Process for preparing olefin-acrylate block copolymers by ATRP

Patent metadata

Field	Value
Publication number	US-12534562-B2
Application number	US-202117997480-A
Country	US
Kind code	B2
Filing date	Apr 29, 2021
Priority date	Apr 30, 2020
Publication date	Jan 27, 2026
Grant date	Jan 27, 2026

Abstract

The present disclosure relates to a process for preparing an olefin-acrylate block copolymer, the process comprising: a) performing atom transfer radical polymerization (ATRP) by combining ATRP materials comprising an acrylate monomer, an initiator having a radically transferrable atom or group, a transition metal compound, and a ligand, thereby forming a macroinitiator; and b) combining reaction materials comprising an alpha-substituted acrylate and the macroinitiator, thereby forming the olefin-acrylate block copolymer.

First claim

What is claimed is:

1. A process for preparing an olefin-acrylate block copolymer, the process comprising:
a) Performing atom transfer radical polymerization (ATRP), by combining ATRP material comprising an acrylate monomer with the formula (III), an initiator having a radically transferrable atom or group, a transition metal compound, and a ligand, thereby forming a macroinitiator; and
b) combining reaction materials comprising an alpha-substituted acrylate and the macroinitiator, thereby forming the olefin-acrylate block copolymer wherein:
the alpha-substituted acrylate has the formula (II)

wherein R is a polyolefinyl group and R1 independently is hydrogen or a C1-C30 hydrocarbyl group;
the acrylate monomer has the formula (III):

wherein R1 independently is hydrogen or a C1-C30 hydrocarbyl group;
each R2 independently is hydrogen or a methyl group;
the initiator has the formula (IV):

the macroinitiator has the formula (V):
polyacrylate-(X) y   (V);

the olefin-acrylate block copolymer has the formula (VI):

 wherein:
each R1 independently is hydrogen or a C1-C30 hydrocarbyl group;
each R2 independently is hydrogen or a methyl group;
each R independently is a polyolefinyl group;
m is from 1 to 50;
each y independently is from 1 to 100;
each X independently is selected from the group consisting of a halide, OR 10 , SR 14 , SeR 14 , —SCN (thiocyanate), OC(═O)R 14 , OP(═O)R 14 , OP(═O)(OR 14 ) 2 , OP(═O)OR 14 , O—N(R 14 ) 2 , and S—C(═S)N(R 14 ) 2 , where R 14 is aryl or a straight or branched C1-C20 alkyl group, or when an N(R 14 ) 2 group is present, the two R 14 groups may be joined to form a 5-, 6-, or 7-membered heterocyclic ring, and where R 10 is alkyl of from 1 to 20 carbon atoms, in which each of the hydrogen atoms may be independently replaced by halide;
R11, R12, and R13 are each independently selected from the group consisting of H, halide, C1-C20 alkyl, C3-C8 cycloalkyl, C(═Y)R5, C(═Y)NR 6 R 7 , COCl, OH, CN, C2-C20 alkenyl or alkynyl, oxiranyl, glycidyl, aryl, heterocyclyl, aralkyl, aralkylene (aryl-substituted alkenyl, and alkenyl is vinyl which may be substituted with one or two C1-C6 alkyl groups and/or halogen atoms), C1-C6 alkyl in which from 1 to all of the hydrogen atoms are replaced with halogen and C1-C6 alkyl substituted with from 1 to 3 substituents selected from the group consisting of C1-C4 alkoxy, aryl, heterocyclyl, C(═Y)R 6 , C(═Y)NR 6 R 7 , oxiranyl and glycidyl; such that no more than two of R11, R12 and R13 are H;
Y may be NR 8 or O;
R 5 is alkyl of from 1 to 20 carbon atoms, alkoxy of from 1 to 20 carbon atoms, aryloxy or heterocyclyloxy, R 6 and R 7 are independently H or alkyl of from 1 to 20 carbon atoms, or R 6 and R 7 may be joined together to form an alkylene group of from 2 to 5 carbon atoms, thus forming a 3- to 6-membered ring, and R 8 is H, straight or branched C1-C20 alkyl and aryl; and
“polyacrylate” represents the polyacrylate resulting from ATRP of the acrylate monomer.

2. The process of claim 1 , wherein the polyolefinyl group is an ethylene-based polymeryl group.

3. The process of claim 1 , wherein the polyolefinyl group is a propylene-based polymeryl group.

4. The process of claim 1 , wherein the polyolefinyl group is defined by properties of R—H, and wherein R—H has a number average molecular weight of greater than 365 g/mol.

5. The process of claim 1 , wherein each of steps a) and b) is performed at a temperature from 40° C. to 150° C.

6. The olefin acrylate block copolymer prepared by the process of claim 1 .

Assignees

• Dow Global Technologies Llc

Inventors

• Krasovskiy Arkady L
• Auyeung Evelyn
• Stubbert Bryan D
• Davis Anna V
• Hou Jianbo
• Cummins Clark H

Classifications

• C08F2438/01

  Atom Transfer Radical Polymerization [ATRP] or reverse ATRP · CPC title

• C08F293/005 Primary

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C08F220/12

  of monohydric alcohols or phenols · CPC title

• C08F220/1804

  C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate · CPC title

• C08F290/042

  Polymers of hydrocarbons as defined in group C08F10/00 · CPC title