Process for the preparation of a mercapto-terminated liquid polymer

Patent metadata

Field	Value
Publication number	US-9745422-B2
Application number	US-201515118604-A
Country	US
Kind code	B2
Filing date	Feb 23, 2015
Priority date	Feb 27, 2014
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

Process for the preparation of a mercapto-terminated liquid polymer comprising the steps of: a) reacting (para)formaldehyde with a halo-alcohol to form a reaction mixture comprising bis(2-dihaloalkyl)formal and b) reacting the reaction mixture of step a) with either (i) sodium polysulfide or (ii) a combination of sodium hydrosulfide and sulfur, wherein the process is performed in the presence of a branching agent selected from the group consisting of di-aldehydes and their corresponding actetals and hemi-acetals.

First claim

The invention claimed is:

1. A process for the preparation of a mercapto-terminated liquid polymer comprising the steps of:
a) reacting (para)formaldehyde with a halo-alcohol to form a reaction mixture comprising bis(2-dihaloalkyl)formal and
b) reacting the reaction mixture of step a) with either (i) sodium polysulfide or (ii) a combination of sodium hydrosulfide and sulfur,
wherein a branching agent is present in step a) and/or step b), said branching agent being selected from the group consisting of di-aldehydes and their corresponding acetals and hemiacetals.

2. The process according to claim 1 wherein the branching agent is a di-aldehyde with the formula (O═)(H)C(CH 2 ) n C(H)(═O), where n is in the range 0-8.

3. The process according to claim 1 wherein the branching agent is a hemi-acetal with the formula (O═)(H)C(CH 2 ) n C(H)(OR 1 )(OH) or (OH)(OR 1 )(H)C(CH 2 ) n C(H)(OR 1 )(OH), in which n is in the range 0-8 and each R 1 is independently selected from alkyl groups with 1-10 carbon atoms.

4. The process according to claim 1 wherein the branching agent is an acetal with the formula (O═)(H)C(CH 2 ) n C(OR 1 )(OR 2 ) or (OR 1 )(OR 2 )(H)C(CH 2 ) n C(H)(OR 1 )(OR 2 ), in which n is in the range 0-8 and each R 1 and R 2 is independently selected from alkyl groups with 1-10 carbon atoms.

5. The process according to claim 2 wherein n is in the range 0-3.

6. The process according to claim 3 wherein each R 1 is independently selected from alkyl groups with 1 or 2 carbon atoms.

7. The process according to claim 4 wherein the acetal is selected from the group consisting of glyoxal dimethyl acetal, glyoxal bis(dimethyl acetal), malonic aldehyde bis(diethyl acetal), and glutaric aldehyde bis(dimethyl acetal).

8. The process according to claim 1 wherein the branching agent is present in step a).

9. The process according to claim 8 wherein branching agent is added during step b).

10. The process according to claim 1 wherein the branching agent is used in an amount of 0.01 to 10 mol %, relative to (para)formaldehyde (calculated as CH 2 O).

11. The process according to claim 1 wherein the halo-alcohol is a chloroalcohol.

12. The process according to claim 1 wherein step b) is conducted in the presence of a dihaloalkane.

13. The process according to claim 1 wherein step a) is conducted in the presence of a polyol.

14. A process for the preparation of a mercapto-terminated liquid polymer comprising the steps of:
a) reacting (para)formaldehyde with a halo-alcohol to form a reaction mixture comprising bis(2-dihaloalkyl)formal and
b) reacting the reaction mixture of step a) with either (i) sodium polysulfide or (ii) a combination of sodium hydrosulfide and sulfur,
wherein a branching agent is present in step a) and/or step b), said branching agent being selected from the group consisting of di-aldehydes and their corresponding acetals and hemiacetals, and

wherein step b) is conducted in the presence of a pre-polymer with the structure
X—(R 2 —O) n —CH 2 —O—(R 1 —O) m —CH 2 —(O—R 2 ) p —X

wherein R 1 and R 2 can be the same or different and are selected from alkane chains containing 2-10 carbon atoms, X is a halogen atom selected from Cl, Br and I, and n, m, and p are integers that can be the same or different and have a value in the range 1-6.

15. The process according to claim 14 wherein X is Cl, R 1 is —CH 2 —CH 2 —, and R 2 is —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —, or —CH 2 —CH 2 —CH 2 —CH 2 —.

16. The process according to claim 3 wherein n is in the range 0-3.

17. The process according to claim 4 wherein n is in the range 0-3.

18. The process according to claim 4 wherein each R 1 and/or R 2 is independently selected from alkyl groups with 1 or 2 carbon atoms.

Assignees

• Akzo Nobel Chemicals Int Bv

Inventors

• Menzel Manfred
• Klobes Olaf
• Burkhardt Volker

Classifications

• C08L81/02

  Polythioethers; Polythioether-ethers · CPC title

• C08G75/00 Primary

  Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule · CPC title

• C08G75/16 Primary

  by polycondensation of organic compounds with inorganic polysulfides · CPC title

• C08L81/00

  Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers · CPC title

• C08G75/10

  from sulfur or sulfur-containing compounds and aldehydes or ketones · CPC title