Olefin-acrylate copolymers with pendant hydroxyl functionality and use thereof

Patent metadata

Field	Value
Publication number	US-11078313-B2
Application number	US-201816021883-A
Country	US
Kind code	B2
Filing date	Jun 28, 2018
Priority date	Feb 11, 2016
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

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.

First claim

We 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.

2. 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.

3. 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.

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

5. 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.

6. 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.

7. 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.

8. An adhesive comprising the copolymer of claim 1 .

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

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.

11. 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.

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

13. 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.

14. 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.

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.

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

Assignees

• Henkel IP & Holding GmbH

Inventors

• Sridhar Laxmisha
• Shah Smita
• Woods John G
• Jacobine Anthony F

Classifications

• C08F220/44

  Acrylonitrile · CPC title

• B32B7/12

  using interposed adhesives or interposed materials with bonding properties · CPC title

• C08F216/04

  Acyclic compounds · CPC title

• C08F220/14

  Methyl esters {, e.g. methyl (meth)acrylate} · CPC title

• C08F210/10

  Isobutene · CPC title