Titanium complexes as vulcanization catalysts

Patent metadata

Field	Value
Publication number	US-10273335-B2
Application number	US-201615371555-A
Country	US
Kind code	B2
Filing date	Dec 7, 2016
Priority date	Jun 26, 2014
Publication date	Apr 30, 2019
Grant date	Apr 30, 2019

Abstract

The invention relates to a curable composition comprising: a) at least one polymer having at least one silicon-containing group of formula —Si(R1)k(Y)3-k as defined herein; b) at least one titanium compound of formula Ti(L)n(NX2)m or Ti(R3)(L)3, where each X is independently a hydrogen atom, a hydrocarbon radical containing 1 to 20 C atoms, which may optionally contain one or more heteroatoms, in particular nitrogen atoms, or a silicon-containing organic group, or two X together with the nitrogen atom to which they are bound form a heterocyclic ring; each L is independently a hydrolyzable oxygen- or nitrogen-containing organic group, in particular an alkoxy group; R3 is a hydrocarbon radical containing 1 to 20 C atoms, which may optionally contain one or more heteroatoms, in particular silicon atoms; and m is 1, 2, 3, or 4 and and n is 0, 1, 2, or 3, where m+n=4; and c) optionally at least one compound which has a hydrolyzable silicon-containing group and a molecular weight in the range of 100 to 1000 g/mol, preparations containing these compositions and use thereof.

First claim

What is claimed is:

1. Curable composition comprising:
a) at least one polymer having at least one silicon-containing group of formula (1)
—Si(R 1 ) k (Y) 3-k   (1),

where R 1 is a hydrocarbon radical containing 1 to 20 C atoms or a triorganosiloxane group of formula —O—Si(R 2 ) 3 , where each R 2 is independently a hydrocarbon radical containing 1 to 20 C atoms;
each Y is independently a hydroxy group or a hydrolyzable group; and
k is 0, 1, or 2;
b) at least one titanium compound of formula (4)
Ti(OR 4 ) 3 (NX 2 )  (4),

where each R 4 is independently C 1-8 alkyl; each X is independently hydrogen, C 1-20 alkyl, or C 6-20 aryl, wherein the alkyl radical optionally contains one or more nitrogen atoms, or a silicon-containing organic group of formula —(CH 2 ) p —Si(Alk) q (OAlk) r , where p is an integer from 0 to 9, q and r in each case are 0, 1, 2, or 3, where q+r=3, and Alk is a C 1-4 alkyl group;
c) optionally at least one compound which has a hydrolyzable silicon-containing group and a molecular weight in the range of 100 to 1000 g/mol.

2. Curable composition according to claim 1 , characterized in that polymer a) has a polymer backbone that is selected from alkyd resins, (meth)acrylates and (meth)acrylamides and the salts thereof, phenolic resins, polyalkylenes, polyamides, polycarbonates, polyols, polyethers, polyesters, polyurethanes, vinyl polymers, siloxanes, and copolymers composed of at least two of the above-mentioned polymer classes.

3. Curable composition according to claim 1 , characterized in that in the titanium compound of formula (4), the ligand of formula (NX 2 ) is selected from diethylamido, bis(trimethylsilyl)amido,
3-(trimethoxysilyl)propyl-1-amido  (4a),

3-(triethoxysilyl)propyl-1-amido  (4b),

bis[(3-triethoxysily)propyl]amido  (4c),

bis[(3-trimethoxysilyl)propyl]amido (4d),
3-[diethoxy(methyl)silyl]propyl-1-amido  (4e),

2-(3-(trimethoxysilyl)propyl)amino)ethyl-1-amido  (4f),

2-((3-(triethoxysilyl)propyl)amino)ethyl-1-amido  (4g),

9-(trimethoxysilyl)-3,6-diazanonane-1-amido  (4h),

phenyl((trimethoxysilyl)methyl)amido  (4i),

phenyl(3-(trimethoxysilyl)propyl)amido  (4j),

and 2-((3-(dimethoxy(methyl)silyl)propyl)amino)ethyl-1-amido  (4k)

NH(CH 2 ) 3 Si(OMe) 3   (4a)

NH(CH 2 ) 3 Si(OEt) 3   (4b)

N[CH 2 ) 3 Si(OEt) 3 ] 2   (4c)

N[(CH 2 ) 3 Si(OMe) 3 ] 2   (4d)

NH(CH 2 ) 3 Si(OEt) 2 (Me)  (4e)

NH(CH 2 ) 2 NH(CH 2 ) 3 Si(OMe) 3   (4f)

NH(CH 2 ) 2 NH(CH 2 ) 3 Si(OEt) 3   (4g)

NH(CH 2 ) 2 NH(CH 2 ) 2 NH(CH 2 ) 3 Si(OMe) 3   (4h)

NPh(CH 2 )Si(OMe) 3   (4i)

NPh(CH 2 ) 3 Si(OMe) 3   (4j)

NH(CH 2 ) 2 NH(CH 2 ) 3 SiMe(OMe) 2   (4k).

4. Curable composition according to claim 1 , characterized in that the composition as compound c) contains an aminosilane selected from bis(trimethylsilyl)amine, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, bis[(3-triethoxysilyl)propyl]amine, bis[(3-trimethoxysily)propyl]amine, aminopropylmethyldiethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane, phenylaminomethyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, 3-(N-phenylamino)propyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3-(N,N-dimethylaminopropyl)aminopropylmethyldimethoxysilane, and combinations of two or more of the above-mentioned compounds.

5. The curable composition of claim 1 wherein Alk is methyl or ethyl.

6. The curable composition of claim 1 wherein the composition as compound c) contains an aminosilane.

7. Curable composition comprising:
a) at least one polymer having at least one silicon-containing group of formula (1)
—Si(R 1 ) k (Y) 3-k   (1),

where R 1 is a hydrocarbon radical containing 1 to 20 C atoms or a triorganosiloxane group of formula —O—Si(R 2 ) 3 , where each R 2 is independently a hydrocarbon radical containing 1 to 20 C atoms;
each Y is independently a hydroxy group or a hydrolyzable group; and
k is 0, 1, or 2;

b) at least one titanium compound of formula (5)
Ti(OR 4 ) 3 (R 5 )  (5),

where each R 4 is independently C 1-8 alkyl; and R 5 is C 1-10 alkyl, cyclopentadienyl, or aryl;

c) optionally at least one compound which has a hydrolyzable silicon-containing group and a molecular weight in the range of 100 to 1000 g/mol.

8. The curable composition of claim 7 wherein the composition as compound c) contains an aminosilane.

9. The curable composition of claim 7 wherein each Y is independently selected from an oxime group or an alkoxy group.

10. The curable composition of claim 7 wherein each R 4 is independently selected from ethyl, isopropyl or n-butyl.

11. The curable composition of claim 7 wherein R 5 is methyl.

12. Titanium compound of formula (6)
Ti(OR 4 ) 3 (NXX′)  (6),

where each R 4 is independently C 1-8 alkyl;
X is hydrogen, C 1-20 alkyl, or aryl, wherein the alkyl radical optionally contains one or more nitrogen atoms, or a silicon-containing organic group of formula —(CH 2 ) p —Si(Alk) q (OAlk) r , where p is an integer from 0 to 9, q is 0, 1, or 2, and r is 1, 2, or 3, where q+r=3, and Alk is a C 1-4 alkyl group; and
X′ is a silicon-containing organic group of formula —(CH 2 ) p —Si(Alk) q (OAlk) r , where p is an integer from 1 to 9, q is 0, 1, or 2, and r is 1, 2, or 3, where q+r=3, and Alk is a C 1-4 alkyl group.

13. A method of curing a silicon-containing polymer, comprising:
providing a curable silicon-containing polymer;
mixing the titanium compound according to claim 12 as catalyst with the curable silicon-containing polymer; and
curing the silicon-containing polymer by forming siloxane bonds.

14. The titanium compound of claim 12 , wherein each R 4 is independently selected from ethyl, isopropyl or n-butyl.

15. The titanium compound of claim 12 , wherein Alk is methyl or ethyl.

Assignees

• Henkel Ag & Co Kgaa

Inventors

• Helpenstein Klaus
• Klein Johann
• Gutacker Andrea
• Mejia Esteban
• Hillbrandt Steve
• Kragl Udo

Classifications

• C08G77/16

  to hydroxy groups · CPC title

• C07F7/28 Primary

  Titanium compounds · CPC title

• C08K5/56

  Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond · CPC title

• C08K5/0025

  Crosslinking or vulcanising agents; including accelerators · CPC title

• C08G77/18

  to alkoxy or aryloxy groups · CPC title