MOISTURE CURABLE ORGANOPOLYSILOXANE COMPOSITION

• US 20150005443A1
• Filed: 12/21/2012
• Published: 01/01/2015
• Est. Priority Date: 12/29/2011
• Status: Active Grant

• Current Assignee: Momentive Performance Materials Incorporated
• Original Assignee: Momentive Performance Materials Incorporated
• Inventors: Byrne, Christopher
• Granted Patent: US 9,527,959 B2
• Time in Patent Office: Days
• US Class Current: 524/570
• CPC Class Codes: B01J 2231/14 Other (co) polymerisation, e.g. of lactides or epoxides
• CPC Class Codes: B01J 2531/54 Bismuth
• CPC Class Codes: B01J 31/0225 comprising sulfonic acid groups or the corresponding salts
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08G 18/837 by silicon containing compounds
• CPC Class Codes: C08G 63/914 derived from polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08G 64/42 Chemical after-treatment
• CPC Class Codes: C08G 65/00 Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
• CPC Class Codes: C08G 77/06 Preparatory processes C08G77/045 takes precedence
• CPC Class Codes: C08G 77/08 characterised by the catalysts used
• CPC Class Codes: C08G 77/44 containing only polysiloxane sequences
• CPC Class Codes: C08L 83/10 Block- or graft-copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00
• CPC Class Codes: C09D 123/26 modified by chemical after-treatment
• CPC Class Codes: C09D 167/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C09D167/06 takes precedence
• CPC Class Codes: C09D 167/025 containing polyether sequences
• CPC Class Codes: C09D 169/00 Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
• CPC Class Codes: C09D 171/00 Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain based on polyacetals C09D159/00; based on epoxy resins C09D163/00; based on polythioether-ethers C09D181/02; based on polyethersulfones C09D181/06; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: C09J 201/10 containing hydrolysable silane groups
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

The present invention provides curable compositions comprising non-tin metal catalysts that accelerate the condensation curing of moisture-curable silicones/non-silicones. In particular, the present invention provides bismuth(III) sulfonate complexes that are particularly suitable as replacements for organotin in sealant and RTV formulations. In one embodiment, the present invention provides bismuth (III) camphorsulfonate and bismuth(III) methanesulfonate complexes. Further, these bismuth(III) sulfonate complexes are comparable or superior to organotin such as DBTDL, exhibit certain behavior in the presence of components that allow for tuning or adjusting the cure characteristics of the present compositions, and provide good adhesion and storage stability.

Claims

1. A composition for forming a cured polymer composition comprising:

(A) a polymer having at least a reactive silyl group;

(B) a crosslinker or chain extender chosen from an alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, an enoxysilane, an enoxysiloxane, an aminosilane, an aminosiloxane, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alklarylaminosiloxane, an alkoxycarbamatosilane, an alkoxycarbamatosiloxane, and combinations of two or more thereof; and

(C) a condensation catalyst comprising a bismuth(III) sulfonate complex of the formula (1);

Bi(O₃SR⁹)_r(Q)_3-r 

 

(1)

where R⁹ is chosen from a linear alkyl, a branched alkyl, a cycloalkyl, a heteroaryl, an aralkyl, a branched aralkyl, a heteroalkyl, a heterocycloalkyl, a heteroaralkyl, an aryl, or a combination of two or more thereof, Q is an anionic ligand, and r is 1 to 3.

2. The composition of claim 1, wherein at least one (O₃SR⁹) group comprises a R⁹ chosen from methyl or (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl.

3. The composition of claim 1, wherein r is 3.

4. The composition of claim 1, wherein r is 3 and R⁹ is methyl.

5. The composition of claim 1, wherein r is 3 and R⁹ is (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl.

6. The composition of claim 1, comprising from about 0.001 to about 7 parts per weight of catalyst component (C) per 100 parts per weight of the polymer (A).

7. The composition of claim 1 comprising from about 0.01 to about 7 parts per weight catalyst (C) per 100 parts per weight of the polymer (A).

8. The composition of claim 1 comprising from about 0.005 to about 0.05 wt. pt. of catalyst component (C) per 100 parts of component.

9. The polymer composition of claim 1, wherein the polymer (A) has the formula (2):

[R¹_aR²_3-aSi—

Z-]_n—

X—

Z—

SiR¹_aR²_3-a 

 

(2)

where X is chosen from a polyurethane;

a polyester;

a polyether;

a polycarbonate;

a polyolefin;

a polyesterether; and

a polyorganosiloxane having units of R₃SiO_1/2, R₂SiO, RSiO_3/2, and/or SiO₂;

n is 0 to 100;

a is 0 to 2;

R and R¹ can be identical or different at the same Si-atom and chosen from a C₁-C₁₀ alkyl;

a C₁-C₁₀ alkyl substituted with one or more of Cl, F, N, O or S;

a phenyl;

a C₇-C₁₆ alkylaryl;

a C₇-C₁₆ arylalkyl;

a C₂-C₄ polyalkylene ether;

or a combination of two or more thereof;

R² is chosen from OH, C₁-C₈ alkoxy, C₂-C₁₈ alkoxyalkyl, oximoalkyl, enoxyalkyl, aminoalkyl, carboxyalkyl, amidoalkyl, amidoaryl, carbamatoalkyl, or a combination of two or more thereof; and

Z is a bond, a divalent unit selected from the group of a C₁-C₈ alkylene, or O.

10. The composition of claim 1, wherein the crosslinker component (B) is chosen from tetraethylorthosilicate (TEOS);

methyltrimethoxysilane (MTMS);

methyltriethoxysilane;

vinyltrimethoxysilane;

vinyltriethoxysilane;

methylphenyldimethoxysilane;

3,3,3-trifluoropropyltrimethoxysilane;

methyltriacetoxysilane;

vinyltriacetoxysilane;

ethyltriacetoxysilane;

di-butoxydiacetoxysilane;

phenyltripropionoxysilane;

methyltris(methylethylketoximo)silane;

vinyltris(methylethylketoximo)silane;

3,3,3-trifluoropropyltris(methylethylketoximo)silane;

methyltris(isopropenoxy)silane;

vinyltris(isopropenoxy)silane;

ethylpolysilicate;

dimethyltetraacetoxydisiloxane;

tetra-n-propylorthosilicate;

methyldimethoxy(ethylmethylketoximo)silane;

methylmethoxybis(ethylmethylketoximo)silane;

methyldimethoxy(acetaldoximo)silane;

methyldimethoxy(N-methylcarbamato)silane;

ethyldimethoxy(N-methylcarbamato)silane;

methyldimethoxyisopropenoxysilane;

trimethoxyisopropenoxysilane;

methyltriisopropenoxysilane;

methyldimethoxy(but-2-en-2-oxy)silane;

methyldimethoxy(1-phenylethenoxy)silane;

methyldimethoxy-2-(1-carboethoxypropenoxy)silane;

methylmethoxydi(N-methylamino)silane;

vinyldimethoxy(methylamino)silane;

tetra-N,N-diethylaminosilane;

methyldimethoxy(methylamino)silane;

methyltri(cyclohexylamino)silane;

methyldimethoxy(ethylamino)silane;

dimethyldi(N,N-dimethylamino)silane;

methyldimethoxy(isopropylamino)silane;

dimethyldi(N,N-diethylamino)silane;

ethyldimethoxy(N-ethylpropionamido)silane;

methyldimethoxy(N-methylacetamido)silane;

methyltris(N-methylacetamido)silane;

ethyldimethoxy(N-methylacetamido)silane;

methyltris(N-methylbenzamido)silane;

methylmethoxybis(N-methylacetamido)silane;

methyldimethoxy(caprolactamo)silane;

trimethoxy(N-methylacetamido)silane;

methyldimethoxy(ethylacetimidato)silane;

methyldimethoxy(propylacetimidato)silane;

methyldimethoxy(N,N′

,N′

-trimethylureido)silane;

methyldimethoxy(N-allyl-N′

,N′

-dimethylureido)silane;

methyldimethoxy(N-phenyl-N′

,N′

-dimethylureido)silane;

methyldimethoxyisocyanatosilane;

dimethoxydiisocyanatosilane;

methyldimethoxyisothiocyanatosilane;

methylmethoxydiisothiocyanatosilane, the condensates thereof, or a combination of two or more thereof.

11. The composition of claim 1, wherein the adhesion promoter component (D) is chosen from an (aminoalkyl)trialkoxysilane, an (aminoalkyl)alkyldialkoxysilane, a bis(trialkoxysilylalkyl)amine, a tris(trialkoxysilylalkyl)amine, a tris(trialkoxysilylalkyl)cyanurate, a tris(trialkoxysilylalkyl)isocyanurate, an (epoxyalkyl)alkyldialkoxysilane, an (epoxyalkyl)trialkoxysilane, or a combination of two or more thereof.

12. The polymer composition of claim 1 wherein the polymer component (A) has the formula (4):

R²_3-aR¹_aSi—

Z—

[R₂SiO]_x[R¹₂SiO]_y—

Z—

SiR¹_3-a 

 

(4)

where x is 0 to 10000;

y is 0 to 1000;

a is 0 to 2;

R is methyl;

R¹ is chosen from a C₁-C₁₀ alkyl;

a C₁-C₁₀ alkyl substituted with one or more of Cl, F, N, O, or S;

a phenyl;

a C₇-C₁₆ alkylaryl;

a C₇-C₁₆ arylalkyl;

a C₂-C₄ polyalkylene ether;

or a combination of two or more thereof, and other siloxane units may be present in amounts less than 10 mol. % preferably methyl, vinyl, phenyl;

R² is chosen from OH, a C₁-C₈ alkoxy, a C₂-C₁₈ alkoxyalkyl, an oximoalkyl, an oximoaryl, an enoxyalkyl, an enoxyaryl, an aminoalkyl, an aminoaryl, a carboxyalkyl, a carboxyaryl, an amidoalkyl, an amidoaryl, a carbamatoalkyl, a carbamatoaryl, or a combination of two or more thereof; and

Z is —

O—

, a bond, or —

C₂H₄—

.

13. The composition of claim 1, wherein the catalyst system (C) is substantially free of tin and substantially free of fluorine.

14. The composition of claim 13, wherein the catalyst system comprises 10 wt. % or less of fluorine.

15. The composition of claim 13, wherein the catalyst system comprises 5 wt. % or less of fluorine.

16. The composition of claim 13, wherein the catalyst system comprises 1 wt. % or less of fluorine.

17. The composition of claim 13, wherein the catalyst system comprises 0.1 wt. % or less of fluorine.

18. The composition of claim 1, wherein catalyst (C) comprises a blend of metal catalyst complexes.

19. A cured polymer formed from the composition or method of claim 1.

20. The cured polymer of claim 19 in the form of an elastomeric seal, duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, or an impression material.

21. A composition for forming a cured polymer composition comprising:

(A) a polymer having at least a reactive silyl group, where the polymer is free of siloxane bonds;

(B) a crosslinker or chain extender chosen from an alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, an enoxysilane, an enoxysiloxane, an aminosilane, an aminosiloxane, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alklarylaminosiloxane, an alkoxycarbamatosilane, an alkoxycarbamatosiloxane, the condensates thereof, and combinations of two or more thereof; and

(C) a condensation catalyst comprising a bismuth(III) sulfonate.

22. The composition of claim 21, comprising a bismuth(III) sulfonate complex of the formula (1):

Bi(O₃SR⁹)_r(Q)_3-r 

 

(1)

where R⁹ is chosen from a linear alkyl, a branched alkyl, a cycloalkyl, a heteroaryl, an aralkyl, a branched aralkyl, a heteroalkyl, a heterocycloalkyl, a heteroaralkyl, an aryl, or a combination of two or more thereof, Q is an anionic ligand, and r is 1 to 3.

23. The composition of claim 21 comprising from about 0.001 to about 7 parts per weight of catalyst component (C) per 100 parts per weight of the polymer (A).

24. The composition of claim 21 comprising from about 0.01 to about 7 parts per weight catalyst (C) per 100 parts per weight of the polymer (A).

25. The composition of claim 21 comprising from about 0.005 to about 0.05 wt. pt. of catalyst component (C) per 100 parts of component.

26. The composition of claim 21, wherein the polymer (A) is chosen from a silylated polyurethane (SPUR), a silylated polyester, a silylated polyether, a silylated polycarbonate, a silylated polyolefin, a silylated polyesterether, or a combination of two or more thereof.

27. The composition of claim 22, wherein R⁹ is chosen from an alkyl, an aryl, an aralkyl, a cycloalkyl, or a combination of two or more thereof;

and Q is chosen from an alkyl, an aryl, an aralkyl, a cycloalkyl, or a combination of two or more thereof.

28. The composition of claim 22, wherein R⁹ is chosen from an alkyl, a cycloalkyl, an aryl, an aralkyl, or a combination thereof, and Q is a hydroxyl.

29. The composition of claim 22, wherein R⁹ is chosen from an alkyl, a cycloalkyl, an aryl, an aralkyl, or a combination of two or more thereof.

30. The composition of claim 22, wherein at least one (O₃SR⁹) group comprises a R⁹ chosen from a spirocyclic compound, a fused cyclic compound, a bridged cyclic compound, or combination of two or more thereof.

31. The composition of claim 22, wherein at least one (O₃SR⁹) group comprises a R⁹ chosen from methyl or (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl.

32. A cured polymer formed from the composition or method of claim 21.

33. The cured polymer of claim 32 in the form of an elastomeric seal, duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, or an impression material.