Granted Patent B2

US 7,301,042 · App. 10/128,804 · Granted Nov 27, 2007

Abstract

Claims (79)

1. A blocked mercaptosilane condensate comprising at least one component whose chemical structure is represented by Formula 1:

(W1) l (W2) m (W3) y (W4) u (W5) v (W6) w   Formula 1

wherein:

l and at least one subscript selected from the group consisting of m, y, u, v, and w is an integer from 1 to 10,000;

W1 is a hydrolyzable blocked mercaptosilane fragment derived from a hydrolyzable blocked mercaptosilane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by either Formula 2 or Formula 3:

{[(ROC(═O)—) p (G-) j ] k Y—S—} r G(—SiX 3 ) s   Formula 2:

{(X 3 Si—) q G} a {Y(—S-G-SiX 3 ) b } c ;  Formula 3:

W2 is a hydrolyzable mercaptosilane fragment derived from a hydrolyzable mercaptosilane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by Formula 4:

{[(ROC(═O)—) p (G-) j ] k Y—S—} r - d G(—SH) d (—SiX 3 ) s ;  Formula 4:

W3 is a hydrolyzable polysulfide silane fragment derived from a polysulfide silane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by Formula 5:

X 1 X 2 X 3 Si-G 1 -S x -G 1 -SiX 1 X 2 X 3 ;  Formula 5:

W4 is a hydrolyzable alkyl silane fragment derived from a hydrolyzable alkyl silane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that can be represented by Formula 6:

Y 1 Y 2 Y 3 Si-R 2 ;  Formula 6:

W5 is a hydrolyzable bis silyl alkane fragment derived from a hydrolyzable bis silyl alkane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by Formula 7:

Z 1 Z 2 Z 3 Si-J-SiZ 1 Z 2 Z 3 ;  Formula 7:

W6 is a hydrolyzable tris silyl alkane fragment derived from a hydrolyzable tris silyl alkane by replacement of at least one hydrolyzable group with one end of a siloxane oxygen (—O—) group that is represented by either Formula 8 or Formula 9:

(Z 1 Z 2 Z 3 Si—CH 2 CH 2 —) 3 C 6 H 9   Formula 8:

(Z 1 Z 2 Z 3 Si—CH 2 CH 2 CH 2 —) 3 N 3 C 3 O 3 ;  Formula 9:

wherein, in the preceding Formulae 2 through 9:

Y is a polyvalent species (Q) z A(=E);

A is selected from the group consisting of carbon, sulfur, phosphorus, and sulfonyl;

E is selected from the group consisting of oxygen, sulfur, and NR;

each G is independently selected from the group consisting of monovalent and polyvalent moieties derived by substitution of alkyl, alkenyl, aryl, or aralkyl moieties, wherein G comprises from 1 to 18 carbon atoms; provided that G is not such that the silane would contain an, alpha, beta-unsaturated carbonyl including a carbon-carbon double bond next to the thiocarbonyl group, and provided that, if G is univalent, i.e., if p is 0, G can be hydrogen;

in each case, the atom A attached to the unsaturated heteroatom E is attached to the sulfur, which in turn is linked via a group G to the silicon atom;

Q is selected from the group consisting of oxygen, sulfur, and (—NR—);

each R is independently selected from the group consisting of hydrogen; straight, cyclic, or branched alkyl that may or may not contain unsaturation; alkenyl groups; aryl groups; and aralkyl groups, wherein each R, other than where R is hydrogen, comprises from 1 to 18 carbon atoms;

each X is independently selected from the group consisting of —Cl, —Br, RO—, RC(═O)O—, R 2 C═NO—, R 2 NO—, R 2 N—, —R, —(OSiR 2 ) t (OSiR 3 ), and (—O—) 0.5 wherein each R is as above and at least one X is not —R;

R 1 , R 2 , and R 3 are independently selected from the group consisting of hydrocarbon fragments obtained by removal of one hydrogen atom from a hydrocarbon having from 1 to 20 carbon atoms including aryl groups and any branched or straight chain alkyl, alkenyl, arenyl, or aralkyl groups;

each J, and G 1 are independently selected from the group consisting of hydrocarbon fragments obtained by removal of two hydrogen atom from a hydrocarbon having from 1 to 20 carbon atoms including arylene groups and any branched or straight chain alkylene, alkenylene, arenylene, or aralkylene groups;

each X 1 is a hydrolyzable moiety independently selected from the group consisting of —Cl, —Br, —OH, —OR 1 , R 1 C(═O)O—, —O—N═CR 1 2 , and (—O—) 0.5 ;

each X 2 and X 3 is independently selected from the group consisting of hydrogen, the members listed above for R 1 , and the members listed above for X 1 ;

at least one occurrence of X 1 , X 2 , and X 3 is (—O—) 0.5 ;

Y 1 is a moiety selected from hydrolyzable groups consisting of —Cl, —Br, —OH, —OR, R 2 C(═O)O—, —O—N═CR 2 2 , and (—O—) 0.5 ;

Y 2 and Y 3 are independently selected from the group consisting of hydrogen, the members listed above for R 2 , and the members listed above for Y 1 ; and

at least one occurrence of Y 1 , Y 2 , and Y 3 is (—O—) 0.5 ;

Z 1 is selected from the hydrolyzable groups consisting of —Cl, —Br, —OH, —OR 3 , R 3 C(═O)O—, —O—N═CR 3 2 , and (—O—) 0.5 ;

Z 2 and Z 3 are independently selected from the group consisting of hydrogen, the members listed above for R 3 , and the members listed above for Z 1 ;

at least one occurrence of Z 1 , Z 2 , and Z 3 in Formula 7 is (—O—) 0.5 ;

C 6 H 9 in Formula 8 represents any cyclohexane fragment obtainable by removal of three hydrogen atoms from a cyclohexane molecule;

N 3 C 3 O 3 in Formula 9 represents N,N′,N″-trisubstituted cyanurate;

a is 0 to 7;

b is 1 to 3;

c is 1 to 6;

d is 1 to r;

j is 0 or 1, but it may be 0 if, and only if, p is 1;

k is 1 to 2;

p is 0 to 5;

q is 0 to 6;

r is 1 to 3;

s is 1 to 3;

t is 0 to 5;

x is 2 to 20;

z is 0 to 2;

provided that:

(a) if A is carbon, sulfur, or sulfonyl, then

(i) a+b is 2, and

(ii) k is 1;

(b) if A is phosphorus, then a+b is 3 unless both

(i) c is greater than 1, and

(ii) b is 1,

in which case a is c+1; and

c) if A is phosphorus, then k is 2.

2. The blocked mercaptosilane condensate of claim 1 wherein l+m+y+u+v+w is equal to at least 2.

3. The blocked mercaptosilane condensate of claim 1 wherein (Q) z A(═E) is selected from the group consisting of —C(═NR)—; —SC(═NR)—; —SC(═O)—; (—NR)C(═O)—; (—NR)C(═S)—; —OC(═O)—; —OC(═S)—; —C(═O)—; —SC(═S)—; —C(═S)—; —S(═O)—; —S(═O) 2 —; —OS(═O) 2 —; (—NR)S(═O) 2 —; —SS(═O)—; —OS(═O)—; (—NR)S(═O)—; —SS(═O) 2 —; (—S) 2 P(═O)—; —(—S)P(═O)—; —P(═O)(—) 2 ; (—S) 2 P(═S)—; —(—S)P(═S)—; —P(═S)(—) 2 ; (—NR) 2 P(═O)—; (—NR)(—S)P(═O)—; (—O)(—NR)P(═O)—; (—O)(—S)P(═O)—; (—O) 2 P(═O)—; —(—O)P(═O)—; —(—NR)P(═O)—; (—NR) 2 P(═S)—; (—NR)(—S)P(═S)—; (—O)(—NR)P(═S)—; (—O)(—S)P(═S)—; (—O) 2 P(═S)—; —(—O)P(═S)—; and —(—NR)P(═S)—.

4. The blocked mercaptosilane condensate of claim 1 wherein the functional groups —YS— present in the hydrolyzable blocked mercaptosilane silane fragments are selected from the group consisting of thiocarboxylate esters, dithiocarboxylate, -thiocarbonate esters, dithiocarbonate esters, trithiocarbonate esters, thiocarbamate esters, dithiocarbamate esters,; thiosulfonate esters, thiosulfate esters, thiosulfamate esters, thiosulfinate esters, thiosulfite esters, thiosulfimate esters, thiophosphate esters, dithiophosphate esters, trithiophosphate esters, tetrathiophosphate esters P(═S)(S—) 3 ; thiophosphamate esters, dithiophosphamate esters, thiophosphorammidate esters, (dithiophosphoramidate esters, and trithiophosphoramidate esters.

5. The blocked mercaptosilane condensate of claim 1 wherein the Y groups are selected from the group consisting of —C(═NR)—; —SC(═NR)—; —SC(═O)—; —OC(═O)—; —S(═O)—; —S(═O) 2 —; —OS(═O) 2 —; —(NR)S(═O) 2 —; —SS(═O)—; —OS(═O)—; —(NR)S(═O)—; —SS(═O) 2 —; (—S) 2 P(═O)—; —(—S)P(═O)—; —P(═O)(—) 2 ; (—S) 2 P(═S)—; —(—S)P(═S)—; —P(═S)(—) 2 ; (—NR) 2 P(═O)—; (—NR)(—S)P(═O)—; (—O)(—NR)P(═O)—; (—O)(—S)P(═O)—; (—O) 2 P(═O)—; —(—O)P(═O)—; —(—NR)P(═O)—; (—NR) 2 P(═S)—; (—NR)(—S)P(═S)—; (—O)(—NR)P(═S)—; (—O)(—S)P(═S)—; (—O) 2 P(═S)—; —(—O)P(═S)—; and —(—NR)P(═S)—.

6. The blocked mercaptosilane condensate of claim 5 wherein the Y groups are selected from the group consisting of —OC(═O)—; —SC(═O)—; —S(═O)—; —OS(═O)—; —(—S)P(═O)—; and —P(═O)(—) 2 .

7. The blocked mercaptosilane condensate of claim 1 wherein Y is RC(═O)— in which R has a primary carbon attached to the carbonyl and is a C 2 -C 12 alkyl.

8. The blocked mercaptosilane condensate of claim 1 wherein the chemical structure is X 3 SiGSC(═O)GC(═O)SGSiX 3 wherein G is a divalent hydrocarbon.

9. The blocked mercaptosilane condensate of claim 1 wherein G is selected from the group consisting of —(CH 2 ) n — wherein n is 1 to 12, diethylene cyclohexane, 1,2,4-triethylene cyclohexane, and diethylene benzene and the sum of the carbon atoms within the G groups within the molecule is from 3 to 18.

10. The blocked mercaptosilane condensate of claim 1 wherein each R group is independently selected from the group consisting of hydrogen, C 6 to C 10 aryl, and C 1 to C 6 alkyl.

11. The blocked mercaptosilane condensate of claim 1 wherein each X is independently selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, isobutoxy, acetoxy, and oximato, provided that at least one X is hydrolyzable and at least one occurrence of X is (—O—) 0.5 .

12. The blocked mercaptosilane condensate of claim 1 wherein p is 0 to 2; X is RO— or RC(═O)O—; R is hydrogen, phenyl, isopropyl, cyclohexyl, or isobutyl; and G is a substituted phenyl or a substituted straight chain C 2 to C 12 alkyl.

13. The blocked mercaptosilane condensate of claim 12 wherein p is zero, X is ethoxy, and G is a C 3 -C 12 alkyl derivative.

14. The blocked mercaptosilane condensate of claim 1 wherein the hydrolyzable blocked mercaptosilane silane fragments are those whose parent silanes are selected from the group consisting of 2-triethoxysilyl-1-ethyl thioacetate; 2-trimethoxysilyl-1-ethyl thioacetate; 2-(methyldimethoxysilyl)-1-ethyl thioacetate; 3-trimethoxysilyl-1-propyl thioacetate; triethoxysilylmethyl thioacetate; trimethoxysilylmethyl thioacetate; triisopropoxysilylmethyl thioacetate; methyldiethoxysilylmethyl thioacetate; methyldimethoxysilylmethyl thioacetate; methyldiisopropoxysilylmethyl thioacetate; dimethylethoxysilylmethyl thioacetate; dimethylmethoxysilylmethyl thioacetate; dimethylisopropoxysilylmethyl thioacetate; 2-triisopropoxysilyl-1-ethyl thioacetate; 2-(methyldiethoxysilyl)-1-ethyl thioacetate; 2-(methyldiisopropoxysilyl)-1-ethyl thioacetate; 2-(dimethylethoxysilyl)-1-ethyl thioacetate; 2-(dimethylmethoxysilyl)-1-ethyl thioacetate; 2-(dimethylisopropoxysilyl)-1-ethyl thioacetate; 3-triethoxysilyl-1-propyl thioacetate; 3-triisopropoxysilyl-1-propyl thioacetate; 3-methyldiethoxysilyl-1-propyl thioacetate; 3-methyldimethoxysilyl-1-propyl thioacetate; 3-methyldiisopropoxysilyl-1-propyl thioacetate; 1-(2-triethoxysilyl-1-ethyl)-4-thioacetylcyclohexane; 1-(2-triethoxysilyl-1-ethyl)-3-thioacetylcyclohexane; 2-triethoxysilyl-5-thioacetylnorbornene; 2-triethoxysilyl-4-thioacetylnorbornene; 2-(2-triethoxysilyl-1-ethyl)-5-thioacetylnorbornene; 2-(2-triethoxysilyl-1-ethyl)-4-thioacetylnorbornene; 1-(1-oxo-2-thia-5-triethoxysilylpentyl)benzoic acid; 6-triethoxysilyl-1-hexyl thioacetate; 1-triethoxysilyl-5-hexyl thioacetate; 8-triethoxysilyl-1-octyl thioacetate; 1-triethoxysilyl-7-octyl thioacetate; 6-triethoxysilyl-1-hexyl thioacetate; 1-triethoxysilyl-5-octyl thioacetate; 8-trimethoxysilyl-1-octyl thioacetate; 1-trimethoxysilyl-7-octyl thioacetate; 10-triethoxysilyl-1-decyl thioacetate; 1-triethoxysilyl-9-decyl thioacetate; 1-triethoxysilyl-2-butyl thioacetate; 1-triethoxysilyl-3-butyl thioacetate; 1-triethoxysilyl-3-methyl-2-butyl thioacetate; 1-triethoxysilyl-3-methyl-3-butyl thioacetate; 3-trimethoxysilyl-1-propyl thiooctoate; 3-triethoxysilyl-1-propyl thiopalmitate; 3-triethoxysilyl-1-propyl thiooctoate; 3-triethoxysilyl-1-propyl thiobenzoate; 3-triethoxysilyl-1-propyl thio-2-ethylhexanoate; 3-methyldiacetoxysilyl-1-propyl thioacetate; 3-triacetoxysilyl-1-propyl thioacetate; 2-methyldiacetoxysilyl-1-ethyl thioacetate; 2-triacetoxysilyl-1-ethyl thioacetate; 1-methyldiacetoxysilyl-1-ethyl thioacetate; 1-triacetoxysilyl-1-ethyl thioacetate; tris-(3-triethoxysilyl-1-propyl)trithiophosphate; bis-(3-triethoxysilyl-1-propyl)methyldithiophosphonate; bis-(3-triethoxysilyl-1-propyl)ethyldithiophosphonate; 3-triethoxysilyl-1-propyldimethylthiophosphonate; 3-triethoxysilyl-1-propyldiethylthiophosphinate; tris-(3-triethoxysilyl-1-propyl)tetrathiophosphate; bis-(3-triethoxysilyl-1-propyl)methyltrithiophosphonate; bis-(3-triethoxysilyl-1-propyl)ethyltrithiophosphonate; 3-triethoxysilyl-1-propyldimethyldithiophosphinate; 3-triethoxysilyl-1-propyldiethyldithiophosphinate; tris-(3-methyldimethoxysilyl-1-propyl)trithiophosphate; bis-(3-methyldimethoxysilyl-1-propyl)methyldithiophosphonate; bis-(3-methyldimethoxysilyl-1-propyl)ethyldithiophosphonate; 3-methyldimethoxysilyl-1-propyldimethylthiophosphinate; 3-methyldimethoxysilyl-1-propyldiethylthiophosphinate; 3-triethoxysilyl-1-propylmethylthiosulphate; 3-triethoxysilyl-1-propylmethanethiosulphonate; 3-triethoxysilyl-1-propylethanethiosulphonate; 3-triethoxysilyl-1-propylbenzenethiosulphonate; 3-triethoxysilyl-1-propyltoluenethiosulphonate; 3-triethoxysilyl-1-propylnaphthalenethiosulphonate; 3-triethoxysilyl-1-propylxylenethiosulphonate; triethoxysilylmethylmethylthiosulphate; triethoxysilylmethylmethanethiosulphonate; triethoxysilylmethylethanethiosulphonate; triethoxysilylmethylbenzenethiosulphonate; triethoxysilylmethyltoluenethiosulphonate; triethoxysilylmethylnaphthalenethiosulphonate; and triethoxysilylmethylxylenethiosulphonate.

15. The blocked mercaptosilane condensate of claim 1 wherein X 1 , Y 1 , and Z 1 are independently selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy, chloro, and acetoxy.

16. The blocked mercaptosilane condensate of claim 1 wherein X 2 , X 3 , Y 2 , Y 3 , Z 2 , and Z 3 are independently selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy, chloro, acetoxy, hydrogen, methyl, ethyl, propyl, isopropyl, sec-butyl, phenyl, vinyl, cyclohexyl, and C 4 -C 20 , straight-chain alkyl groups.

17. The blocked mercaptosilane condensate of claim 1 wherein X 1 , X 2 , and X 3 are the same alkoxy group; Y 1 , Y 2 , and Y 3 are the same alkoxy group; and Z 1 , Z 2 , and Z 3 are the same alkoxy group.

18. The blocked mercaptosilane condensate of claim 1 wherein R 2 is selected from the group consisting of methyl, vinyl, ethyl, propyl, allyl, butyl, methallyl, pentyl, hexyl, phenyl, tolyl, benzyl, octyl, xylyl, mesityl, decyl, dodecyl, hexadecyl, and octadecyl.

Assignments (19)