Production method for polyacetal copolymer

Patent metadata

Field	Value
Publication number	US-9657136-B2
Application number	US-201314442659-A
Country	US
Kind code	B2
Filing date	Oct 25, 2013
Priority date	Nov 27, 2012
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

A production method for a polyacetal copolymer that makes deactivation of a catalyst simple and efficient and that achieves a high polymerization yield and high quality using equipment that does not require a cleaning step and a process that involves a simple operation technique. The production method for a polyacetal copolymer uses trioxane as a main monomer and a cyclic ether and/or a cyclic formal having at least one carbon-carbon bond as a comonomer. In the production method, a predetermined heteropoly acid is used as a polymerization catalyst to perform copolymerization, a predetermined salt is added to the reaction product, melt kneading processing is performed, and the polymerization catalyst is deactivated.

First claim

The invention claimed is:

1. A production method for a polyacetal copolymer with trioxane as a main monomer (a) and a cyclic ether and/or cyclic formal having at least one carbon-carbon bond as a comonomer (b), wherein when producing the polyacetal copolymer, copolymerization is carried out using a heteropoly acid shown by the below General Formula (1) as a polymerization catalyst (c), and the polymerization catalyst (c) is deactivated by adding to a reaction product a carbonate, bicarbonate, or carboxylate of an alkali metal or alkali earth metal or a hydrate thereof (d), and performing a melt kneading treatment,
H m [M 1 x .M 2 y O z ].n H 2 O  (1)

wherein, M 1 is a central element consisting of P and/or Si,
M 2 is one or more coordination elements selected from the group consisting of W, Mo, and V, and
x is an integer from 1 to 10, y is an integer from 6 to 40, z is an integer from 10 to 100, m is an integer of 1 or more, and n is an integer of 0 to 50, and
wherein an added amount of the carbonate, bicarbonate or carboxylate of an alkali metal or alkali earth metal or a hydrate thereof (d) with respect to 1 kg of the crude polyacetal copolymer obtained by the copolymerization reaction is 0.006 to 0.34 mEq.

2. A production method for a polyacetal copolymer according to claim 1 , wherein the comonomer (b) is at least one selected from the group consisting of 1,3-dioxolane, diethylene glycol formal, 1,4-butanediol formal, 1,3-dioxane, and ethylene oxide.

3. A production method for a polyacetal copolymer according to claim 1 , wherein the heteropoly acid is at least one selected from phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomolybdotungstovanadic acid, phosphotungstovanadic acid, silicotungstic acid, silicomolybdic acid, silicomolybdotungstic acid, or silicomolybdotungstovanadic acid.

4. A production method for a polyacetal copolymer according to claim 1 , wherein the carbonate, bicarbonate, or carboxylate of an alkali metal element or alkali earth metal element or a hydrate thereof (d) is:
(i) at least one carbonate selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate or barium carbonate, and a hydrate thereof,
(ii) at least one bicarbonate selected from the group consisting of lithium bicarbonate, sodium bicarbonate, or potassium bicarbonate, and a hydrate thereof,
(iii) at least one aliphatic carboxylate selected from the group consisting of lithium formate, sodium formate, potassium formate, magnesium formate, calcium formate, barium formate, lithium acetate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate, barium acetate, lithium laurate, sodium laurate, potassium laurate, lithium stearate, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, monosodium succinate, disodium succinate, dipotassium succinate, lithium citrate, monosodium citrate, trisodium citrate, sodium aspartate, or disodium glutamate, and a hydrate thereof,
(iv) at least one unsaturated aliphatic carboxylate selected from the group consisting of sodium acrylate, potassium acrylate, sodium sorbate, potassium sorbate, or monosodium fumarate, and a hydrate thereof, or
(v) at least one aromatic carboxylate selected from the group consisting of lithium benzoate, sodium benzoate, potassium benzoate, potassium biphthalate, lithium salicylate, sodium salicylate, potassium salicylate, and a hydrate thereof.

5. A production method for a polyacetal copolymer according according to claim 4 , wherein the carbonate, bicarbonate, or carboxylate of an alkali metal or alkali earth metal or a hydrate thereof (d) is at least one selected from the group consisting of sodium formate, sodium acetate, sodium carbonate, sodium bicarbonate, disodium succinate, sodium laurate, sodium stearate and calcium stearate.

6. A production method for a polyacetal copolymer according to claim 1 , wherein an addition of the carbonate, bicarbonate, or carboxylate of an alkali metal or alkali earth metal or a hydrate thereof (d) to the reaction product is:
(i) the carbonate, bicarbonate, or carboxylate of an alkali metal or alkali earth metal or a hydrate thereof (d) is directly added as a solution to the crude polyacetal copolymer obtained by the copolymerization reaction, or
(ii) a powder of a polyacetal copolymer is soaked with a solution of the carbonate, bicarbonate, or carboxylate of an alkali metal or alkali earth metal or a hydrate thereof (d), and is uniformly dispersed, then the powder after the dispersal is added to the crude polyacetal copolymer, or
(iii) the carbonate, bicarbonate, or carboxylate of an alkali metal or alkali earth metal or a hydrate thereof (d) in the form of a solid is uniformly dispersed in a polyacetal copolymer powder, then the powder after the dispersal is added to the crude polyacetal copolymer, and
a b value of polyacetal copolymer pellets after deactivation of the polymerization catalyst (c), measured using a differential colorimeter, is 2.0 or less.

Assignees

• Polyplastics Co

Inventors

• Masuda Eiji
• Monma Tomohiro
• Horiguchi Tadahiro

Classifications

• C08G2/10 Primary

  Polymerisation of cyclic oligomers of formaldehyde · CPC title

• C08G65/266 Primary

  Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof · CPC title

• C08G2/18

  Copolymerisation of aldehydes or ketones · CPC title

• C08G2/06

  Catalysts (Catalysts in general B01J) · CPC title

• C08G2/28

  Post-polymerisation treatments · CPC title