Silicone-polyether copolymer, isocyanate-functional silicone-polyether copolymer formed therewith, silicone-polyether-urethane copolymer, sealants comprising same, and related methods

Patent metadata

Field	Value
Publication number	US-10738191-B2
Application number	US-201816626383-A
Country	US
Kind code	B2
Filing date	Jun 26, 2018
Priority date	Jun 26, 2017
Publication date	Aug 11, 2020
Grant date	Aug 11, 2020

Abstract

A silicone-polyether copolymer has the formula X—Y, where X is a silicone moiety having a particular structure and Y is a polyether moiety. An isocyanate-functional silicone-polyether copolymer formed therewith is also disclosed. Further, a silicone-polyether-urethane copolymer formed with the isocyanate-functional silicone-polyether copolymer is disclosed. Related methods of preparation as well as sealants and cured products thereof are further disclosed.

First claim

What is claimed is:

1. A silicone-polyether copolymer having the formula X-Y,
wherein X is a silicone moiety having one of formulas (I)-(III):

wherein each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group having from 1 to 18 carbon atoms; each R 2 is an independently selected substituted or unsubstituted hydrocarbyl group having from 1 to 18 carbon atoms; each D 1 is an independently selected divalent hydrocarbon group having from 2 to 18 carbon atoms; each subscript a is independently 0 or 1; subscript f is 0 or 1; subscript t is ≥0; and subscript u is >0; and
wherein Y is a polyether moiety.

2. The silicone-polyether copolymer of claim 1 , wherein the polyether moiety Y has the formula
—(C n H 2n O) w H,

wherein each subscript n is independently selected from 2 to 4 in each moiety indicated by subscript w; and wherein subscript w is from 1 to 200.

3. The silicone-polyether copolymer of claim 1 , wherein:
(i) the polyether moiety Y has the formula
—(C 2 H 4 O) x (C 3 H 6 O) y (C 4 H 8 O) z H,

wherein subscript x is from 0 to 200; subscript y is from 1 to 200; and subscript z is from 0 to 200; and wherein units indicated by subscripts x, y and z may be in randomized or block form in the polyether moiety Y;

(ii) the polyether moiety Y has a number average molecular weight of at least about 100; or
(iii) both (i) and (ii).

4. The silicone-polyether copolymer of claim 1 , wherein:
(i) each R 1 is methyl;
(ii) R 2 is propyl;
(iii) each a is 0;
(iv) each D 1 is C 2 H 4 ; or
(v) any combination of (i) to (iv).

5. A method of preparing a silicone-polyether copolymer, said method comprising:
reacting a polyether compound having one terminal unsaturated group and one terminal hydroxyl group and an organosilicon compound in the presence of a hydrosilylation catalyst to give the silicone-polyether copolymer;
wherein the silicone-polyether copolymer is according to claim 1 .

6. The method of claim 5 , wherein one of provisos I) and II) below is true:
I) the polyether compound has the formula
R 3 O(C n H 2n O) w′ H,
wherein R 3 is an unsaturated group having from 2 to 6 carbon atoms; each subscript n is independently selected from 2 to 4 in each moiety indicated by subscript w′; and subscript w′ is from 1 to 200;

II)
(i) the polyether compound has the formula
—R 3 O(C 2 H 4 O) x′ (C 3 H 6 O) y′ (C 4 H 8 O) z′ H,

wherein R 3 is an unsaturated group having from 2 to 6 carbon atoms; subscript x′ is from 0 to 200; subscript y′ is from 1 to 200; and subscript z′ is from 0 to 200; and wherein units indicated by subscripts x′, y′ and z′ may be in randomized or block form in the polyether compound;

(ii) the polyether compound has a number average molecular weight of at least about 100; or
(iii) both (i) and (ii).

7. The method of claim 5 , wherein the organosilicon compound is an organohydrogensiloxane compound having one of formulas (IV)-(VI):

wherein each R 1 , R 2 , D 1 , subscript a, subscript f, subscript t, and subscript u are as defined above; and optionally, wherein: (i) each R 1 is methyl; (ii) R 2 is propyl; (iii) each a is 0; (iv) each D 1 is ethylene; or (v) any combination of (i) to (iv).

8. A method of preparing an isocyanate-functional silicone-polyether copolymer, said method comprising:
reacting a silicone polyether copolymer with a polyisocyanate to give the isocyanate-functional silicone-polyether copolymer;
wherein the silicone polyether copolymer is according to claim 1 ;
wherein the isocyanate-functional silicone-polyether copolymer has the following formula:

wherein X is defined above; Y′ is a polyether moiety; and Z 1 is a residue of the polyisocyanate having at least one isocyanate functional group; and
optionally, wherein the polyisocyanate: (i) has a nominal functionality of at least 1.6; or (ii) comprises a diisocyanate compound having the formula NCO-D′-OCN, wherein D′ is a divalent linking group.

9. An isocyanate-functional silicone-polyether copolymer formed in accordance with the method of claim 8 .

10. A sealant, comprising:
a silicone-polyether copolymer; and
a condensation reaction catalyst;
wherein the silicone-polyether copolymer is according to claim 1 .

11. A cured product of the sealant of claim 10 .

12. A composite article comprising a substrate and the cured product of claim 11 disposed on the substrate.

13. An isocyanate-functional silicone-polyether copolymer having the following formula:

wherein X is a silicone moiety having one of formulas (I)-(III):

wherein each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group having from 1 to 18 carbon atoms; each R 2 is an independently selected substituted or unsubstituted hydrocarbyl group having from 1 to 18 carbon atoms; each D 1 is an independently selected divalent hydrocarbon group having from 2 to 18 carbon atoms; each subscript a is independently 0 or 1; subscript f is 0 or 1; subscript t is ≥0; and subscript u is >0;
Y′ is a polyether moiety; and
Z 1 is an isocyanate moiety having at least one isocyanate functional group.

14. A method of preparing a silicone-polyether-urethane copolymer, said method comprising:
reacting an isocyanate-functional silicone-polyether copolymer with a coupling agent having an average of more than one isocyanate-reactive functional group to give the silicone-polyether-urethane copolymer;
wherein the isocyanate-functional silicone-polyether copolymer is according to claim 13 .

15. The method of claim 14 , wherein the coupling agent comprises at least one of a diol, a triol, a tetraol, a pentaol, and a hexaol.

16. The method of claim 15 , wherein the silicone-polyether-urethane copolymer has the formula Q-D″-Q, wherein D″ is a divalent linking group, and each Q has the following formula:

wherein each X is as defined above; and each Y′ is a polyether moiety.

17. A silicone-polyether-urethane copolymer prepared in accordance with the method of claim 14 .

18. A sealant, comprising:
an isocyanate-functional silicone-polyether copolymer; and
a condensation reaction catalyst;
wherein the isocyanate-functional silicone-polyether copolymer is according to claim 13 .

19. A silicone-polyether-urethane copolymer having an average of more than one functional group of the following formula:

wherein X is a silicone moiety having one of formulas (I)-(III):

wherein each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group having from 1 to 18 carbon atoms; each R 2 is an independently selected substit

Assignees

• Dow Silicones Corp
• Dow Global Technologies Llc

Inventors

• Grasmann Martin
• Hagan David
• Harkness Brian
• Heath William H
• Hlinka Ii Stephen Michael
• Joffre Eric
• Johnson William
• Krishnan Bindu
• Xu Qiuyun
• Zhu Bizhong

Classifications

• C09K3/10

  {Materials in mouldable or extrudable form} for sealing or packing joints or covers (filling pastes C09D5/34) · CPC title

• C09D183/12

  containing polyether sequences · CPC title

• C08K5/57

  Organo-tin compounds · CPC title

• C08G77/46 Primary

  containing polyether sequences · CPC title

• C08G65/336

  containing silicon · CPC title