Continuous esterification and/or amidification method, without organic solvent, of an acid homopolymer or copolymer

Patent metadata

Field	Value
Publication number	US-10207446-B2
Application number	US-201515516733-A
Country	US
Kind code	B2
Filing date	Dec 7, 2015
Priority date	Dec 8, 2014
Publication date	Feb 19, 2019
Grant date	Feb 19, 2019

Abstract

The present invention relates to a continuous process for preparing a comb polymer, without organic solvent, by esterification and/or amidification of an acidic homopolymer or copolymer, which consists in performing the esterification and/or amidification of said homopolymer/copolymer by reaction at elevated temperature in the mixing and transportation zone of a tubular reactor, optionally equipped with a water removal system, in the presence of at least one poly(alkylene glycol) in solid or molten form and of an antioxidant, said esterification and/or amidification taking place at a temperature greater than or equal to 170° C.

First claim

The invention claimed is:

1. A continuous process for preparing a comb polymer, without organic solvent, by esterification and/or amidification of an acidic homopolymer or copolymer, the process comprising:
performing the esterification and/or amidification of said homopolymer/copolymer by reaction at elevated temperature in a mixing and transportation zone of a tubular reactor, optionally equipped with a water removal system, in the presence of at least one poly(alkylene glycol) in solid form or in molten form and of an antioxidant, said esterification and/or amidification taking place at a temperature of greater than or equal to 170° C., optionally in the presence of an esterification and/or amidification catalyst, optionally at reduced pressure and/or under a stream of inert gas,
wherein said acidic homopolymer or copolymer to be esterified and/or amidated is an acrylic acid and/or methacrylic acid polymer with a molecular weight Mw of between 1,000 and 20,000 g/mol, as determined by GPC.

2. The continuous process according to claim 1 , wherein said acidic homopolymer or copolymer results from the polymerization or copolymerization of at least one of the monomers chosen from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic anhydride.

3. The continuous process according to claim 1 , according to which said poly(alkylene glycol) has a formula (I):
R a -A-OH  (I)

wherein:
A represents a polymer chain comprising:
m alkylene oxide units of formula —O—CH 2 —CHR 4 — with R 4 representing an alkyl group comprising from 1 to 4 carbon atoms, and m ranging from 0 to 150,
p alkylene oxide units of formula —O—CH 2 —CHR 5 — with R 5 representing an alkyl group comprising from 1 to 4 carbon atoms, and p ranging from 0 to 150,
n ethylene oxide units —O—CH 2 —CH 2 — with n ranging from 1 to 150,
m+n+p >4 and
the alkylene oxide units of formula —O—CH 2 —CHR 4 —, alkylene oxide units of formula —O—CH 2 —CHR 5 — and the ethylene oxide units —O—CH 2 —CH 2 — are arranged alternately or statistically or in blocks; and

R a represents a linear or branched hydrocarbon-based chain comprising from 1 to 100 carbon atoms.

4. The continuous process according to claim 3 , wherein the esterification and/or amidification is performed in the further presence of a poly(alkylene glycol) having a formula (II):
HO —[(CHR 6 —CH 2 —O) r (CHR 7 —CH 2 —O) s —(CH 2 —CH 2 —O) t ]—H  (II)

wherein:
R 6 and R 7 , independently of each other, represent an alkyl group comprising from 1 to 4 carbon atoms,
r and s, independently of each other, range from 0 to 150,
t ranges from 1 to 150,
r+s+t >4 and
the alkylene oxide units of formula —CHR 6 —CH 2 —O—, alkylene oxide units of formula —CHR 7 —CH 2 —O— and the ethylene oxide units —CH 2 —CH 2 —O— are arranged alternately or statistically or in blocks.

5. The continuous process according to claim 4 , wherein the poly(alkylene glycol) of formula (II) is present in a content of less than 5% by weight, relative to the total amount of the comb polymer obtained at the outcome of the process.

6. The continuous process according to claim 1 , wherein said acidic homopolymer or copolymer to be esterified and/or amidated is in the form of an aqueous solution.

7. The continuous process according to claim 1 , wherein said acidic homopolymer or copolymer to be esterified and/or amidated is in dry form.

8. The continuous process according to claim 1 , wherein said acidic homopolymer or copolymer has a polydispersity index IP (ratio Mw/Mn) of between 1.5 and 3.

9. The continuous process according to claim 1 , wherein the antioxidant comprises an aromatic amine, a phosphine group, an organophosphate group and/or a piperidine cycle.

10. The continuous process according to claim 1 , wherein a mole ratio between said poly(alkylene glycol) and said acidic homopolymer or copolymer ranges between 100:1 and 1:1.

11. The continuous process according to claim 1 , wherein the tubular reactor comprises several reaction zones with different temperatures ranging between room temperature and 250° C., at least one reaction zone of which having a temperature greater than or equal to 170° C.

12. The continuous process according to claim 1 , comprising:
a) mixing said acidic homopolymer or copolymer and said at least one poly(alkylene glycol) in molten form before introduction into the tubular reactor to obtain a mixture,
b) introducing the mixture from a) into the tubular reactor,
c) introducing the antioxidant during a) and/or into the tubular reactor in one or several times, and
d) performing the esterification and/or amidification of said homopolymer/copolymer by kneading at elevated temperature in the mixing and transportation zone of the tubular reactor, which is optionally equipped with a water removal system, said esterification and/or amidification taking place at a temperature greater than or equal to 170° C., optionally in the presence of an esterification and/or amidification catalyst, optionally at reduced pressure and/or under a stream of inert gas.

13. The continuous process according to claim 1 , wherein the tubular reactor is an extruder.

14. A process for preparing a comb polymer, said process comprising:
a) preparing an acidic homopolymer or copolymer by controlled radical polymerization,
b) performing the process according to claim 1 , which comprises continuous esterification/amidification of said homopolymer/copolymer obtained according to a), in the presence of at least one poly(alkylene glycol) in solid or molten form and of an antioxidant,
c) optionally, performing dissolution of the polymer obtained in b),
d) optionally, performing total or partial neutralization of the polymer obtained in b) and/or c), and
e) optionally, forming into powder of the polymer obtained in b) and/or c) and/or d).

15. A continuous process for preparing a comb polymer, without organic solvent, by esterification and/or amidification of an acidic homopolymer or copolymer, the process comprising:
a) mixing said acidic homopolymer or copolymer and said at least one poly(alkylene glycol) in molten form before introduction into the tubular reactor to obtain a mixture,
b) introducing the mixture from a) into the tubular reactor,
c) introducing the antioxidant during a) and/or into the tubular reactor in one or several times, and
d) performing the esterification and/or amidification of said homopolymer/copolymer by kneading at elevated temperature in the mixing and transportation zone of the tubular reactor, which is optionally equipped with a water removal system, said esterification and/or amidification taking place at a temperature greater than or equal to 170° C., optionally in the presence of an esterification and/or amidification catalyst, optionally at reduced pressure and/or under a stream of inert gas.

16. The process according to claim 15 , wherein said acidic homopolymer or copolymer to be esterified and/or amidated is in the form of an aqueous solution.

17. A continuous process for preparing a comb polymer, without organic solvent, by esterification and/or amidification of an acidic homopolymer or copolymer, the process comprising:
performing the esterification and/or amidification of said homopolymer/copolymer by reaction at elevated temperature in a mixing and transportation zone of a tubular reactor, optionally equipped with a water removal system, in the presence of at least one poly(alkylene glycol) in solid form or in molten form and of an antioxidant, said esterification and/or amidificati

Assignees

• Coatex Sas

Inventors

• Suau Jean-Marc
• Platel David
• Champagne Clementine
• Matter Yves

Classifications

• B29C48/40

  using two or more parallel screws {or at least two parallel non-intermeshing screws}, e.g. twin screw extruders · CPC title

• B29C48/405

  Intermeshing co-rotating screws · CPC title

• C04B24/2647

  containing polyether side chains · CPC title

• B29C48/402

  the screws having intermeshing parts · CPC title

• B29B7/38

  rotary (B29B7/52 takes precedence) · CPC title