Moisture curable compositions

• US 9,663,621 B2
• Filed: 08/18/2014
• Issued: 05/30/2017
• Est. Priority Date: 08/23/2013
• Status: Expired due to Fees

• Current Assignee: Momentive Performance Materials Incorporated (Momentive Performance Materials Holdings LLC)
• Original Assignee: Momentive Performance Materials Incorporated (Momentive Performance Materials Holdings LLC)
• Inventors: Patel, Mihirkumar Maheshbhai, Dhanabalan, Anantharaman
• Primary Examiner(s): Loewe, Robert S
• Application Number:
  US14/913,769
• Publication Number:
  US 20160200875A1
• Time in Patent Office: 1,016 Days
• Field of Search: None
• CPC Class Codes: C07C 2603/68 Dicyclopentadienes; Hydrogenated dicyclopentadienes
• CPC Class Codes: C07C 277/00 Preparation of guanidine or its derivatives, i.e. compounds containing the group , the singly-bound nitrogen atoms not being part of nitro or nitroso groups
• CPC Class Codes: C07C 279/04 having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton
• CPC Class Codes: C07C 279/16 having nitrogen atoms of guanidine groups bound to carbon atoms of rings other than six-membered aromatic rings
• CPC Class Codes: C07F 7/0838 Compounds with one or more Si-O-Si sequences compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21
• CPC Class Codes: C08G 59/40 characterised by the curing agents used
• CPC Class Codes: C08G 77/08 characterised by the catalysts used
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• CPC Class Codes: C08G 77/388 containing nitrogen
• CPC Class Codes: C08G 77/442 containing vinyl polymer sequences
• CPC Class Codes: C08K 5/54 Silicon-containing compounds C08K5/0091 takes precedence
• CPC Class Codes: C08L 101/10 containing hydrolysable silane groups

Abstract

The present invention provides curable compositions comprising non-tin metal accelerators that accelerate the condensation curing of moisture-curable silicones/non-silicones. In particular, the present invention provides an accelerator comprising guanidine-containing compounds that are particularly suitable as replacements for organotin in sealant and RTV formulations. Further, the compositions employing a guanidine-containing compound is comparable or superior to organotin such as DBTDL, exhibits certain behavior in the presence of components that allow for tuning or adjusting the cure characteristics of the compositions, and provides good adhesion and storage stability.

Claims

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

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

(B) a crosslinker or chain extender; and

(C) a condensation accelerator comprising a guanidine-containing compound, wherein the guanidine-containing compound comprises a plurality of guanidine functional groups, the guanidine-containing compound being chosen from a compound of the formula (i) or (ii);

2. The composition of claim 1, wherein R⁹-R¹² are individually chosen from branched or straight chain C₁-C₃₀ alkyl radical, and R¹³ is chosen from a C₁-C₃₀ alkylene.

3. The composition of claim 1, wherein the guanidine-containing compound is of the formula:

4. The composition of claim 1, wherein R⁹-R¹² are independently chosen from a branched or straight chain C₁-C₃₀ alkyl radical, and R¹³ is chosen from an alkylene comprising a carbocycle.

5. The composition of claim 4, wherein the carbocycle comprises a bridging group, a fused ring, or a fused ring system with at least one ring in the fused ring system comprising a bridging group.

6. The composition of claim 1, wherein the guanidine-containing compound is of the formula:

7. The composition of claim 1, wherein R¹³ and R²⁰ are independently chosen from a siloxane derivative of the formula:

8. The composition of claim 1, wherein the guanidine-containing compound is of the formula:

9. The composition of claim 1 comprising from about 0.0001 to about 10 parts per weight of accelerator (C) per 100 parts per weight of the polymer (A).

10. The composition of claim 1 comprising from about 0.005 to about 0.05 wt. pt. of accelerator (C) per 100 parts of the polymer (A).

11. The composition of claim 1, wherein the accelerator (C) is substantially free of tin.

12. The composition of claim 1, wherein the accelerator (C) further comprises a blend of a metal accelerator, a salt of a metal accelerator, a carboxylic acid, an alkyl-sulfonic acid, an aryl sulfonic acid, an inorganic acid, an amine, a guanidine, an amidine, an inorganic base, or a combination of two or more thereof.

13. 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.

14. 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_aR²_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—

.

15. The composition of claim 1, wherein the polymer (A) is chosen from silylated polyurethane (SPUR), silylated polyester, silylated polyether, silylated polycarbonate, silylated polyolefins like polyethylene, polypropylene, silylated polyesterether and combinations of two or more thereof.

16. The composition of claim 1, wherein the crosslinker (B) is 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, a hydridosilane, a hydridosiloxane, and combinations of two or more thereof.

17. 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, a hydridosilane, a hydridosiloxane, or a combination of two or more thereof.

18. The composition of claim 1, wherein the composition is free of an adhesion promoter.

19. The composition of claim 1 comprising an adhesion promoter component (D).

20. The composition of claim 19, wherein the adhesion promoter 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.

21. The composition of claim 1 comprising a filler component (E).

22. The composition of claim 1 comprising at least one acidic compound (F) chosen from a phosphate ester, a phosphonate ester, a phosphonic acid, a phosphorous acid, a phosphite, a phosphonite ester, a sulfate, a sulfite, a pseudohalogenide, a branched C₄-C₂₅ alkyl carboxylic acid, or a combination of two or more thereof.

23. The composition of claim 1, wherein the composition is a two-part composition comprising:

(i) a first portion comprising the polymer component (A), optionally a filler component (E), and optionally an acidic compound (F); and

(ii) a second portion comprising the crosslinker (B), the accelerator (C), optionally an adhesion promoter (D), and the acidic compound (F), whereby (i) and (ii) are stored separately until applied for curing by mixing of the components (i) and (ii).

24. A cured polymer formed from the composition of claim 1.

25. The cured polymer of claim 24 in the form of an elastomeric seal, duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, or an impression material.

26. The cured polymer material of claim 24, wherein the polymer is formed by crosslinking via a condensation reaction and/or a dehydrogenative condensation reaction.

27. The composition of claim 1, wherein R⁹-R¹² and R¹⁴-R¹⁹ are independently chosen from a substituted or unsubstituted, branched or straight chain C₁-C₃₀ alkyl;

a substituted or unsubstituted, branched or straight chain C₂-C₁₈ alkenyl;

a substituted or unsubstituted, branched or straight chain C₂-C₁₈ alkynyl;

—

(OCH₂CH₂)_1-15OH;

—

(OC₃H₆)_1-15OH;

a substituted or unsubstituted, saturated or unsaturated, carbocycle or heterocycle;

or a substituted or unsubstituted aryl or heteroaryl.

28. The composition of claim 1, wherein R⁹-R¹² and R¹⁴-R¹⁹ are independently chosen from a substituted or unsubstituted, branched or straight chain C₁-C₉ alkyl;

a substituted or unsubstituted, branched or straight chain C₂-C₉ alkenyl;

a substituted or unsubstituted, branched or straight chain C₂-C₉ alkynyl;

substituted or unsubstituted, saturated or unsaturated, carbocycles or heterocycles;

or substituted or unsubstituted aryl or heteroaryl.

29. The composition of claim 1, wherein R⁹-R¹² and R¹⁴-R¹⁹ are independently chosen from substituted or unsubstituted, branched or straight chain C₁-C₅ alkyl;

substituted or unsubstituted, branched or straight chain C₂-C₅ alkenyl;

substituted or unsubstituted, branched or straight chain C₂-C₅ alkynyl;

substituted or unsubstituted, saturated or unsaturated, carbocycle or heterocycle selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, pyrrolidinyl, piperidyl, imidazolidinyl, pyrazolidinyl, pyrazolinyl, piperazinyl, morpholinyl, chromanyl, and indolinyl, including their corresponding iso-forms;

or a substituted or unsubstituted fused or unfused aryl or heteroaryl selected from phenyl, benzyl, naphthyl, furyl, benzofuranyl, pyranyl, pyrazinyl, thienyl, pyrrolyl, imidazolyl, pyridyl, pyrimidinyl, pyridazinyl, indolyl, indolizinyl, indoazolyl, purinyl, quinolyl, thiazolyl, phthalazinyl, quinoxalinyl, quinazolinyl, benzothienyl, anthryl, and phenathtryl, including their corresponding iso-forms.

30. The composition of claim 1, wherein R⁹-R¹² and R¹⁴-R¹⁹ are independently chosen from are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, 2-ethyl-hexyl, cyclopentyl, cyclohexyl, phenyl, pyridinyl, or pyrrolidinyl.

31. The composition of claim 1, wherein R¹³ and R²⁰ are independently chosen from an alkylene group having 1 to 30 carbon atoms, an aralkylene group having 7 to 30 carbon atoms, or an arylene group having 6 to 30 carbon atoms.

32. The composition of claim 1, wherein R¹³ and R²⁰ are independently chosen from an alkylene group having 1 to 12 carbon atoms, an aralkylene group having even 7 to 13 carbon atoms, or an arylene group having 6 to 15 carbon atoms.