Cyanoacrylate composition with hazardless stabilizer

Patent metadata

Field	Value
Publication number	US-11891496-B2
Application number	US-202217653578-A
Country	US
Kind code	B2
Filing date	Mar 4, 2022
Priority date	Mar 5, 2021
Publication date	Feb 6, 2024
Grant date	Feb 6, 2024

Abstract

The present invention relates to a curable cyanoacrylate composition comprising (i) at least one cyanoacrylate monomer, and (ii) at least one free radical stabilizer, wherein the free radical stabilizer is non-hazardous and shows good compatibility to the cyanoacrylate but does not impair the reactivity of the cyanoacrylate and its performance after curing.

First claim

What is claimed:

1. A curable cyanoacrylate composition comprising
(i) at least one cyanoacrylate monomer, and
(ii) at least one free radical stabilizer,
wherein the free radical stabilizer comprises one or more compound(s) of formula (I)

wherein (x) denotes either a double bond and R 3 is absent, or (x) denotes a single bond and R 3 is hydrogen, linear C 1 -C 8 alkyl, branched or cyclic C 3 -C 8 alkyl, linear C 1 -C 8 alkoxy, branched or cyclic C 3 -C 8 alkoxy, linear C 2 -C 8 alkenyl, or branched or cyclic C 3 -C 8 alkenyl;
R 1 is hydrogen, linear C 1 -C 8 alkyl, branched or cyclic C 3 -C 8 alkyl, linear C 1 -C 8 alkoxy, branched or cyclic C 3 -C 8 alkoxy, linear C 2 -C 8 alkenyl, branched or cyclic alkenyl, or a group —C(O)—O—R 2′ , wherein is linear C 1 -C 12 alkyl, branched or cyclic C 3 -C 12 alkyl, linear C 2 -C 12 alkenyl, or branched or cyclic C 3 -C 12 alkenyl, which linear C 1 -C 12 alkyl, branched or cyclic C 3 -C 12 alkyl, linear C 2 -C 12 alkenyl, or branched or cyclic C 3 -C 12 alkenyl optionally may be interrupted by one or more oxygen atoms;
R 2 is linear C 1 -C 12 alkyl, branched or cyclic C 3 -C 12 alkyl, linear C 2 -C 12 alkenyl, or branched or cyclic C 3 -C 12 alkenyl, which linear C 1 -C 12 alkyl, branched or cyclic C 3 -C 12 alkyl, linear C 2 -C 12 alkenyl, or branched or cyclic C 3 -C 12 alkenyl optionally, may be interrupted by one or more oxygen atoms;
R 4 is hydrogen, linear C 1 -C 8 alkyl, branched or cyclic C 3 -C 8 alkyl, linear C 1 -C 8 alkoxy, branched or cyclic C 3 -C 8 alkoxy, linear C 2 -C 8 alkenyl, or branched or cyclic C 3 -C 8 alkenyl; and
R 5 and R 5′ independently are hydrogen or a group —O—R 6 , wherein R 6 independently is hydrogen, linear C 1 -C 8 alkyl, branched or cyclic C 3 -C 8 alkyl, linear C 2 -C 8 alkenyl, or branched or cyclic C 3 -C 8 alkenyl,
wherein one of R 3 or R 4 together with R 1 may form a 5- to 18-membered saturated or unsaturated ring together with the carbon atoms to which they are attached, which is optionally interrupted by one or more oxygen atoms; or R 3 and R 4 may form a 5- to 18-membered saturated or unsaturated ring together with the carbon atom to which they are attached which is optionally interrupted by one or more oxygen atoms; or R 1 with R 3 and R 4 together with the carbon atoms to which they are attached may form a 5- to 12-membered saturated or unsaturated bicyclic ring, which is optionally interrupted by one or more oxygen atoms.

2. The curable cyanoacrylate composition according to claim 1 , wherein in the formula (I)
R 1 is a group —C(O)—O—R 2′ , wherein R 2′ is branched or cyclic C 3 -C 12 alkyl, which is optionally interrupted by one or two oxygen atoms;
R 2 is branched or cyclic C 3 -C 12 alkyl, which is optionally interrupted by one or two oxygen atoms;
R 3 is hydrogen, linear C 1 -C 4 alkyl, or branched C 3 -C 4 alkyl in case (x) denotes a single bond; and is absent when (x) denotes a double bond
R 4 is hydrogen, linear C 1 -C 4 alkyl, or branched C 3 -C 4 alkyl; and
R 5 and R 5′ independently are hydrogen or a group —O—R 6 , wherein R 6 independently is hydrogen, linear C 1 -C 4 alkyl, or branched C 3 -C 4 alkyl,
wherein R 3 and R 4 may form a 5- or 6-membered ring together with the carbon atom to which they are attached which is optionally interrupted by one or two oxygen atoms.

3. The curable cyanoacrylate composition according to claim 2 , wherein in the formula (I)
R 1 is a group —C(O)—O—R 2′ , wherein R 2′ is branched C 6 -C 10 alkyl;
R 2 is branched C 6 -C 10
R 3 is hydrogen or methyl in case (x) denotes a sing bond; and is absent when (x) denotes a double bond;
R 4 is hydrogen or methyl; and.
R 5 and independently are —O—CH 3 or —OCH 2 CH 3.

4. The curable cyanoacrylate composition according to claim 3 , wherein in the formula (I)
R 3 is hydrogen in case (x) denotes a covalent single bond; and is absent when (x) denotes a covalent double bond;
R 4 is hydrogen; and
R 5 and R 5′ are —O—CH 3.

5. The curable cyanoacrylate composition according to claim 1 , wherein the cyanoacrylate monomer is selected from at least one compound of the formula
R 7 HC═C(CN)—COOR 8 , wherein

R 7 is hydrogen, linear or branched C 1 -C 15 alkyl, linear or branched C 2 -C 15 alkenyl, linear or branched C 2 -C 15 alkenyl, linear or branched C 2 -C 15 alkoxy, cycloalkyl, aralkyl, allyl or aryl, wherein R 7 optionally may be further substituted with at least one halogen and/or at least one C 1 -C 15 alkoxy group; and
R 8 is hydrogen, linear or branched C 1 -C 15 is alkyl, linear or branched C 2 -C 15 alkenyl, linear or branched C 2 -C 15 alkynyl, linear or branched C 2 -C 15 alkoxy, cycloalkyl, aralkyl or aryl, wherein R 8 optionally may be further substituted with at least one halogen and/or at least one C 1 -C 15 alkoxy group; and
wherein the cyanoacrylate monomer is selected from the group consisting of methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylates, butyl cyanoacrylates, octyl cyanoacrylates, allyl cyanoacrylate, β-methoxyethyl cyanoacrylate, β-ethoxyethyl cyanoacrylate and combinations thereof.

6. The curable cyanoacrylate composition according to claim 1 , wherein the composition comprises the at least one free radical stabilizer in an amount of 0.1 to 5.0 weight %, based on the total weight of the curable cyanoacrylate composition.

7. The curable cyanoacrylate composition according to claim 1 , wherein the composition comprises the at least one cyanoacrylate monomer in an amount of 60.0 to 99.9 weight %, based on the total weight of the curable cyanoacrylate composition.

8. The curable cyanoacrylate composition according to claim 1 further comprising an anionic stabilizer, wherein the anionic stabilizer is a Lewis acid or a Brønsted acid and is selected from the group consisting of boron trifluoride (BF 3 ) and its complexes, sulfur dioxide (SO 2 ), or hydrogen fluoride (HF).

9. The curable cyanoacrylate composition according to claim 8 , wherein the composition comprises the anionic stabilizer in an amount of 0.0005 to 5.0 weight %, based on the total weight of the curable cyanoacrylate composition.

10. The curable cyanoacrylate composition according to claim 1 further comprising additional additives selected from the group consisting of thickeners, thixotroping agents, accelerators, retarders, plasticizers, adhesion promoters, pigments or dyes.

11. The curable cyanoacrylate composition according to claim 10 , wherein the additional additives are present in an amount of up to 60 weight %, based on the total weight of the curable cyanoacrylate composition.

12. The curable cyanoacrylate composition according to claim 1 further comprising a metallocene compound, and a photoinitiator.

13. The curable cyanoacrylate composition of claim 1 comprising:
from 88.0 to 99.8% by weight of the cyanoacrylate monomer, and
from 0.2 to 4.0% by weight of the free radical stabilizer.

14. The curable cyanoacrylate composition of claim 1 comprising:
from 97.0 to 99.5% by weight of the cyanoacrylate monomer, and
from 0.3 to 3.0% by weight of the free radical stabilizer.

15. The curable cyanoacrylate composition of claim 13 further comprising an anionic stabilizer.

16. An article comprising the curable cyanoacrylate composition of claim 1 .

17. The article of claim 16 selected from the group consisting of f

Assignees

• Fuller H B Co

Inventors

• Hoyer Lars P
• Wittwer Wolfgang

Classifications

• C08K5/134 Primary

  Phenols containing ester groups · CPC title

• C08F120/36

  containing oxygen in addition to the carboxy oxygen {, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate} · CPC title

• C08F122/32 Primary

  Alpha-cyano-acrylic acid; Esters thereof · CPC title

• C08F22/32 Primary

  Alpha-cyano-acrylic acid; Esters thereof · CPC title

• C09J4/00

  Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16} · CPC title