Method for preparing a polymer from at least one cyclic monomer

Abstract

The present invention relates to a method for preparing a copolymer from at least one cyclic monomer selected from: a lactone, a lactam, a carbonate, a lactide and a glycolide, an oxazoline, an epoxide, a cyclosiloxane, comprising the step consisting of reacting said cyclic monomer in the presence of a substituted phosphorus-containing compound. It also relates to the polymer composition obtained according to this method, as well as the uses thereof, notably as antistatic additives, biocompatible materials, as membranes for treatment of effluents or in electrochemical systems for energy storage.

Claims

1. A method for preparing a (co)polymer from at least one cyclic monomer selected from the group consisting of a lactone, a lactam, a carbonate, a lactide, a glycolide, an oxazoline, an epoxide, and a cyclosiloxane, wherein the method comprises a step of polymerizing, without using as a catalyst any metal compounds or species, the cyclic monomer or monomers, wherein a substituted phosphorus-containing compound selected from the following compounds is used as a catalyst for the polymerizing: ##STR00004##

2. The method as claimed in claim 1, wherein an initiator is used.

3. The method as claimed in claim 1, wherein the cyclic monomer is selected from saturated or unsaturated, substituted or unsubstituted β-, γ-, δ- and ε-lactones, having from 4 to 11 carbon atoms.

4. The method as claimed in claim 3, wherein the cyclic monomer is ε-caprolactone.

5. The method as claimed in claim 1, wherein the cyclic monomer is a lactam selected from the group consisting of caprolactam, enantholactam, lauryllactam, pyrrolidinone and piperidone.

6. The method as claimed in claim 1, wherein the cyclic monomer is a cyclic carbonate of the following formula I: ##STR00005## where R denotes a linear alkyl group containing from 2 to 20 carbon atoms or a branched alkyl or alkaryl group containing from 2 to 20 carbon atoms, optionally substituted with one or more substituents selected independently from oxo and halo groups.

7. The method as claimed in claim 1, wherein the cyclic monomer is selected from the group consisting of lactides in racemic, enantiomerically pure or meso form.

8. The method as claimed in claim 1, wherein the cyclic monomer is glycolide.

9. The method as claimed in claim 2, wherein the initiator is water, pentanol or a polymer bearing at least one hydroxyl function.

10. The method as claimed in claim 2, wherein the initiator is selected from the group consisting of (alkoxy)polyalkylene glycols; poly(alkyl)alkylene adipate diols; optionally hydrogenated, α-hydroxylated or α,ω-dihydroxylated polydienes; mono- and polyhydroxylated polyalkylenes; polylactides containing terminal hydroxyl functions; polyhydroxyalkanoates; polysaccharides and mono- and oligo-saccharides, modified or unmodified; and mixtures thereof.

11. The method as claimed in claim 2, wherein the inititiator is a polymer bearing at least one hydroxyl function selected from the group consisting of (methoxy)polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(2-methyl-1,3-propylene adipate)diol, poly(1,4-butylene adipate)diol, polybutadiene α,ω-dihydroxylated, polyisoprene α,ω-dihydroxylated, mono- and polyhydroxylated polyisobutylene, poly(3-hydroxybutyrate), poly(3-hydroxyvalerate), starch, chitin, chitosan, dextran, cellulose, sucrose, and isomaltulose and mixtures thereof.

12. The method as claimed in claim 2, wherein the initiator is a polymer bearing at least one thiol function.

13. The method as claimed in claim 12, wherein the initiator is selected from the group consisting of α-thiolated and α,ω-thiolated polystyrenes, α-thiolated and α,ω-thiolated poly(meth)acrylates, α-thiolated and α,ω-thiolated polybutadienes, and mixtures thereof.

14. The method as claimed in claim 2, wherein the initiator is a vinyl co-oligomer or copolymer from the family of acrylic, methacrylic, styrene or diene polymers, resulting from copolymerization between acrylic, methacrylic, styrene or diene monomers and functional monomers having either a hydroxyl group, or a thiol group.

15. The method as claimed in claim 1, wherein the substituted phosphorus-containing compound is diphenylphosphate.

16. The method as claimed in claim 1, wherein the substituted phosphorus-containing compound is (R)-3,3′-bis[3,5-bis(trifluoromethyl)phenyl]-1,1′-binaphthyl-2,2′-diyl hydrogen phosphate.

17. The method as claimed in claim 1, wherein the substituted phosphorus-containing compound is N-[(trifluoromethyl)sulfonyl]-,diphenyl ester of phosphoramidic acid.

18. The method as claimed in claim 1, wherein the molar ratio of the cyclic monomer to the polymeric initiator is in the range from 5 to 500.

19. The method as claimed in claim 2, wherein the molar ratio of the substituted phosphorus-containing compound to each hydroxyl or thiol function of the initiator is from 1 to 3.

20. The method as claimed in claim 1, the reaction is carried out at a temperature in the range from 0° C. at 230° C.

21. A method for improving the antistatic properties of a polymeric resin, improving the impact toughness of a resin, or plasticizing PVC, comprising using a copolymer prepared in accordance with the method of claim 1 as an additive.

Description

EXAMPLES

Example 1: Preparation of Polylactones and Polycarbonates

Example 1A

(1) A solution of ε-caprolactone (75 μl, 40 eq., 0.9 mol.Math.l.sup.−1) in CDCl.sub.3 (425 μl) with pentanol (1.8 μl, 1 eq.) is poured into a solution of (R)-3-3′-bis[3,5-bis(trifluoromethyl)phenyl]-1,1′-binaphthyl-2,2′-diyl hydrogen phosphate (13 mg, 1 eq.). The reaction mixture is stirred under argon at 30° C. until there is complete conversion of the monomer, established on the basis of NMR, i.e. 4 h.

(2) Conversion: ≧95%

(3) .sup.1H NMR: DP=33

(4) GPC: M.sub.n=7600 g/mol, PDI=1.09

Example 1B

(5) n-Pentanol (13 μl, 1 eq.) and diphenylphosphate (85 mg, 3 eq.) are added successively to a solution of ε-caprolactone (1 ml, 80 eq., 0.9 mol.Math.l.sup.−1) in toluene (9 ml). The reaction mixture is stirred under argon at 30° C. until there is complete conversion of the monomer, established on the basis of NMR, i.e. 3 h.

(6) Conversion: ≧95%

(7) .sup.1H NMR: DP=76

(8) GPC: M.sub.n=16 000 g/mol, PDI=1.10

Example 1C

(9) n-Pentanol (15 μl, 1 eq.) and diphenylphosphate (26 mg, 1 eq.) are added successively to a solution of trimethylenecarbonate (550 mg, 40 eq., 0.9 mol.Math.l.sup.−1) in toluene (6 ml). The reaction mixture is stirred under argon at 30° C. until there is complete conversion of the monomer, established on the basis of NMR, i.e. 20 h.

(10) Conversion: ≧95%

(11) .sup.1H NMR: DP=31 and 0% decarboxylation

(12) GPC: M.sub.n=6000 g/mol, PDI=1.05

Example 1D

(13) n-Pentanol (10 μl, 1 eq.) and N-[(trifluoromethyl)sulfonyl]-, diphenyl ester of phosphoramidic acid (103 mg, 3 eq.) are added successively to a solution of ε-caprolactone (400 μl, 40 eq., 0.9 mol.Math.l.sup.−1) in toluene (3.6 ml). The reaction mixture is stirred under argon at 30° C. until there is complete conversion of the monomer, established on the basis of NMR, i.e. 45 min. Then ε-caprolactone (400 μl, 40 eq.) is added to the reaction mixture. After complete conversion, 800 μl, 80 eq. is again introduced into the reaction mixture. Complete conversion is established by NMR 3 h after the last addition.

(14) Conversion: ≧99%

(15) .sup.1H NMR: DP=148

(16) GPC: M.sub.n=26 500 g/mol, PDI=1.11

Example 1E

(17) N-[(Trifluoromethyl)sulfonyl]-, diphenyl ester of phosphoramidic acid (34 mg, 1 eq.) is added to a solution of ε-caprolactone (400 μl, 40 eq., 0.9 mol.Math.l.sup.−1) in toluene (3.6 ml). The reaction mixture is stirred under argon at 30° C. until there is complete conversion of the monomer, established on the basis of NMR, i.e. 6 h.

(18) Conversion: ≧99%

(19) .sup.1H NMR: DP=140

(20) GPC: M.sub.n=24 000 g/mol, PDI=1.34

Example 1F

(21) n-Pentanol (25 μl, 1 eq.) and N-[(trifluoromethyl)sulfonyl]-diphenyl ester of phosphoramidic acid (85 mg, 3 eq.) are added successively to a solution of ε-caprolactone (1 ml, 80 eq., 0.9 mol.Math.l.sup.−1) in toluene (9 ml). The reaction mixture is stirred under argon at 30° C. until there is complete conversion of the monomer, established on the basis of NMR, i.e. 3 h.

(22) Conversion: ≧95%

(23) .sup.1H NMR: DP=62

(24) GPC: M.sub.n=12 600 g/mol, PDI=1.11

Example 1G: Continuous Polymerization

(25) n-Pentanol (25 μl, 1 eq.) and diphenylphosphate (56 mg, 1 eq.) are added successively to a solution of ε-caprolactone (250 μl, 10 eq., 0.9 mol.Math.l.sup.−1) in toluene (2.25 ml). The reaction mixture is stirred under argon at 30° C. A solution of ε-caprolactone (1.75 ml, 70 eq., 0.9 mol.Math.l.sup.−1) in toluene (17.25 ml) is added continuously at a flow rate of 0.03 ml/min for 10 h. Complete conversion of the monomer is established on the basis of NMR, 30 minutes after the end of addition, i.e. 10 h 30 min.

(26) Conversion: ≧95%

(27) .sup.1H NMR: DP=59

(28) GPC: M.sub.n=12 100 g/mol, PDI=1.06

Example 1H: Continuous Polymerization

(29) n-Pentanol (25 μl, 1 eq.) and N-[(trifluoromethyl)sulfonyl]-diphenyl ester of phosphoramidic acid (90 mg, 1 eq.) are added successively to a solution of ε-caprolactone (250 μl, 10 eq., 0.9 mol.Math.l.sup.−1) in toluene (2.25 ml). The reaction mixture is stirred under argon at 30° C. A solution of ε-caprolactone (1.75 ml, 70 eq., 0.9 mol.Math.l.sup.−1) in toluene (17.25 ml) is added continuously at a flow rate of 0.06 ml/min for 5 h. Complete conversion of the monomer is established on the basis of NMR, 15 minutes after the end of addition, i.e. 5 h 15 min.

(30) Conversion: ≧95%

(31) .sup.1H NMR: DP=68

(32) GPC: M.sub.n=13 700 g/mol, PDI=1.09

Example 2: Preparation of Polylactones and Polycarbonates at High Temperature

Example 2A

(33) n-Pentanol (13 μl, 1 eq.) and diphenylphosphate (85 mg, 3 eq.) are added successively to a solution of ε-caprolactone (1 ml, 80 eq., 0.9 mol.Math.l.sup.−1) in toluene (9 ml). The reaction mixture is stirred under argon at 80° C. until there is complete conversion of the monomer, established on the basis of NMR, i.e. 1 h 30 min.

(34) Conversion: ≧95%

(35) .sup.1H NMR: DP=80

(36) GPC: M.sub.n=16 000 g/mol, PDI=1.11

Example 2B

(37) n-Pentanol (7 μl, 1 eq.) and diphenylphosphate (34 mg, 2 eq.) are added successively to a solution of trimethylenecarbonate (550 mg, 80 eq., 0.9 mol.Math.l.sup.−1) in toluene (6 ml). The reaction mixture is stirred under argon at 80° C. until there is complete conversion of the monomer, established on the basis of NMR, i.e. 6 h.

(38) Conversion: ≧95%

(39) .sup.1H NMR: DP=60 and 0% decarboxylation

(40) GPC: M.sub.n=10 200 g/mol, PDI=1.08

Example 2C

(41) n-Pentanol (25 μl, 1 eq.) and N-[(trifluoromethyl)sulfonyl]-diphenyl ester of phosphoramidic acid (85 mg, 1 eq.) are added successively to a solution of ε-caprolactone (1 ml, 80 eq., 0.9 mol.Math.l.sup.−1) in toluene (9 ml). The reaction mixture is stirred under argon at 80° C. until there is complete conversion of the monomer, established on the basis of NMR, i.e. 5 h.

(42) Conversion: ≧100%

(43) .sup.1H NMR: DP=67

(44) GPC: M.sub.n=13 950 g/mol, PDI=1.14

Example 3: Preparation of Copolymers Based on Polylactones

(45) Polyethylene glycol (M.sub.n=2000, IP=1.06) (75 mg, 1 eq.) and N-[(trifluoromethyl)sulfonyl]-, diphenyl ester of phosphoramidic acid (34 mg, 1 eq.) are added successively to a solution of ε-caprolactone (400 μl, 40 eq., 0.9 mol.Math.l.sup.−1) in toluene (3.6 ml). The reaction mixture is stirred under argon at 30° C. until there is complete conversion of the monomer, established on the basis of NMR, i.e. 1 h 30 min.

(46) Conversion: ≧99%

(47) GPC: M.sub.n=6500 g/mol, PDI=1.13