# US 11,078,313 B2 · Olefin-acrylate copolymers with pendant hydroxyl functionality and use thereof

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- Number: US 11,078,313 B2
- Document ID: US11078313B2
- Status: Granted
- Kind: B2
- Application number: 16/021,883
- Filed: 2018-06-28
- Published: 2018-10-25
- Granted: 2021-08-03
- Earliest claimed: 2016-02-11
- Assignees: Henkel IP & Holding GmbH
- Applicants: Henkel IP & Holding GmbH
- Inventors: Laxmisha Sridhar; Smita Shah; John G. Woods; Anthony F. Jacobine
- Web page: https://patentgrep.com/patent/US11078313B2

## CPC

- C08F 210/14: Monomers containing five or more carbon atoms
- B32B 7/12: using interposed adhesives or interposed materials with bonding properties
- C08F 220/20: of polyhydric alcohols or phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate}
- C09J 123/20: having four to nine carbon atoms
- C08F 210/02: Ethene
- C08F 210/06: Propene
- C08F 210/08: Butenes
- C08F 210/10: Isobutene
- C08F 216/04: Acyclic compounds
- C08F 216/08: Allyl alcohol
- C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate}
- C08F 220/16: of phenols or of alcohols containing two or more carbon atoms
- C08F 220/44: Acrylonitrile
- C08F 220/54: Amides {, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide}
- C08F 220/56: Acrylamide; Methacrylamide
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)

## Abstract

Copolymers prepared by a reaction of (1) an unactivated olefin, (2) an activated olefin, and (3) a hydroxyl functional activated olefin and/or a hydroxyl functional unactivated olefin are described. The copolymers have a backbone of polar vinyl monomers and non-polar alkene monomers, with pendant hydroxyl functional groups. The copolymers are well suited for optically clear, pressure sensitive, polyurethane and/or barrier adhesives.

## Claims

### Claim 1

A copolymer prepared by the reaction of:
(A) 10-89 mol % of an unactivated olefin;
(B) 10-89 mol % of an activated olefin; and
(C) 1-50 mol % of a hydroxyl functional unactivated olefin selected from the group consisting of allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 9-decen-1-ol, 10-undecen-1-ol, and mixtures thereof;
wherein the total mol % is 100 mol %;
wherein the copolymer comprises a plurality of pendant hydroxyl groups; and
wherein the weight average molecular weight (Mw) is from about 84,000 to about 2,000,000.

### Claim 2 (depends on 1)

The copolymer of claim 1, wherein the unactivated olefin is selected from the group consisting of an unsubstituted alkene, monosubstituted alkene, disubstituted alkene, and trisubstituted alkene.

### Claim 3 (depends on 1)

The copolymer of claim 1, wherein the unactivated olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 2-methyl-pentene, 3-methyl-1-butene, diisobutylene, diisobutylene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, dimethylpentene, vinylcyclohexane, cyclopropene, cyclobutene, cyclopentene, cyclohexane, norbornene, limonene, α-pinene, β-pinene, camphene, cis-cyclooctene and trans-cyclooctene.

### Claim 4 (depends on 3)

The copolymer of claim 3, wherein the unactivated olefin is 2-methylpentene, isobutylene or 1-octene.

### Claim 5 (depends on 1)

The copolymer of claim 1, wherein the activated olefin is selected from the group consisting of (meth)acrylate ester, acrylonitrile, (meth)acrylamide, maleimide, itaconimide, citroconimide, maleic anhydride, (meth)acrylate ester, maleate ester, fumarate ester, crotonates and cinnamates.

### Claim 6 (depends on 5)

The copolymer of claim 5, wherein the (meth)acrylate is methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isooctyl(meth)acrylate, glycidyl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, benzyl(meth)acrylate, 2-hydroxy(meth)acrylate, trimethoxybutyl(meth)acrylate, ethylcarbitol(meth)acrylate, phenoxyethyl(meth)acrylate, 2-hydroxy ethyl(meth)acrylate, trimethylolpropanetri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butyleneglycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethyleneglycol di(meth)acrylate and oligoester(meth)acrylate.

### Claim 7 (depends on 6)

The copolymer of claim 6, wherein the (meth)acrylate is methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, 2-ethylhexyl(meth) acrylate, isooctyl(meth)acrylate, glycidyl(meth)acrylate or cyclohexyl(meth)acrylate.

### Claim 8 (depends on 1)

An adhesive comprising the copolymer of claim 1.

### Claim 9 (depends on 8)

The adhesive of claim 8 further comprising a tackifier, plasticizer, filler, antioxidant, adhesion promoters, desiccants, UV stabilizers, preservatives, emollients, excipients, opacifiers or mixtures thereof.

### Claim 10

A method of forming a copolymer having a backbone of olefin-acrylate with pendant hydroxyl functionality comprising the steps of:
(1) pre-complexing a first amount of an activated olefin and a Lewis acid to form a pre-complex;
(2) adding the pre-complex to a solution of (i) an unactivated olefin, (ii) a second amount of the activated olefin, and (iii) a hydroxyl functional unactivated olefin in (iv) a solvent to form a mixture; and
(3) polymerizing the mixture in a temperature range of −78° C. to 100° C.;
wherein the first amount of the activated olefin is an equimolar amount of the activated olefin with the Lewis acid, and the second amount of the activated olefin is the rest of the molar amount of the activated olefin;
wherein the amount of Lewis acid ranges from about 1 to about 99 mol % of the activated olefin;
wherein the copolymer is the reaction product of:
(A) 10-89 mol % of an unactivated olefin;
(B) 10-89 mol % of an activated olefin; and
(C) 1-50 mol % of a hydroxyl functional unactivated olefin selected from the group consisting of allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 9-decen-1-ol, 10-undecen-1-ol, and mixtures thereof;
wherein the total mol % is 100 mol %;
wherein the copolymer comprises a plurality of pendant hydroxyl groups; and
wherein the weight average molecular weight (Mw) is from about 84,000 to about 2,000,000.

### Claim 11 (depends on 10)

The method of claim 10, wherein a coordinating solvent is added to the solution, wherein the coordinating solvent that has a heteroatom in the structure.

### Claim 12 (depends on 10)

The method of claim 10, wherein a radical initiator is added after step (2) (iii) and before step (3).

### Claim 13 (depends on 10)

The method of claim 10, wherein the unactivated olefin is selected from the group consisting of an unsubstituted alkene, monosubstituted alkene, disubstituted alkene, and trisubstituted alkene.

### Claim 14 (depends on 10)

The method of claim 10, wherein the activated olefin is selected from the group consisting of (meth)acrylate, acrylonitrile, (meth)acrylamide, maleimide, itaconimide, citroconimide, maleic anhydride, cyanoacrylate, maleate, and fumarate.

### Claim 15

A pressure sensitive hot melt adhesive comprising:
(i) a copolymer prepared by the reaction of:
(A) 10-89 mol % of an unactivated olefin;
(B) 10-89 mol % of an activated olefin; and
(C) 1-50 mol % of a hydroxyl functional unactivated olefin selected from the group consisting of allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 9-decen-1-ol, 10-undecen-1-ol, and mixtures thereof;
wherein the total mol % is 100 mol %;
wherein the copolymer comprises a plurality of pendant hydroxyl groups; and
wherein the weight average molecular weight (Mw) is from about 84,000 to about 2,000,000; and
(ii) optionally, tackifier, plasticizer, antioxidant, inorganic fillers, desiccants, and/or adhesion promoters;
wherein the pressure sensitive hot melt adhesive is optically clear.

### Claim 16 (depends on 15)

An article comprising the pressure sensitive hot melt adhesive of claim 15.