Method for manufacturing polyalkoxylated polymers

Patent metadata

Field	Value
Publication number	US-10968312-B2
Application number	US-201716319192-A
Country	US
Kind code	B2
Filing date	Jul 19, 2017
Priority date	Jul 20, 2016
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

The present invention relates to a method for the manufacture of polyalkoxylated polymers.

First claim

The invention claimed is:

1. A process for the manufacture of an alkoxylated derivative of a hydrogenated or (per)halogenated polymer comprising at least one —OH group [polymer (P ALK-OH )], said process comprising the steps of:
(a) contacting at least one pre-catalyst C complying with formula (1)
E(Q) t   (1)

wherein
E is an element selected from IV-group metals, post-transition metals and silicon,
Q is chlorine, bromine, iodine or an optionally fluorinated alkoxy or aryloxy group, and

t is an integer corresponding to the valence of E;
with
(a-i) at least one polymer (P OH ), wherein polymer (P OH ) is a hydrogenated or (per)halogenated polymer comprising at least one —OH group,
thus providing a mixture (M a-1 ) comprising said polymer P OH and a product (C-P OH ) obtained by the reaction between said pre-catalyst C and said polymer (P OH ), or
(a-ii) at least one compound (I), wherein compound (I) is a source of iodine, thus providing a mixture (M a-2 ) comprising said pre-catalyst C and said compound (I);
(b) contacting said mixture (M a-1 ) with at least one compound (I), wherein compound (I) is a source of iodine or
contacting said mixture (M a-2 ) with at least one polymer (P OH ),
thus obtaining mixture (M b ) comprising said polymer (P OH ), said product (C-P OH ) and said compound (I);
(c) contacting said mixture (M b ) with at least one alkylene oxide,
thus obtaining polymer (P ALK-OH ), optionally in admixture [mixture (M c )] with said polymer (P OH ), said product (C-P OH ) and/or said compound (I).

2. The process according to claim 1 , wherein E is an element selected from the group consisting of IV-group metals selected from titanium and zirconium; post-transitional metals selected from gallium, indium, tin and aluminium; and silicon.

3. The process according to claim 1 , wherein Q is an optionally fluorinated alkoxy or aryloxy group.

4. The process according to claim 1 , wherein said pre-catalyst C is selected from the group consisting of: titanium(IV) isopropoxide, titanium(IV) propoxide, titanium(IV) tert-butoxide, titanium(IV) methoxide, zirconium(IV) propoxide, aluminium isopropoxide, tin(IV) isopropoxide, tetraethyl orthosilicate, indium alkoxide and gallium alkoxide.

5. The process according to claim 1 , wherein said pre-catalyst C is used in an amount in the range from 0.01 to 10% expressed as moles of pre-catalyst C per number of equivalents of —OH groups in polymer (P OH ).

6. The process according to claim 1 , wherein said compound (I) is selected from the group consisting of: alkali metal or alkaline-earth metal iodides; ammonium and alkyl-ammonium iodides; elemental iodine; and combinations thereof.

7. The process according to claim 1 , wherein said compound (I) is used in an amount in the range from 0.01 to 8% expressed as moles of the source of iodine per number of equivalents of —OH groups in polymer (P OH ).

8. The process according to claim 1 , wherein said hydrogenated polymer (P OH ) is selected from the group consisting of polymers of formula Rx-OH, wherein R H is a linear or branched alkyl chain comprising from 3 to 12 carbon atoms.

9. The process according to claim 1 , wherein said (per)halogenated polymer (P OH ) is selected from the group consisting of:
polymers complying with general formula R FH —CF 2 CH 2 CH 2 OH wherein R FH is a linear or branched alkyl chain comprising from 1 to 12 carbon atoms; and
(per)fluoropolyether polymers (P OH-PFPE ) comprising a partially or fully fluorinated, straight or branched, polyoxyalkylene chain (R f ) having at least two chain ends, wherein at least one chain end comprises at least one group of formula —CF 2 CH 2 O— and at least one hydroxy group.

10. The process according to claim 9 , wherein said polymer (P OH-PFPE ) complies with formula (I):
A-O—(R f )—(CFX*) z1 -D*-O—(R a ) z3 —H  (I)

wherein
A is linear or branched (per)fluoroalkyl chain comprising from 1 to 6 carbon atoms or a group of formula H—(R a ) z4 —O-D-(CFX # ) z2 ;
z1 and z2, equal or different from each other, are equal to or higher than 1;
z3 and z4, equal or different from each other, are 0 or 1;
each of R a , equal to or different from each other, is a group of formula —[CH 2 CH(J)O] na [CH(J)CH2O] na′ —, wherein each of J is independently selected from hydrogen atom, straight or branched alkyl chain, or aryl group, and each of na and na′ is independently zero or an integer up to 15, with the proviso that na+na′ is from 1 to 15; X # and X*, equal or different from each other, are F or —CF 3 ,
provided that when z1 and/or z2 are higher than 1, X # and X* are —F;
D and D*, equal or different from each other, are an alkylene chain comprising from 1 to 6 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms;
(R f ) comprises repeating units R o , said repeating units being independently selected from the group consisting of:
(i) —CFXO—, wherein X is F or CF 3 ;
(ii) —CFXCFXO—, wherein X, equal or different at each occurrence, is F or CF 3 , with the proviso that at least one of X is —F;
(iii) —CF 2 CF 2 CW 2 O—, wherein each of W, equal or different from each other, are F, Cl, or H;
(iv) —CF 2 CF 2 CF 2 CF 2 O—;
(v) —(CF2) j -CFZ—O— wherein j is an integer from 0 to 3 and Z is a group of general formula
—O—R (f-a) -T, wherein R (f-a) is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen from: —CFXO—, —CF 2 CFXO—, —CF 2 CF 2 CF 2 O—, and —CF 2 CF 2 CF 2 CF 2 O—, with each of X being independently F or CF 3 and T being a C 1 -C 3 perfluoroalkyl group.

11. The process according to claim 10 , wherein said polymer (P OH-PFPE ) complies with formula (I-A) here below:
A-O—(R f )—CF 2 CH 2 O—(R a ) z3 —H  (I-A)

wherein:
R f comprises repeating units R o , said repeating units being independently selected from the group consisting of:
(i) —CFXO—, wherein X is F or CF 3 ;
(ii) —CFXCFXO—, wherein X, equal or different at each occurrence, is F or CF 3 , with the proviso that at least one of X is —F;
(iii) —CF 2 CF 2 CW 2 O—, wherein each of W, equal or different from each other, are F, Cl, or H;
(iv) —CF 2 CF 2 CF 2 CF 2 O—;
(v) —(CF 2 ) j —CFZ—O— wherein j is an integer from 0 to 3 and Z is a group of general formula
—O—R (f-a) -T, wherein R (f-a) is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen from: —CFXO—, —CF 2 CFXO—, —CF 2 CF 2 CF 2 O—, and —CF 2 CF 2 CF 2 CF 2 O—, with each of X being independently F or CF 3 and T being a C 1 -C 3 perfluoroalkyl group;

A is —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF 2 Cl, —CF 2 CF 2 Cl, —C 3 F 6 Cl or a group of formula —CF 2 CH 2 O—(R a ) z4 —H;
z3 and z4, equal or different from each other, are 0 or 1;
each of (R a ), equal or different from each other, is a group of formula
—[CH 2 CH(J)O] na [CH(J)CH 2 O] na′ —, wherein each of J is independently hydrogen atom or methyl, and each of na and na′ is independently zero or an integer from 1 to 7, with the proviso that na+na′ is from 1 to 7.

12. The process according to claim 10 , wherein said polymer (P OH-PFPE ) complies with formula (1-B):
A-O—(R f )—CF2CH 2 —OH  (1-B)

wherein
R f comprises repeating units R o , said repeating units being independently selected from the group consisting of:
(i) —CFXO—, wherein X is F or CF 3 ;
(ii) —CFXCFXO—, wherein X, equal or different at each occurrence, is F or CF 3 , with the proviso that at least one of X is —F;
(iii) —CF 2 CF 2 CW 2 O—, wherein each of W, equal or different from each other, are F, Cl, or H;
(iv

Assignees

• Solvay Specialty Polymers It

Inventors

• Guarda Pier Antonio
• Spataro Gianfranco

Classifications

• C08G65/007 Primary

  containing fluorine · CPC title

• C08G65/2609

  containing aliphatic hydroxyl groups · CPC title

• C08G65/331

  containing oxygen {(cyclic ether compounds C08G65/26)} · CPC title

• C08G65/266

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

• C08L71/02

  Polyalkylene oxides · CPC title