Process for producing oxymethylene polymers
View Patent ↗The present invention relates to a process for the preparation of oxymethylene polymers, the oxymethylene polymers obtained therefrom as well as their use.
1. A process for the preparation of oxymethylene polymers comprising the following steps:
a) heterogeneous polymerization, in the presence of a chain transfer agent and an initiator for cationic polymerization, of a mixture comprising
a-1) at least one monomer that forms —CH 2 —O—units, and
a-2) optionally at least one comonomer copolymerizable therewith and having at least one C—C bond,
b) raising the temperature during the course of the polymerization sufficiently far that a substantially homogeneous polymer melt is present at the end of polymerization prior to deactivation alongside remaining residual monomers,
c) deactivating the active polymer chains in a substantially homogeneous phase by feeding a deactivator into the polymer and monomer mixture,
d) feeding the deactivated homogeneous polymer mixture prepared in step a) to c) to a hydrolysis zone as a hydrolysis mixture comprising one or more protic solvent(s) and wherein said polymer mixture is subjected to hydrolysis in the presence of protic solvent at a temperature which is higher than the melting point of the polymer mixture prepared in step a) to c); and
e) precipitating the hydrolyzed oxymethylene polymer from the solution prepared in step d).
2. The process according to claim 1 , wherein the chain transfer agent is an acetal of formaldehyde.
3. The process according to claim 2 , wherein the chain transfer agent is a compound of the following formula (I):
R 1 —(—O—CH 2 ) q —O—R 2 (I)
in which
R 1 and R 2 represent independently of each other alkyl groups, and q is an integer from 1 to 100.
4. The process according to claim 3 , wherein R 1 and/or R 2 is methyl.
5. The process according to claim 3 , wherein q is 1.
6. The process according to claim 1 wherein the initiator for cationic polymerization comprises at least one protic acid and at least one salt of a protic acid, wherein said at least one protic acid is sulfuric acid, tetrafluoroboric acid, perchloric acid, fluorinated alkyl sulfonic acid, chlorinated alkyl sulfonic acid or aryl sulfonic acid, and wherein said salt of protic acid is an alkali metal or alkaline earth metal salt of protic acid and/or a substituted ammonium salt of protic acid, the cations of the ammonium salt having the general formula (III)
wherein R 1 -R 4 are independently hydrogen, an alkyl group or an aryl group.
7. The process according to claim 6 wherein the molar ratio of protic acid to salt is in the range from 1:0.01 to 1:2000.
8. The process according to claim 6 , wherein the molar ratio of protic acid to salt is in the range from 1:0.5 to 1:10.
9. The process according to claim 6 , wherein the molar ratio of protic acid to salt is in the range from 1:1 to 1:4.
10. The process according to claim 1 , wherein the initiator comprises a mixture of trifluoromethane sulfonic acid and the salt of triethylamine and trifluoromethane sulfonic acid.
11. The process according to claim 1 , wherein the heterogeneous polymerization in step a) is carried out at a temperature ranging from 60° C. to 150° C.
12. The process according to claim 1 , wherein the heterogeneous polymerization in step a) is carried out at a temperature ranging from 80° C. to 140 ° C.
13. The process according to claim 1 , wherein in step b) the temperature is raised to a range of from 150° C. to 250° C.
14. The process according to claim 1 , wherein in step b) the temperature is raised to a range of from 160° C. to 200° C.
15. The process according to claim 1 , wherein the deactivator added to the homogeneous phase in step c) is a tertiary amine.
16. The process according to claim 15 , wherein the tertiary amine is triethylamine.
17. The process according to claim 1 , wherein the temperature of the hydrolysis mixture is from 160° C. to 220° C.
18. The process according to claim 1 , wherein the temperature of the hydrolysis is from 170° C. to 200° C.
19. The process according to claim 1 , wherein the hydrolysis mixture comprises one or more solvents selected from the group consisting of water, methanol, ethanol and isopropanol.
20. The process according to claim 1 , wherein the hydrolysis mixture comprises water and methanol.
21. The process according to claim 20 , wherein the water and methanol are in a weight ratio of from 1:3 to 1:20.
22. The process according to claim 20 , wherein the water and methanol are in a weight ratio of from 1:5 to 1:15.
23. The process according to claim 1 , wherein step e) is conducted by feeding the solution prepared in step d) into a precipitating solution or by decreasing the temperature of the solution.