Granted Patent B2

US 9,890,303 · App. 15/626,340 · Granted Feb 13, 2018

Abstract

Claims (58)

1. A composition comprising:

(a) flexibilizer (i) having the general formula (I):

wherein:

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 R 2 is independently an alkyl group having from 1 to 6 carbon atoms;

each occurrence of R 3 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, or an alkoxy group having from 1 to 6 carbon atoms and at least one ether or ester functional group;

each occurrence of X 2 is independently a hydroxyl group, an alkoxy group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms and at least one ether or ester functional group, or a group with the formula (II):

wherein:

R 1 , R 2 and R 3 are the same as defined above;

each occurrence of subscripts a, b, c, d, e and f is independently an integer wherein a is 1 to 3; b is 0 to 500, c is 1 to 500, d is 0 to 10, e is 0 to 50, and f is 0 to 50 with the provisos that

(1) the molar ratio of b to c is from 0:1 to 15:1, and

(2) the molar ratio of d to c is from 0:1 to 1:1;

(b) at least one resin selected from the group consisting of an amine-functional resin (iv), a mercapto-functional resin (v), a resin containing silanol-reacting groups and a resin containing alkoxysilyl-reacting group,

with the proviso that when the resin (b) is the amino-functional resin (iv) or mercapto-functional resin (v), the composition further comprises,

(c) at least one curing agent (vi) selected from the group consisting of isocyanate-containing compound (vii), blocked isocyanate-containing compound (viii) and aminoplast (ix).

2. The composition of claim 1 wherein each occurrence of X 1 is independently hydroxyl, methoxy, ethoxy, propoxy or isopropoxy; R 1 is methyl or phenyl; R 2 is methyl; R 3 is phenyl; b is 1 to 100: c is 2 to 100; d is 0; and the molar ratio of b to c is from 1:1 to 10:1.

3. The composition of claim 1 wherein flexibilizer (i) has a silanol content or a SiX 1 content of from 2 to 15 mole %, based upon the total number of silicon atoms.

4. The composition of claim 1 wherein flexibilizer (i) has a weight average molecular weight of from 500 to 50,000.

5. The composition of claim 1 wherein flexibilizer (i) 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, CH 3 O—Si(CH 3 )—O—[Si(CH 3 ) 2 O] u —[Si(Ph) 2 O] w —Si(CH 3 ) 2 —OCH 3 where u/w is 3, Ph is phenyl, and mixtures thereof.

6. The composition of claim 1 wherein amine-functional resin (iv) is represented by general formula (VI):

[H(R 9 )N-] g R 10   (VI)

wherein

R 9 is hydrogen, a linear, cyclic or branched hydrocarbon group having from 1 to 18 carbon atoms, which is optionally substituted by heteroatoms, an alkyl radical which is interrupted by nonadjacent oxygen atoms, an alkoxy group —OR 11 or an acyloxy group —O—C(═O)—R 12 wherein R 11 is hydrogen or a linear, cyclic or branched hydrocarbon group having from 1 to 18 carbon atoms and R 12 is a hydrogen or a hydrocarbon contain from 1 to 18 carbon atoms;

R 10 is a linear or branched polymer group having a number average molecular weight of from 500 to 25,000, as determined in accordance with DIN Standard 55672 (1) using polystyrene standards; and

g is an integer of greater than 1.

7. The composition of claim 1 wherein mercapto-functional resin (v) is represented by general formula (VII):

R 13 SH) h   (VII)

wherein

R 13 is a linear or branched polymer group having a number average molecular weight of from 500 to 25,000, as determined in accordance with DIN Standard 55672 (1) using polystyrene standards; and,

h is an integer greater than 1.

8. The composition of claim 1 wherein curing agent (vi) is an isocyanate containing compound (vii) selected from the group consisting of 1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, omega,omega′-diisocyanatodipropyl ether, cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, 2,2- and 2,6-diisocyanato-1-methylcyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 2,5- and 3,5-bis(isocyanatomethyl)-8-methyl-1,4-methano-decahydronaphthalene, 1,5-, 2,5-, 1,6- and 2,6-bis(isocyanatomethyl)-4,7-methanohexahydroindane, 1,5-, 2,5-, 1,6- and 2,6-bis(isocyanato)-4,7-methylhexahydroindane, dicyclohexyl-2,4′-diisocyanate, 4,4′-diisocyanate, 2,4- and 2,6-hexahydrotolylene diisocyanate, perhydro 2,4′- and 4,4′-diphenylmethane diisocyanate, omega,omega′-diisocyanato-1,4-diethylbenzene, 1,3- and 1,4-phenylene diisocyanate, 4,4′-diisocyanatobiphenyl, 4,4′-diisocyanato-3,3′-dichlorobiphenyl, 4,4′-diisocyanato-3,3′-dimethoxybiphenyl, 4,4′-diisocyanato-3,3′-dimethylbiphenyl, 4,4′-diisocyanato-3,3′-diphenylbiphenyl, 2,4′- and 4,4′-diisocyanatodiphenylmethane, naphthylene-1,5-diisocyanate, 2,4- and 2,6-tolylene diisocyanate, N,N′-(4,4′-dimethyl-3,3′-diisocyanatodiphenyl)uretdione, m-xylylene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, 2,4,4′-triisocyanatodiphenyl ether, 4,4′,4″-triisocyanatotriphenyl methane, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, diphenylmethane 4,4′-diisoyanate, diphenylmethane 2,4′-diisocyanate, p-phenylene diisocyanate, biphenyl diisocyanates, 3,3′-dimethyl-4,4′-diphenylene diisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, isophorone diisocyanate, ethylene diisocyanate, dodecane 1,12-diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate, methylcyclohexyl diisocyanates, hexahydrotoluene 2,4-diisocyanate, hexahydrotoluene 2,6-diisocyanate, hexahydrophenylene 1,3-diisocyanate, hexahydrophenylene 1,4-diisocyanate, perhydrodiphenylmethane 2,4′-diisocyanate, 4,4′-methylenedicyclohexyl diisocyanate, tetramethylxylyl diisocyanates, biuret dimers and the isocyanurate trimers thereof.

9. The composition of claim 1 containing from 1.0 to 98 percent by weight resin having an active hydrogen (ii) based on the total weight of the composition, from 0.1 to 80 parts by weight flexibilizer (i) based on one hundred parts of resin having an active hydrogen (ii), and from 0.1 to 90 parts by weight curing agent (vi) based on one hundred parts of resin having an active hydrogen (ii).

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

11. The composition of claim 10 , wherein the catalyst is at least one member 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.

12. The composition of claim 10 wherein the filler is selected from the group consisting of particulate metal, fumed metal oxide, precipitated metal oxide, precipitated and ground metal carbonate and carbon black, metal sulfate, metal phosphate, silicate, and having a concentration in the range of from 0 to 50 weight percent based on the total weight of components (i), (ii), (vi) and filler.

13. The composition of claim 10 wherein the plasticizer is liquid organic compound selected from the group consisting of alkyl phthalate, alkyl sulphate and polyether, alkyl acrylate, and having a concentration in the range up to 40 parts by weight per hundred parts of resin having an active hydrogen (ii).

14. The composition of claim 10 wherein the water scavenger agent is an alkoxysilane selected from the group consisting of vinyltrimethoxysilane and methyltrimethoxysilane, and having a concentration in the range up to 5 percent by weight, based on the weight of resin having an active hydrogen (ii).

15. The composition of claim 10 wherein the adhesion promoter is an organofunctional alkoxysilane, and having a concentration in the range up to 5 percent by weight, based on the weight of resin having an active hydrogen (ii).

16. The composition of claim 1 wherein the composition is an adhesive, a sealant, a composite or a coating.

17. The cured composition of claim 1 .

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

19. The substrate having the composition of claim 1 applied thereto, wherein said composition is cured.

20. The composition of claim 1 wherein the resin (b) is a resin containing alkoxysilyl-reacting group.

21. A composition comprising:

(a) flexibilizer (i) having the general formula (I):

wherein:

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 R 2 is independently an alkyl group having from 1 to 6 carbon atoms;

each occurrence of R 3 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, or an alkoxy group having from 1 to 6 carbon atoms and at least one ether or ester functional group;

each occurrence of X 2 is independently a hydroxyl group, an alkoxy group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms and at least one ether or ester functional group, or a group with the formula (II):

wherein:

R 1 , R 2 and R 3 are the same as defined above;

each occurrence of subscripts a, b, c, d, e and f is independently an integer wherein a is 1 to 3; b is 0 to 500, c is 1 to 500, d is 0 to 10, e is 0 to 50, and f is 0 to 50 with the provisos that

(1) the molar ratio of b to c is from 0:1 to 15:1, and

(2) the molar ratio of d to c is from 0:1 to 1:1;

(b) at least one resin selected from the group consisting of an amine-functional resin (iv), a mercapto-functional resin (v), a resin containing silanol-reacting groups and a resin containing alkoxysilyl-reacting group.

Assignments (9)