] A comparison of comparative Example 1 with Examples 4 to 6 shows comparable conversion rates and molecular weight as with GaCl.sub.3, however, with the much easier to handle catalyst complex BF.sub.3.Math.(0.92MeOH) according to the present invention.

[0124] The catalyst system BF.sub.3.Math.(OEt).sub.2 does not yield any significant amounts of a copolymer of anisaldehyde and iso-butyl vinyl ether.

[0125] A comparison of Example 4 with Examples 15 and 16 shows an increase in the glass temperature of the polymer as measured by differential scanning calorimetry (DSC). This can be explained by the higher molecular weight/crosslinking of Example 15 and 16 versus Example 4.

TABLE-US-00002 Addition of Mw T.sub.g Example TEG-DVE (g/mol) ( C.) Example 4 None 14700 27 Example 15 7.5 mmol 25600 32 Example 16 15 mmol 59400 34