Granted Patent B2

US 9,156,981 · App. 13/949,473 · Granted Oct 13, 2015

Abstract

Claims (50)

1. A moisture-curable composition comprising:

(a) a moisture-curable silylated resin having the general Formula (I):

P[-L-SiR 1 a (OR 1 ) 3-a ] m   Formula (I)

wherein:

P is a polymer residue derived from at least one addition or condensation monomer, wherein the polymer residue P has a polymer backbone selected from the group consisting of polyether, polyester, polyether-co-polyester, polyester-co-polyether, polythioether, polyamine, polyamide, polyester-co-polyamide, polyacrylate, polyacetal, polycarbonate, polybutadiene, polyurethane and polyurea;

L is a divalent linking group;

each occurrence of R 1 is independently an alkyl group having from 1 to 6 carbon atoms, a phenyl group or an arenyl group having 7 to 12 carbon atoms;

each occurrence of subscript a is independently 0, 1 or 2; and

m is an integer from 1 to 15;

(b) a flexibilizer having the general Formula (II):

wherein:

each occurrence of R 4 is independently an alkyl group having from 1 to 6 carbon atoms, a phenyl group or an arenyl group having 7 to 12 carbon atoms:

each occurrence of R 5 is independently an alkyl group having from 1 to 6 carbon atoms;

each occurrence of R 6 is independently a phenyl group or an arenyl group having 7 to 12 carbon atoms;

each occurrence of X 1 is independently a hydroxyl group, an alkoxy group having from 1 to 6 carbon atoms;

each occurrence of X 2 is independently a hydroxyl group, an alkoxy group having from 1 to 6 carbon atoms, or a group with the Formula (IIa):

R 4 , R 5 and R 6 are the same as defined above;

each occurrence of subscripts e, n, p, q, x and y is independently an integer wherein c is 1 to 3; n is to 500, p is 1 to 500, q is 0 to 10, x is 0 to 50, and y is 0 to 50 with the provisos that

(1) the molar ratio of n to p is from 0 to 15, and

(2) the molar ratio of q to p is from 0 to 1; and,

(c) at least one curing catalyst.

2. The moisture-curable composition of claim 1 wherein linking group L in moisture-curable silylated resin (I) has the general Formula (Ia):

-[A 1 -C(O)-A 2 ] b -R 2 —  Formula (Ia);

wherein:

each occurrence of R 2 is independently a divalent hydrocarbylene group containing from 1 to 12 carbon atoms;

each occurrence of A 1 is independently selected from divalent oxygen (—O—), sulfur (—S—) or substituted nitrogen of the structure (—) 2 NR 3 , wherein R 3 is hydrogen, alkyl, alkenyl, arenyl, aryl, aralkyl, alkyl containing at least one ester functional group or —R 2 SiX 1 X 2 X 3 group, wherein each R 3 , other than hydrogen, contains from 1 to 18 carbon atoms, and with the provisos that when A 1 is oxygen or sulfur, then A 2 is (—)NR 3 and when a is 0, then A 1 is oxygen;

each occurrence of A 2 is independently selected from divalent oxygen (—O—), sulfur (—S—) or substituted nitrogen of the structure (—) 2 NR 3 , wherein R 3 is hydrogen, alkyl, alkenyl, arenyl, aryl, aralkyl, alkyl containing at least one ester functional group or —R 2 SiX 1 X 2 X 3 group, wherein each R 3 , other than hydrogen, contains from 1 to 18 carbon atoms, and with the proviso that when A 2 is oxygen or sulfur, then A 1 is (—) 2 NR 3 ; and,

subscript b is 0 or 1.

3. The moisture-curable composition of claim 1 wherein polymer residue P of Formula (I) is selected from the group consisting of polyether, polyamine, polyurethane,and polyurea.

4. The moisture-curable composition of claim 1 wherein moisture-curable silylated resin of Formula (I) is obtained by the silylation of at least one silylatable polymer selected from the group consisting of polyether polyol, polyester polyol, hydroxyl-terminated polyacrylate, hydroxyl-terminated polybutadiene, polyether possessing terminal olefinic unsaturation, hydroxyl-terminated polyurethane, isocyanate-terminated polyurethanes, primary amine-terminated polyurea and secondary amine-terminated polyurea.

5. The moisture-curable composition of claim 3 wherein moisture-curable silylated resin of Formula (I) is obtained by the silylation of hydroxyl-terminated polyurethane with an isocyanatosilane.

6. The moisture-curable composition of claim 1 wherein each occurrence of X 1 is independently hydroxyl, methoxy, ethoxy, propoxy or isopropoxy; R 4 is methyl or phenyl; R 5 is methyl; R 6 is phenyl; n is 1 to 100; p is 2 to 100; q is 0; and the molar ratio of n to p is from 1 to 10.

7. The moisture-curable composition of claim 1 wherein flexibilizer of Formula (II) has a silanol content or a SiX 1 content of from 2 to 15 mole %, based upon the total number of silicon atoms.

8. The moisture-curable composition of claim 1 wherein flexibilizer of Formula (II) has a weight average molecular weight of from 500 to 50,000.

9. The moisture-curable composition of claim 1 wherein flexibilizer of Formula (II) is HO—Si(CH 3 ) 2 —O—[Si(CH 3 ) 2 O] r —[Si(Ph) 2 O] s —Si(CH 3 ) 2 —OH where r/s is 4.42, CH 3 O—Si(CH 3 ) 2 —O—[Si(CH 3 ) 2 O] u —[Si(Ph) 2 O] w —Si(CH 3 ) 2 —OCH 3 , where u/w is 2.99, or mixtures thereof.

10. The moisture-curable composition of claim 1 containing from 10 to 98 percent by weight moisture-curable silylated resin of Formula (I) based on the total weight of the moisture-curable composition, from 1 to 50 parts by weight flexibilizer of Formula (II) based on one hundred parts of the moisture-curable silylated resin, and from 0.001 to 10 parts by weight curing catalyst based on one hundred parts of the moisture-curable silylated resin.

11. The moisture-curable composition of claim 1 containing from 20 to 70 percent by weight moisture-curable silylated resin of Formula (I), from 1 to 30 parts by weight flexibilizer of Formula (II) based on one hundred parts of the moisture-curable silylated resin, and from 0.1 to 0.15 parts by weight curing catalyst based on one hundred parts of the moisture-curable silylated resin.

12. The moisture-curable composition of claim 1 wherein the curing catalyst is selected from the group consisting of organic tin, zirconium complex, aluminum chelate, titanic chelate, organic zinc, organic cobalt, organic iron, organic nickel and organobismuth, amine catalyst, dibutyltin oxide, dimethyltin diacetate, dimethyltin dilaurate, dimethyltin dineodecanote, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, stannous octoate, stannous acetate, stannous oxide, morpholine, tri-isopropylamine, bis-(2-dimethylaminoethyl) ether and piperazine, and mixtures thereof.

13. The moisture-curable composition of claim 1 , further comprising at least one additional component selected from the group consisting of organic solvent, aminosilane, polysiloxane resin other than Formula (II), isocyanate-reactive scavenging agent, water scavenger agent, desiccant, non-silicon-based epoxy hardener, surfactant, colorant, plasticizer, extender, filler, reinforcing agent, adhesion promoter, hydrocarbon resin modifier, UV stabilizer, wetting agent, flow and leveling additive, thixotrope and defoamer.

14. The moisture-curable composition of claim 13 wherein the filler is selected from the group consisting of fumed metal oxide, precipitated metal oxide, precipitated metal carbonate and carbon black, and having a concentration in the range of from 0 to 50 weight percent based on the total weight of components (a), (b), (c) and filler.

15. The moisture-curable composition of claim 13 wherein the plasticizer is liquid organic compound selected from the group consisting of alkyl phthalate, alkyl sulphate and polyether, and having a concentration in the range of from 0 to 40 parts by weight per hundred parts of the moisture-curable silylated resin of Formula (I).

16. The moisture-curable composition of claim 13 wherein the water scavenger agent is an alkoxysilane selected from the group consisting of vinyltrimethoxysilane and methyltrimethoxysilane, and having a concentration in the range of from 0 to 5 percent by weight, based on the weight of the moisture-curable silylated resin of Formula (I).

17. The moisture-curable composition of claim 13 wherein the adhesion promoter is an organofunctional alkoxysilane selected from the group consisting of 3-aminopropyltrimethoxysilane and gamma-glycidoxypropyltrimethoxysilane, and having a concentration in the range of from 0 to 5 percent by weight, based on the weight of the moisture-curable silylated resin of Formula (I).

18. The moisture-curable composition of claim 1 wherein the composition is an adhesive, a sealant, a composite or a coating.

19. The cured composition of claim 1 .

20. A substrate having the cured composition of claim 19 .

21. A substrate having the composition of claim 1 applied thereto.

22. The cured composition of claim 1 exhibiting at least one improved property compared to substantially the same cured moisture-curable composition lacking a flexibilizer.

23. The cured composition of claim 22 wherein the improved property is at least one of elongation and tear strength.

24. The cured composition of claim 23 wherein the improvement in elongation is at least 10% and the improvement in tear strength is at least 20%.

Assignments (24)