Cyanoacrylate compositions

Patent metadata

Field	Value
Publication number	US-10947418-B2
Application number	US-201815972944-A
Country	US
Kind code	B2
Filing date	May 7, 2018
Priority date	Nov 6, 2015
Publication date	Mar 16, 2021
Grant date	Mar 16, 2021

Abstract

Cyanoacrylate compositions that include, in addition to an allyl-2-cyanoacrylate, a rubber toughening component and a component functionalized with at least two blocked hydroxyl groups are provided.

First claim

What is claimed is:

1. A cyanoacrylate composition, comprising:
(a) allyl-2-cyanoacrylate,
(b) a rubber toughening agent comprised of (i) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (ii) dipolymers of ethylene and methyl acrylate, and combinations of (i) and (ii), and
(c) a component represented by:

wherein A is a C 4 to C 30 aliphatic chain which can optionally comprise heteroatoms selected from the group consisting of O, N and S, and wherein said chain is optionally substituted with one or more acrylate and/or methacrylate functional groups, and/or one or more C 1 -C 10 alkyl groups; and wherein R 1 and R 2 are the same or different and are each optionally selected from the group consisting of H and C 1 to C 6 alkyl.

2. The composition according to claim 1 , further comprising a filler.

3. The composition according to claim 2 , wherein the filler is selected from the group consisting of carbon black, silica and combinations thereof.

4. The composition according to claim 1 , further comprising an acidic stabilizer and a free radical inhibitor.

5. The composition of claim 1 , wherein the rubber toughening agent is present in an amount from 1.5% to 20% by weight.

6. The composition according to claim 1 , further comprising the cyanoacrylate component having the structure H 2 C═C(CN)—COOR, wherein R is selected from the group consisting of C 1-15 alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, and haloalkyl groups.

7. The composition according to claim 6 , wherein the cyanoacrylate component comprises ethyl-2-cyanoacrylate.

8. The composition according to claim 1 , further comprising an accelerator component selected from the group consisting of calixarene, oxacalixarene, silacrown, cyclodextrin, crown ether, poly(ethyleneglycol) di(meth)acrylate, ethoxylated hydric compound, and combinations thereof.

9. The composition according to claim 8 , wherein the calixarene is tetrabutyl tetra[2-ethoxy-2-oxoethoxy]calix-4-arene.

10. The composition according to claim 8 , wherein the crown ether is selected from the group consisting of 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5-dibenzo-24-crown-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclohexyl-12-crown-4, 1,2-decalyl-15-crown-5, 1,2-naphtho-15-crown-5, 3,4,5-naphtyl-16-crown-5, 1,2-methyl-benzo-18-crown-6, 1,2-methylbenzo-5, 6-methylbenzo-18-crown-6, 1,2-t-butyl-18-crown-6, 1,2-vinylbenzo-15-crown-5, 1,2-vinylbenzo-18-crown-6, 1,2-t-butyl-cyclohexyl-18-crown-6, asym-dibenzo-22-crown-6, and 1,2-benzo-1,4-benzo-5-oxygen-20-crown-7 and combinations thereof.

11. The composition according to claim 8 , wherein the poly(ethyleneglycol) di(meth)acrylate is within the following structure:

wherein n is greater than 3.

12. The composition according to claim 1 , further comprising additives selected from the group consisting of shock resistant additives, thixotropy conferring agents, thickeners, dyes, thermal degradation resistance enhancers, and combinations thereof.

13. The composition according to claim 12 , wherein the shock resistant additive is citric acid.

14. The composition according to claim 1 , wherein the component (c) is hexane diol diacrylate.

15. The composition according to claim 1 , further comprising at least one additive selected from the group consisting of: 2-sulfobenzoic acid anhydride, triethylene glycol di(para-toluene sulfonate), trifluoroethyl para-toluene sulfonate, dimethyl dioxolen-4-ylmethyl para-toluene sulfonate, para-toluene sulfonic anhydride, methane sulfonic anhydride, 1,3 propylene sulfite, dioxathiolene dioxide, 1,8-naphthosultone, sultone 1,3-propane, sultone 1,4-butene, allyl phenyl sulfone, 4-fluorophenyl sulfone, dibenzothiophene sulfone, bis(4-fluorophenyl) sulfone, ethyl p-toluenesulfonate, trifluoromethanesulfonic anhydride, ethylene sulphite and tetrafluoroisophthalonitrile and combinations thereof.

16. The composition according to claim 15 , wherein the additive is selected from the group consisting of 1,8-naphthosultone and ethylene sulphite and tetrafluoroisophthalonitrile.

17. The composition according to claim 15 wherein the thermal resistance conferring agent is a mixture of 1,8-naphthosultone and ethylene sulphite.

18. The composition according to claim 1 further comprising a maleimide component.

19. The composition according to claim 18 , wherein the maleimide component has one of the following structures:

R 6 and R 7 are independently selected from C 1 -C 50 alkyl, and C 4 -C 20 aryl, wherein R 6 and R 7 are each independently optionally substituted with one or more of nitro, hydroxyl, halogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 7 -C 20 aralkyl and C 7 -C 20 alkaryl; and R 8 and R 9 are independently selected from H, C 1 -C 50 alkyl, and C 1 -C 50 aryl, or together R 8 and R 9 may form a ring comprising from 5 to 20 carbon atoms.

20. The composition according to claim 19 , wherein the maleimide component is selected from the group consisting of:

21. A method of bonding together two substrates, comprising the steps of:
applying the cyanoacrylate composition according to claim 1 , to at least one of the substrates and
mating together the substrates to permit an adhesive bond to form from the cyanoacrylate composition between the mated substrates.

22. A method of preparing the cyanoacrylate composition according to claim 1 , comprising the steps of:
providing allyl-2-cyanoacrylate component, a rubber toughening agent comprised of (a) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (b) dipolymers of ethylene and methyl acrylate, and combinations of (a) and (b), and a component represented by:

wherein A is a C 4 to C 30 aliphatic chain which can optionally comprise heteroatoms selected from the group consisting of O, N and S, and wherein said chain is optionally substituted with one or more acrylate and/or methacrylate functional groups, and/or one or more C 1 -C 10 alkyl groups; and wherein R 1 and R 2 are the same or different and are each optionally selected from the group consisting of H and C 1 to C 6 alkyl, and
mixing to form the cyanoacrylate composition.

Assignees

• Henkel IP & Holding GmbH

Inventors

• Tully Raymond
• Barnes Rory
• Loane Mark
• Lambert Robert
• Ollagnier Cecile

Classifications

• C08F222/322

  Alpha-cyano-acrylic acid ethyl ester, e.g. ethyl-2-cyanoacrylate · CPC title

• C08F222/323

  Alpha-cyano-acrylic acid propyl ester · CPC title

• C08K5/103

  with polyalcohols · CPC title

• C09J11/04

  inorganic · CPC title

• B32B37/12

  characterised by using adhesives · CPC title