Catalyst containing guanidine groups

Patent metadata

Field	Value
Publication number	US-10414875-B2
Application number	US-201615572331-A
Country	US
Kind code	B2
Filing date	May 10, 2016
Priority date	May 11, 2015
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

The use of a catalyst of the formula (I) for the crosslinking of a curable composition. The catalyst of the formula (I) contains at least one aliphatic guanidine group. It is substantially odorless and nonvolatile at room temperature and accelerates the crosslinking of curable compositions very efficiently, without impairing the storage stability thereof. It is particularly suitable for compositions based on polymers containing silane groups, where it has very good compatibility, as a result of which such compositions do not have a tendency to separation or migration or evaporation of the catalyst.

First claim

The invention claimed is:

1. A method of crosslinking a curable composition, comprising crosslinking the curable composition with a catalyst of formula (I)

formed from a reaction of a group L-Q p+r and p (HX-A-Z) groups
where
p is an integer from 1 to 6 and r is an integer from 0 to 5, where (p+r) is an integer from 1 to 6,
L is
a (p+r)-valent hydrocarbyl radical having a mean molecular weight in the range from 14 to 20,000 g/mol, optionally having heteroatoms,
or is a (p+r+1)-valent hydrocarbyl radical having 4 to 12 carbon atoms, which together with Q′ forms an optionally substituted 5- or 6-membered ring,
or is a covalent bond,
or is a hydrogen radical,
Q is a reactive group selected from epoxide, aziridine, carbonate, carboxylic anhydride, carboxylic acid, carboxylic ester, lactone, carbonyl chloride, ketone, aldehyde, 1,3-diketone, 1,3-keto ester, 1,3-keto amide, cyanate, thiocyanate, isocyanate, isothiocyanate, (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, maleate, maleamide, maleimide, fumarate, fumaramide, itaconate, itaconamide, crotonate and crotonamide,
Q′ is a di- or trivalent connecting unit residue formed from the reaction of Q with HX,
Y is N or X, where X is O or S or NR 3 where R 3 is a hydrogen radical or is an alkyl or cycloalkyl or aralkyl radical which has 1 to 8 carbon atoms and optionally contains a tertiary amino group or a guanidine group,
A is a divalent hydrocarbyl radical which has 2 to 30 carbon atoms and optionally contains unsaturated components and optionally ether oxygen or secondary or tertiary amine nitrogen,
where A together with R 3 may also be a trivalent hydrocarbyl radical which has 5 to 10 carbon atoms and optionally contains a tertiary amine nitrogen, and
Z is a guanidine group which is bonded via a nitrogen atom and does not contain any nitrogen atom which is bonded directly to an aromatic ring or is part of a heteroaromatic ring system.

2. The method as claimed in claim 1 , wherein A is either selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,3-pentylene, 1,1-dimethyl-1,2-ethyl, 1,5-pentylene, 2-methyl-1,5-pentylene, 1,6-hexylene, 2,2(4),4-trimethyl-1,6-hexamethylene, 1,8-octylene, 1,10-decylene, 1,12-dodecylene, (1,5,5-trimethylcyclohexan-1-yl)methane-1,3, 1,3-cyclohexylenebis(methylene), 1,4-cyclohexylene-bis(methylene), 1,3-phenylenebis(methylene), 2- and/or 4-methyl-1,3-cyclohexylene, N-methyl-4-aza-1,7-heptylene, 3-oxa-1,5-pentylene, 3,6-dioxa-1,8-octylene, 4,7-dioxa-1,10-decylene and a polyoxypropylene radical having a mean molecular weight in the range from about 200 to 250 g/mol, or A together with R 3 including the nitrogen atom of X is a radical selected from the group consisting of piperidin-4-ylmethyl, 2-(piperidin-4-yl)ethyl and 2-piperazinoethyl.

3. The method as claimed in claim 1 , wherein Z is

where
R 0 and R 1 are independently a hydrogen radical or an alkyl or cycloalkyl or aralkyl radical having 1 to 8 carbon atoms,
R 2 is a hydrogen radical or an alkyl, cycloalkyl or aralkyl radical which has 1 to 18 carbon atoms and optionally contains ether oxygen or tertiary amine nitrogen,
R 4 and R 5 are each independently a hydrogen radical or an alkyl, cycloalkyl or aralkyl radical which has 1 to 18 carbon atoms and optionally contains an ether oxygen or a tertiary amine nitrogen,
where
R 2 and R 0 together may also be an alkylene radical which has 3 to 6 carbon atoms and optionally contains an ether oxygen or a tertiary amine nitrogen,
R 4 and R 5 together may also be an alkylene radical which has 4 to 7 carbon atoms and optionally contains an ether oxygen or a tertiary amine nitrogen, and
R 2 and R 5 together may also be an alkylene radical having 2 to 12 carbon atoms.

4. The method as claimed in claim 3 , wherein Z is

5. The method as claimed in claim 1 , wherein Q′ is selected from the group consisting of

where
D is O or S,
W is O or NR 6 where R 6 is a hydrogen radical or is a monovalent hydrocarbyl radical having 1 to 8 carbon atoms,
E 0 is a hydrogen radical or is a methyl radical,
E 1 is a carboxyl-substituted alkylene, alkenediyl or phenylene radical having 2 to 8 carbon atoms,
E 2 is a hydroxyalkylene radical having 2 to 5 carbon atoms or is an O-bonded hydroxyalkyleneoxy radical having 2 or 3 carbon atoms,
E 3 is a hydrogen radical or is a monovalent hydrocarbyl radical which has 1 to 6 carbon atoms and optionally has heteroatoms in the form of ether, ester, amino or amide groups, or together with L is an optionally substituted 1,4-butylene or 1,5-pentylene radical,
E 4 is a hydrogen or methyl or alkoxycarbonylmethyl radical having 2 to 9 carbon atoms,
E 5 is an alkoxycarbonyl radical having 1 to 8 carbon atoms or is a methyl radical,
E 6 is a hydrogen radical or is an alkyl radical having 1 to 8 carbon atoms,
E 7 is a monovalent hydrocarbyl radical having 1 to 6 carbon atoms,
E 8 is a hydrogen radical or is a monovalent hydrocarbyl radical having 1 to 6 carbon atoms, and
d is 0 or 1.

6. The method as claimed in claim 1 , wherein p is 1 or 2 or 3 and r is 0.

7. The method as claimed in claim 1 , wherein the curable composition is an epoxy resin composition or a polyurethane composition or an epoxy resin/polyurethane composition or a cyanate ester resin composition or a composition containing silane groups.

8. The method as claimed in claim 1 , wherein the curable composition is a composition based on polymers containing silane groups.

9. The method as claimed in claim 8 , wherein the polymer containing silane groups is selected from the group consisting of polyorganosiloxanes having terminal silane groups and organic polymers containing silane groups.

10. A process for preparing a catalyst of formula (I):

formed from a reaction of a group L-Q p+r and p (HX-A-Z) groups
where
p is an integer from 1 to 6 and r is an integer from 0 to 5, where (p+r) is an integer from 1 to 6,
L is
a (p+r)-valent hydrocarbyl radical having a mean molecular weight in the range from 14 to 20′000 g/mol, optionally having heteroatoms,
or is a (p+r+1)-valent hydrocarbyl radical having 4 to 12 carbon atoms, which together with Q′ forms an optionally substituted 5- or 6-membered ring,
or is a covalent bond,
or is a hydrogen radical,
Q is a reactive group selected from epoxide, aziridine, carbonate, carboxylic anhydride, carboxylic acid, carboxylic ester, lactone, carbonyl chloride, ketone, aldehyde, 1,3-diketone, 1,3-keto ester, 1,3-keto amide, cyanate, thiocyanate, isocyanate, isothiocyanate, (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, maleate, maleamide, maleimide, fumarate, fumaramide, itaconate, itaconamide, crotonate and crotonamide,
Q′ is a di- or trivalent connecting unit residue formed from the reaction of Q with HX,
Y is N or X, where X is O or S or NR 3 where R 3 is a hydrogen radical or is an alkyl or cycloalkyl or aralkyl radical which has 1 to 8 carbon atoms and optionally contains a tertiary amino group or a guanidine group,
A is a divalent hydrocarbyl radical which has 2 to 30 carbon atoms and optionally contains unsaturated components and optionally ether oxygen or secondary or tertiary am

Assignees

• Sika Tech Ag

Inventors

• Cannas Rita
• Burckhardt Urs

Classifications

• C08K5/31

  Guanidine; Derivatives thereof · CPC title

• C09D183/12

  containing polyether sequences · CPC title

• C07C277/08 Primary

  of substituted guanidines · CPC title

• C08J2383/12

  containing polyether sequences · CPC title

• C07C279/04

  having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton · CPC title