Granted Patent B2

US 10,106,671 · App. 15/095,539 · Granted Oct 23, 2018

Abstract

Claims (89)

1. A silylated resin comprising the reaction products of the

(a) at least one mercapto-functional silicon compound having the general formula (I):

wherein A is —OR 3 , —OCR 2 2 (CR 2 2 ) f CR 2 2 OH, or

 and

B is H, or

wherein each occurrence of Z is independently selected from the group consisting of —OR 3 ,

—OCR 2 2 (CR 2 2 ) f CR 2 2 OH,

wherein each occurrence of R 1 is a divalent group independently selected from the group consisting of alkylene having 1 to 10 carbon atoms, cycloalkylene having from 5 to 12 carbon atoms, phenylene, and aralkyl having 6 to 10 carbon atoms;

wherein each occurrence of R 2 is a monovalent group independently selected from the group consisting of alkyl having 1 to 4 carbon atoms and hydrogen;

wherein each occurrence of R 3 is independently selected from the group consisting of hydrogen, alkyl having 1 to 12 carbon atoms, a cycloalkyl having 5 to 12 carbon atoms, phenyl and benzyl;

wherein each occurrence of the subscript f is independently an integer from 0 to 4; and

wherein the subscript n is an integer from 0 to 15, with the proviso that when n is 0, ps then B is

 and/or a partial hydrolyzate or condensate thereof having the general formula (II):

wherein A, B, R 1 and Z are defined above and the subscript n 1 is an integer from 2 to 15; and

(b) a reactive resin having at least one epoxy group and/or at least one (meth)acrylate group.

2. The silylated resin of claim 1 wherein R 1 is selected from the group consisting of —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH(CH 3 )CH 2 —, and —CH 2 CH(CH 3 )CH 2 CH 2 —, R 2 is hydrogen, —CH 3 or —CH 2 CH 3 , f is 0 or 1; and, n is 0, 1, 2 or 3.

3. The silvlated resin of claim 1 wherein R 1 is —CH 2 CH 2 CH 2 —; R 2 is chosen from hydrogen or —CH 3 ; f is 1; and n is 0 or 1.

4. The silylated resin of claim 1 wherein the mercapto-functional silicon compound (a) is

5. The silylated resin of claim 1 wherein the reactive resin (b) is at least one organic compound having at least one 1,2-epoxy group per molecule and an epoxide equivalent weight of from about 100 to about 2,000 grams per equivalent.

6. The silylated resin of claim 1 , wherein the reactive resin (b) has the general formula (IV):

wherein:

each occurrence of R 4 is independently hydrogen, or an alkyl group of from 1 to 8 carbon atoms, a phenyl group or an aralkyl or arenyl group of from 7 to 12 carbon atoms;

each occurrence of R 5 is a divalent organic group of from 1 to 12 carbon atoms or a chemical bond;

G 1 is a divalent or polyvalent organic group containing from 1 to 2,000 carbon atoms; and b is an integer of from 2 to 8.

7. The silylated resin of claim 1 wherein the reactive resin (b) is an organic compound or mixtures of organic compounds having at least one (meth)acrylate group per molecule with a number average molecular weight in the range of from about 100 to about 12,000.

8. The silylated resin of claim 1 wherein the reactive resin (b) has the general formula (V):

wherein:

wherein each occurrence of R 6 is independently hydrogen or methyl;

wherein G 2 is a divalent or a polyvalent organic group containing from 1 to 2,000 carbon atoms, with the proviso that the oxygen of the H 2 C═C(R 6 )C(═O)O— group is bonded to the carbon atom of the G 2 group; and

wherein d is an integer of from 2 to 8.

9. A composition comprising a silylated resin of claim 1 and a curing agent.

10. The composition of claim 9 wherein the curing agent is selected from the group consisting of ultraviolet radiation, gamma-radiation, a catalyst, a hardener and combinations thereof.

11. The composition of claim 9 wherein the silylated resin is derived from the reactive resin (b), which is an epoxy resin, and the curing agent is a tertiary amine catalyst selected from the group consisting of dimethyl propyl amine, dimethyl phenylamine, triethylamine and combinations thereof.

12. The composition of claim 10 wherein the curing agent is a hardener.

13. The composition of claim 12 wherein the hardener is selected from the group consisting of aliphatic primary amines, aromatic primary amines, aliphatic secondary amines, aromatic secondary amines, aliphatic primary polyamines, aromatic primary polyamines, aliphatic secondary polyamines, aromatic secondary polyamines, polyamides, amidoamines, ketimines, aldimines, mercaptans, isocyanates, melamine formaldehyde resins, urea formaldehyde resins, phenol formaldehyde resins, carboxylic acids, carboxylic acid anhydrides, and combinations thereof.

14. The composition of claim 9 wherein the silylated resin is derived from reactive resin (b), which is a (meth)acrylate resin, and the curing agent is radiation in combination with a radiation active initiator.

15. The silylated resin of claim 1 having the general formulae (XII)-(XIII):

wherein A 1 is —OR 3 , —OCR 2 2 (CR 2 2 ) f CR 2 2 OH or

B 1 is H or

wherein each occurrence of Z is independently selected from the group consisting of —OR 3 , —OCR 2 2 (CR 2 2 ) f CR 2 2 OH,

wherein each occurrence of R 1 is a divalent group independently selected from the group consisting of alkylene having 1 to 10 carbon atoms, cycloalkylene having from 5 to 12 carbon atoms, phenylene, and aralkyl having 6 to 10 carbon atoms;

wherein each occurrence of R 2 is a monovalent group independently selected from the group consisting of alkyl having 1 to 4 carbon atoms and hydrogen;

wherein each occurrence of R 3 is independently selected from the group consisting of hydrogen, alkyl having 1 to 12 carbon atoms, a cycloalkyl having 5 to 12 carbon atoms, phenyl and benzyl;

wherein each occurrence of the subscript f is independently an integer from 0 to 4;

wherein the subscript n 1 is an integer from 2 to 15; and

wherein the subscript n is an integer from 0 to 15, with the proviso that when n is 0,

then B 1 is

 and

and each occurrence of Q 1 is hydrogen,

wherein each occurrence of R 4 is independently hydrogen, or an alkyl group of from 1 to 8 carbon atoms, a phenyl group or an aralkyl or arenyl group of from 7 to 12 carbon atoms;

wherein each occurrence of R 5 is a divalent organic group of from 1 to 12 carbon atoms or a chemical bond;

wherein each occurrence of R 6 is hydrogen or methyl,

wherein G 1 is a divalent or polyvalent organic group containing from 1 to 2,000 carbon atoms;

wherein G 2 is a divalent or polyvalent organic group containing from 1 to 2,000 carbon atoms, with the proviso that the oxygen of the H 2 C═C(R 6 )C(═O)O— group is bonded to the carbon atom the G 2 group;

wherein b is an integer of from 2 to 8, and

wherein d is and integer of from 2 to 8, with the proviso that at least one Q 1 is

16. The silylated resin of claim 1 , wherein the silylated resin has the general formulae (XIV)-(XV):

wherein where each occurrence of R 4 is independently hydrogen, an alkyl group of from 1 to 8 carbon atoms, more specifically from 1 to 6 carbon atoms, a phenyl group or an aralkyl or arenyl group of from 7 to 12 carbon atoms, more specifically from 7 to 10 carbon atoms;

wherein each occurrence of R 5 is a divalent organic group of from 1 to 12 carbon atoms or a chemical bond;

wherein each occurrence of R 6 is hydrogen or methyl,

wherein G 1 is a divalent or polyvalent organic group containing from 1 to 2,000 carbon atoms;

wherein G 2 is a divalent or polyvalent organic group containing from 1 to 2,000 carbon atoms, with the proviso that the oxygen of the —CH 2 —CH(R 6 )C(═O)O— group is bonded to the carbon atom the G 2 group;

wherein b is an integer of from 2 to 8, and

wherein d is and integer of from 2 to 8,

and wherein each occurrence of Q 2 is independently

wherein A 2 is —OR 3 , —OCR 2 2 (CR 2 2 ) f CR 2 2 OH or

B 2 is H or

wherein each occurrence of Z is independently selected from the group consisting of —OR 3 , —OCR 2 2 (CR 2 2 ) f CR 2 2 OH,

wherein each occurrence of R 1 is a divalent group independently selected from the group consisting of alkylene having 1 to 10 carbon atoms, cycloalkylene having from 5 to 12 carbon atoms, phenylene, and aralkyl having 6 to 10 carbon atoms;

wherein each occurrence of R 2 is a monovalent group independently selected from the group consisting of an alkyl having 1 to 4 carbon atoms and hydrogen;

wherein each occurrence of R 3 is independently selected from the group consisting of hydrogen, an alkyl having 1 to 12 carbon atoms, a cycloalkyl having 5 to 12 carbon atoms, phenyl and benzyl;

wherein E 1 is hydrogen or a chemical bond between the sulfur atom and the carbon atom;

wherein each occurrence of the subscript f is independently an integer from 0 to 4;

wherein the subscript n is an integer from 0 to 15, n 1 is an integer from 2 to 15, with the provisos that (i) when n is 0, then B 2 is

 and (ii) only one E 1 in the structures for Q 2 is a chemical bond.

17. The silylated resin of claim 16 , wherein Q 2 is A 2 -B 2 , wherein A 2 is —OR 3 , —OCR 2 2 (CR 2 2 ) f CR 2 2 OH and B 2 is

wherein each occurrence of R 1 is a divalent group independently selected from the group consisting of alkylene having 1 to 10 carbon atoms, cycloalkylene having from 5 to 12 carbon atoms, phenylene, and aralkyl having 6 to 10 carbon atoms;

wherein each occurrence of R 2 is a monovalent group independently selected from the group consisting of an alkyl having 1 to 4 carbon atoms and hydrogen;

wherein each occurrence of R 3 is independently selected from the group consisting of hydrogen, an alkyl having 1 to 12 carbon atoms, a cycloalkyl having 5 to 12 carbon atoms, phenyl and benzyl;

wherein E 1 is hydrogen or a chemical bond between the sulfur atom and the carbon atom;

wherein each occurrence of the subscript f is independently an integer from 0 to 4.

18. The silylated resin of claim 16 wherein Q 2 is

wherein A 2 is —OR 3 or —OCR 2 2 (CR 2 2 ) f CR 2 2 OH, B 2 is hydrogen, Z is —OR 3 or —OCR 2 2 (CR 2 2 ) f CR 2 2 OH, E 1 is a chemical bond and n is 1.

19. The silylated resin of claim 1 , wherein the silylated resin has the general formula (XVI):

wherein each R 1 is independently —CH 2 —, —CH 2 CH 2 — or —CH 2 CH 2 CH 2 —; each R 2 is independently hydrogen or methyl; R 4 is hydrogen or methyl, R 5 is a chemical bond, or a —C(═O)—, —C(═O)O—, —C c H 2c — or —C c H 2c O— group wherein the subscript c is an integer of from 1 to 4; G 1 is a divalent or polyvalent organic group containing from 1 to 2,000 carbon atoms; and b and f are integers where b is 2 to 8 and f is 0 or 1.

20. A composition comprising the silylated resin of claim 1 and a filler.

21. A coating composition comprising the silylated resin of claim 1 .

22. A sealant composition comprising the silylated resin of claim 1 .

23. A primer comprising the silylated resin of claim 1 .

Assignments (6)