MOISTURE CURABLE ORGANOPOLYSILOXANE COMPOSITION

• US 20120065308A1
• Filed: 09/08/2011
• Published: 03/15/2012
• Est. Priority Date: 09/08/2010
• Status: Active Grant

• Current Assignee: Anantharaman Dhanabalan, Edward J. Nesakumar, Shahid Murtuza, Shayne J. Landon, SUMI
• Original Assignee: Anantharaman Dhanabalan, Edward J. Nesakumar, Shahid Murtuza, Shayne J. Landon, SUMI
• Inventors: Sumi, Nesakumar, Edward J., Dhanabalan, Anantharaman, Murtuza, Shahid, Landon, Shayne J.
• Granted Patent: US 8,937,141 B2
• Time in Patent Office: Days
• US Class Current: 524/139
• CPC Class Codes: C08K 5/0091 Complexes with metal-heteroatom-bonds
• CPC Class Codes: C08K 5/49 Phosphorus-containing compounds C08K5/0091 takes precedence
• CPC Class Codes: C08K 5/5419 containing at least one Si—C bond
• CPC Class Codes: C08L 83/04 Polysiloxanes

Abstract

The present invention provides curable compositions comprising non-Sn organo-metal catalysts that accelerate the condensation curing of moisture curable silicones/non-silicones. In particular, the present invention provides Mn(III) complexes that are particularly suitable as replacements for organotin for sealant and RTV formulations. The Mn(III) complexes are comparable or superior to organotin such as DBTDL, superior to Mn(II) compounds, and 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, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alkaryaminosiloxane, an alkoxycarbamatosilane, an alkoxycarbamatosiloxane, and combinations of two or more thereof;

(C) about 0.01-7 parts per weight per 100 parts per weight of the polymer (A) of a catalyst selected from the group of organometallic compounds or salts of manganese (III) (Mn-III);

(D) at least one adhesion promoter chosen from a silane or siloxane other than the compounds listed under (B);

(E) optionally, a filler component; and

(F) at least one acidic compound chosen from a phosphate ester, a phosphonate, a phosphite, a phosphine, a sulfite, a pseudohalogenide, a branched alkyl carboxylic acid, and a combination of two or more thereof.

2. The composition of claim 1, wherein the metal catalyst component (C) comprises a Mn(III) complex of the formula (1):

Mn^IIIY_3-cA_c 

 

(1)

wherein Y is a chelating ligand chosen from a diketonate, a diamine, a triamine, an aminoacetate, a nitriloacetate, a bypyridin, a glyoxime, or a combination of two or more thereof; and

A is an anion, and c is a number between 0 to 2 or an integer.

3. The composition of claim 2, wherein the chelating agent Y comprises a substituted or unsubstituted diketonate.

4. The composition of claim 2, wherein the anion A is chosen from a branched C4-C19-alkyl carboxylic acid, a C4-C12-alkylsulfonate, or a combination thereof.

5. The composition of claim 1, wherein the component (F) is chosen from a mono ester of a phosphate;

a phosphonate of the formula (R³O)PO(OH)₂, (R³O)P(OH)₂, or R³P(O)(OH)₂ where R³ is a C₁-C₁₈-alkyl, a C₂-C₂₀-alkoxyalkyl, phenyl, a C₇-C₁₂-alkylaryl, a poly(C₂-C₄-alkylene) oxide ester or its mixtures with diesters;

a branched alkyl C₄-C₁₄-alkyl carboxylic acid;

or a combination of two or more thereof.

6. 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 polypropylene;

a polyesterether; and

a polyorganosiloxane having units of R₃SiO_1/2, R₂SiO, RSiO_3/2, and/or SiO_4/2,

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, a C₁-C₈-alkoxy, a C₂-C₁₈-alkoxyalkyl, an oximoalkyl, an enoxyalkyl, an aminoalkyl, a carboxyalkyl, an amidoalkyl, an amidoaryl, a 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.

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

methyltrimethoxysilane (MTMS);

vinyl-trimethoxysilane;

methylvinyldimethoxysilane;

dimethyldiethoxysilane;

vinyltriethoxysilane;

tetra-n-propylorthosilicate;

vinyltris(methylethylketoxime)silane;

methyltris(methylethylketoxime)silane;

trisacetamidomethylsilane;

bisacetamidodimethylsilane;

tris(N-methyl-acetamido)methylsilane;

bis(N-methylacetamido)dimethylsilane;

(N-methylacetamido)methyldialkoxysilane;

trisbenzamidomethylsilane;

trispropenoxymethylsilane;

alkyldialkoxyamidosilanes;

alkylalkoxybisamidosilanes;

CH₃Si(OC₂H₅)_1-2(NHCOR)_2-1;

(CH₃Si(OC₂H₅)(NCH₃COC₆H₅)₂;

CH₃Si(OC₂H₅)—

(NHCOC₆H₅)₂;

methyldimethoxy(ethylmethylketoximo)silane;

methylmethoxybis-(ethylmethylketoximo)silane;

methyldimethoxy(acetaldoximo)silane;

methyldimethoxy(N-methylcarbamato)silane;

ethyldimethoxy(N-methylcarbamato)silane;

methyldimethoxyisopropenoxysilane;

trimethoxyisopropenoxysilane;

methyltri-iso-propenoxysilane;

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

methyldimethoxy(1-phenylethenoxy)silane;

methyldimethoxy-2(1-carboethoxypropenoxy)silane;

methylmethoxydi-N-methylaminosilane;

vinyldimethoxymethylaminosilane;

tetra-N,N-diethylaminosilane;

methyldimethoxymethylaminosilane;

methyltricyclohexylaminosilane;

methyldimethoxyethylaminosilane;

dimethyldi-N,N-dimethylaminosilane;

methyldimethoxyisopropylaminosilane dimethyldi-N,N-diethylaminosilane. ethyldimethoxy(N-ethylpropionamido)silane;

methyldimethoxy(N-methylacetamido)silane;

methyltris(N-methylacetamido)silane;

ethyldimethoxy(N-methylacetamido)silane;

methyltris(N-methylbenzamido)silane;

methylmethoxybis(N-methyl acetamido)silane;

methyldimethoxy(caprolactamo)silane;

trimethoxy(N-methylacetamido)silane;

methyldimethoxyethylacetimidatosilane;

methyldimethoxypropylacetimidatosilane;

methyldimethoxy(N,N′

,N′

-trimethylureido)silane;

methyldimethoxy(N-allyl-N′

,N′

-dimethylureido)silane;

methyldimethoxy(N-phenyl-N′

,N′

-dimethylureido)silane;

methyldimethoxyisocyanatosilane;

dimethoxydiisocyanatosilane;

methyldimethoxythioisocyanatosilane;

methylmethoxydithioisocyanatosilane, or a combination of two or more thereof.

8. The composition of claim 1, wherein the adhesion promoter component (D) is chosen from an aminoalkyltrialkoxysilane, an aminoalkylalkyldialkoxysilane, a bis(alkyl-trialkoxysilyl)amine, a tris(alkyltrialkoxysilyl)amine, a tris(alkyltrialkoxysilyl)cyanuarate, and a tris(alkyltrialkoxysilyl)isocyanuarate, or a combination of two or more thereof.

9. The composition of claim 1, comprising about 1 to about 10 wt. % of the crosslinker component (B) based on 100 wt. % of the polymer component (A).

10. The composition of claim 1, wherein the crosslinker component (B) is chosen from a silane or a siloxane, the silane or siloxane having two or more reactive groups that can undergo hydrolysis and/or condensation reaction with polymer (A) or on its own in the presence of water and component (F).

11. The composition of claim 1, wherein the polymer component (A) is chosen from a polyorganosiloxane comprising divalent units of the formula [R₂SiO] in the backbone, wherein R 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.

12. The polymer composition of claim 11 wherein the polymer component (A) has the formula (3):

R²_3-aR¹_aSi—

Z—

[R₂SiO]_x[R¹₂SiO]_y—

Z—

SiR¹_aR²_3-a 

 

(3)

whereby

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 enoxyalkyl, an aminoalkyl, a carboxyalkyl, an amidoalkyl, an amidoaryl, a carbamatoalkyl, or a combination of two or more thereof, and

Z is —

O—

, bond, or —

C₂H₄—

.

13. The composition of claim 1 further comprising a solvent chosen from an alkylbenzene, a trialkyphosphophate, a triarylphosphate, a phthalic acid ester, an arylsulfonic acid ester having a viscosity-density constant (VDC) of at least 0.86 that is miscible with a polyorganosiloxanes and catalyst component (C), a polyorganosiloxane devoid of reactive groups and having a viscosity of less than 2000 mPa·

s at 25°

C., or a combination of two or more thereof.

14. The composition of claim 1, wherein the composition is provided as a one part composition.

15. The composition of any of claims claim 1 comprising:

100 pt. wt of component (A),

0.1 to about 10 pt. wt of at least one crosslinker (B),

0.01 to about 7 pt. wt. of a catalyst (C),

0.1 to about 5 pt. wt. of an adhesion promoter (D),

0 to about 300 pt. wt of component (E),

0.01 to about 8 pt. wt. of component (F),

whereby this composition can be stored in the absence of humidity and is curable in the presence of humidity upon exposure to ambient air.

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

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

(ii) a second portion comprising the crosslinker (B), the catalyst component (C), the adhesive 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).

17. The two-part composition of claim 16 where:

portion (i) comprises 100 p. wt of component (A), and 0 to 70 p. wt of component (E); and

portion (ii) comprises 0.1 to 10 p. wt of at least one crosslinker (B), 0.01 to 7 p. wt. of a catalyst (C), 0 to 5 p. wt. of an adhesion promoter (D), and 0.02 to 3 p. wt. component (F).

18. A method of providing a cured material comprising exposing the composition of any of claims 1 to ambient air.

19. A method of providing a cured material comprising combining the first portion and the second portion of claim 16 and curing the mixture.

20. A method of providing a cured material comprising combining the first portion and the second portion of claim 17 and curing the mixture.

21. The method of claim 18 whereby the composition is stored in a sealed cartridge or flexible bag having outlet nozzles for extrusion and/or shaping of the uncured composition prior to cure.

22. A cured polymer material formed from the composition of any of claims 1.

23. The cured polymer material of claim 22 in the form of an elastomeric or duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, and an impression material.