Branched polymers, their preparation process, and uses therof

Patent metadata

Field	Value
Publication number	US-10087281-B2
Application number	US-201515518374-A
Country	US
Kind code	B2
Filing date	Oct 16, 2015
Priority date	Oct 16, 2014
Publication date	Oct 2, 2018
Grant date	Oct 2, 2018

Abstract

A polymer is provided having at least one repetitive unit represented by the following formula:

And, preferably at least one, preferably at least two, repetitive units represented by the following formula:

First claim

The invention claimed is:

1. A polymer comprising:
i) at least one repetitive unit (V) having the following formula (T):

and
ii) at least one repetitive unit(s) (U) having the following formula (D):

or
at least one repetitive unit(s) (Q) having the following formula (S):

or
at least one repetitive unit(s) (Q) having the following formula (S′):

wherein:
A 1 represents H or a linear or branched divalent alkyl group comprising from 1 to 20 carbon atoms;
A 4 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms;
A 2 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms;
A 3 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms;

R 1 , R′ 1 , R 2 and R 3 are or H;
i is 0, 1 or 2;
j is 0 or 1;

i being 0 when j is 1 and j being 0 when i is 1 or 2;
when A 1 is H and i is 0, then A 2 is a bond, and wherein:
in the unit (U) having the formula (S), only one of R 1 , R 2 and R 3 is H;
in the unit (U) having the formula (S′), one or two of R 1 , R′ 1 , R 2 and R 3 is H.

2. The polymer according to claim 1 , further comprising at least one repetitive unit (W) having the following formula (L):

wherein:
A 1 , A 2 , A 3 , A 4 , i and j are as defined in claim 1 ; and
R 1 , R 2 , R 3 and R 4 being

or H, three of R 1 , R 2 , R 3 and R 4 being H.

3. The polymer according to claim 1 , wherein the number-average molecular weight M n is comprised between 3 000 g/mol and 500 000 g/mol.

4. The polymer according to claim 1 , comprising at least three repetitive units (V) having the formula (T).

5. The polymer according to claim 1 , wherein the repetitive unit (U) has one of the following formulae (D1), (D2) or (D3):

wherein A 1 , A 2 , A 3 and A 4 are as defined in claim 1 .

6. The polymer according to claim 1 , wherein the repetitive unit (V) has the one of the following formulae (T1), (T2) or (T3):

wherein A 1 , A 2 , A 3 and A 4 are as defined in claim 1 .

7. The polymer according to claim 1 , comprising:
at least one repetitive unit (W) having the following formula (L1):

and/or
at least one repetitive unit (W) having the following formula (L2):

wherein A 1 , A 2 , A 3 and A 4 are as defined in claim 1 ;
or
at least one repetitive unit (W) having the following formula (L3):

and/or
at least one repetitive unit (W) having the following formula (L4):

and/or
at least one repetitive unit (W) having the following formula (L5):

wherein A 1 , A 2 , A 3 and A 4 are as defined in claim 1 ;
or
at least one repetitive unit (W) having the following formula (L6):

and/or
at least one repetitive unit (W) having the following formula (L7):

and/or
at least one repetitive unit (W) having the following formula (L8):

and/or
at least one repetitive unit (W) having the following formula (L9):

wherein A 1 , A 2 , A 3 and A 4 are as defined in claim 1 .

8. The polymer according to claim 1 , wherein:
A 1 represents H, i is 0, j is 0, A 2 represents a bond, and A 3 and A 4 represent a butylene radical; or
A 1 represents H, i is 1, j is 0, A 2 represents a pentylene radical, A 3 represents a propylene radical and A 4 represents a butylene radical; or
A 1 represents a hexyl group, i is 0, j is 0, A 2 represents an ethylene radical, A 3 represents a pentylene radical and A 4 represents a hexylene radical; or
A 1 represents a pentyl group, i is 2, j is 0, A 2 represents a methylene radical, A 3 represents a propylene radical and A 4 represents a butylene radical; or
A 1 represents a heptyl group, i is 0, j is 0, A 2 represents a methylene radical, A 3 represents a methylene radical and A 4 represents a hexylene radical; or
A 1 represents a hexyl group, i is 1, j is 0, A 2 represents a methylene radical, A 3 represents a methylene radical and A 4 represents a hexylene radical.

9. A process for preparing a polymer according to claim 1 , comprising a step of polymerization of at least one monomer of formula (IV):

wherein:
A 1 , A 2 , A 3 and A 4 are as defined in claim 1 ;
Y represents —OR a , R a being a linear or branched alkyl radical comprising from 1 to 20 carbon atoms or an aryl radical comprising from 6 to 22 carbon atoms;

said step being carried out in the presence of a catalyst selected from the group consisting of: NaOMe, Zn(OAc) 2 , Ti(OBu) 4 , Ti(OiPr) 4 , Sb 2 O 3 , stannous octanoate, dibutyltin oxide, 7-methyl-1,5,7-triazabicyclo(4.4.0)dec-5-ene, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene,
said process optionally comprising a step of recovering said polymer.

10. The process of claim 9 , wherein the catalyst is Zn(OAc) 2 , NaOMe or 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

11. The process according to claim 9 , wherein the amount of catalyst is comprised from 0.05% to 10% by weight relative to the weight of the monomer of formula (IV).

12. The process according to claim 9 , wherein the polymerization step is carried out by heating the monomer of formula (IV) as defined in claim 9 in the presence of the catalyst, at a temperature T1 comprised from 90° C. to 130° C. for 1 hour to 48 hours, then by heating further at a temperature T2 comprised from 90° C. to 180° C. for 1 hour to 48 hours.

13. A polymer susceptible to be obtained according to the process according to claim

Assignees

• Pivert
• Univ Bordeaux
• Institut Des Corps Gras Etudes Et Rech Techniques—Iterg
• Centre Nat Rech Scient
• Inst Polytechnique Bordeaux

Inventors

• Cramail Henri
• Grau Etienne
• Testud Blandine
• Taton Daniel
• Pintori Didier

Classifications

• C08G2261/1424

  containing ether groups, including alkoxy · CPC title

• C08G63/06 Primary

  derived from hydroxycarboxylic acids · CPC title

• C08G2261/1422

  containing OH groups · CPC title

• C08G2261/132

  branched or hyperbranched · CPC title

• C08L47/00

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers (C08L45/00 takes precedence; of conjugated diene rubbers C08L9/00 - C08L21/00) · CPC title