Silicone-acrylate polymers, copolymers, and related methods and compositions

Patent metadata

Field	Value
Publication number	US-12503556-B2
Application number	US-202117793845-A
Country	US
Kind code	B2
Filing date	Jan 21, 2021
Priority date	Jan 22, 2020
Publication date	Dec 23, 2025
Grant date	Dec 23, 2025

Abstract

A curable composition is disclosed. The curable composition comprises (I) an epoxide-functional silicone-acrylate polymer and (II) an aminosiloxane. The epoxide-functional silicone-acrylate polymer comprises acrylate-derived monomeric units comprising siloxane moieties, epoxide-functional moieties, and optionally, hydrocarbyl moieties, and the aminosiloxane comprises an average of at least two amine functional groups per molecule. A method of preparing the curable composition is also disclosed, and includes reacting (A) an acryloxy-functional organosilicon component, (B) an epoxy-functional acrylate component, and optionally (C) an acrylate component, to give the epoxide-functional silicone-acrylate polymer (I), and combining the epoxide-functional silicone-acrylate polymer (I) with the aminosiloxane (II). An aminosiloxane-silicone-acrylate copolymer prepared with the composition, a cured product comprising the same, and methods of preparing the same, are also disclosed.

First claim

What is claimed is:

1 . A curable composition, comprising:
(I) an epoxide-functional silicone-acrylate polymer having the following general unit formula:

wherein: each R 1 is independently selected from H and CH 3 ; each R 2 is an independently selected substituted or unsubstituted hydrocarbyl group; each D 1 is a divalent linking group; each Y 1 is an independently selected siloxane moiety; each X 1 is an independently selected epoxide-functional moiety; subscript a≥1; subscript b≥1; subscript c≥0; and units indicated by subscripts a, b, and c may be in any order in the silicone-acrylate polymer; and

(II) an aminosiloxane comprising an average of at least two amine functional groups per molecule.

2 . The curable composition of claim 1 , wherein in the epoxide-functional silicone-acrylate polymer (I) at least one siloxane moiety Y 1 comprises a siloxane group having general formula —Si(R 3 ) 3 , where each R 3 is independently selected from R 4 and —OSi(R 5 ) 3 , with the proviso that at least one R 3 is —OSi(R 5 ) 3 ; where each R 5 is independently selected from R 4 , —OSi(R 6 ) 3 , and —[—D 2 —SiR 4 2 ] m OSiR 4 3 ; where each R 6 is independently selected from R 4 , —OSi(R 7 ) 3 , and —[—D 2 —SiR 4 2 ] m OSiR 4 3 ; where each R 7 is independently selected from R 4 and —[—D 2 —SiR 4 2 ] m OSiR 4 3 ; where 0≤m≤100; where each D 2 is a divalent linking group; and where each R 4 is independently a substituted or unsubstituted hydrocarbyl group.

3 . The curable composition of claim 2 , wherein in the epoxide-functional silicone-acrylate polymer (I): (i) each R 3 is —OSi(R 5 ) 3 ; (ii) each R 4 is methyl; (iii) at least one R 5 is —OSi(R 6 ) 3 or —[—D 2 —SiR 4 2 ] m OSiR 4 3 ; (iv) each D 2 is independently O or ethylene; or (v) any combination of (i)-(iv).

4 . The curable composition of claim 1 , wherein in the epoxide-functional silicone-acrylate polymer (I) at least one siloxane moiety Y 1 comprises a siloxane group having the following general formula:

where 0≤n≤100, subscript o is from 2 to 6, subscript p is 0 or 1, subscript q is 0 or 1, subscript r is from 0 to 9, subscript s is 0 or 1, and subscript t is 0 or 2, with the provisos that subscript t is 0 when subscript s is 1, and subscript t is 2 when subscript s is 0.

5 . The curable composition of claim 1 , wherein in the epoxide-functional silicone-acrylate polymer (I) each siloxane moiety Y 1 is independently a siloxane group having one of the following formulas (i)-(vii):

where 1<n≤100 and subscript r is from 3 to 9.

6 . The curable composition of claim 1 , wherein in the epoxide-functional silicone-acrylate polymer (I) each divalent linking group D 1 comprises: (i) an independently selected linear alkylene group having from 2 to 6 carbon atoms; (ii) a tertiary amino group; or (iii) both (i) and (ii).

7 . The curable composition of claim 1 , wherein in the epoxide-functional silicone-acrylate polymer (I): (i) R 1 is CH 3 in each moiety indicated by subscript a; (ii) R 1 is CH 3 in each moiety indicated by subscript b; (iii) R 1 is H in each moiety indicated by subscript c; (iv) each R 2 is butyl; (v) each X 1 is an epoxypropyl group of formula

(vi) subscript b is comprises at least 30% of the total units indicated by subscripts a, b, and c; or (vii) any combination of (i)-(vi).

8 . The curable composition of claim 1 , wherein the aminosiloxane (II) has the general average unit formula [R 8 i SiO (4-i)/2 ] h , where: subscript h≥1; subscript i is independently selected from 1, 2, and 3 in each moiety indicated by subscript h, with the proviso that h+i>2; and each R 8 is independently selected from hydrocarbyl groups, alkoxy and/or aryloxy groups, siloxy groups, and amine groups, with the proviso that an average of at least two R 8 are amine groups per molecule.

9 . The curable composition of claim 1 , wherein the aminosiloxane (II) has the following general formula:
[R 10 R 9 2 SiO 1/2 ] x [R 10 R 9 SiO 2/2 ] y [R 10 siO 3/2 ] z , where each R 9 is an independently selected hydrocarbyl group; each R 10 is independently R 9 or an amino-functional hydrocarbon group, with the proviso that the aminosiloxane (II) comprises an average of at least two R 10 that are amino-functional hydrocarbon groups per molecule; and subscripts x, y, and z are each mole fractions such that x+y+z=1, with the provisos that 0≤x<1, 0<y<1, and 0<z<1.

10 . The curable composition of claim 9 , wherein: (i) each R 9 is CH 3 ; (ii) each amino-functional hydrocarbon group R 10 is an alkylamine having from 1 to 10 carbon atoms; (iii) subscript z is 0; (iv) the aminosiloxane (II) has a degree of polymerization of from 5 to 100; (v) the aminosiloxane (II) is miscible with the epoxide-functional silicone-acrylate polymer (I); or (vi) any combination of (i)-(v).

11 . A method of preparing the curable composition of claim 1 , said method comprising:
reacting (A) an acryloxy-functional organosilicon component, (B) an epoxy-functional acrylate component, and optionally (C) an acrylate component, to give the epoxide-functional silicone-acrylate polymer (I); and combining the epoxide-functional silicone-acrylate polymer (I) and the aminosiloxane (II) to give the curable composition;
wherein the acryloxy-functional organosilicon component (A) comprises an acryloxy-functional organosilicon monomer having the general formula:

the epoxy-functional acrylate component (B) comprises an oxiranyl acrylate ester monomer having the general formula:

and the optional acrylate component (C) comprises an acrylic ester monomer having the general formula:

where each R 1 , R 2 , D 1 , Y 1 , and X 1 is independently selected and as defined above.

12 . The method of claim 11 , wherein the acryloxy-functional organosilicon component (A) comprises an acryloxy-functional organosilicon monomer;
(i) R 1 is CH 3 ; (ii) D 1 comprises an independently selected linear alkylene group having from 2 to 6 carbon atoms, optionally substituted with an alkyl amino group; (iii) Y 1 comprises a siloxane group having general formula-Si (R 3 ) 3, where each R 3 is independently selected from R 4 and-OSi (R 5 ) 3, with the proviso that at least one R 3 is —OSi(R 5 ) 3 ; where each R 5 is independently selected from R 4 , —OSi(R 6 ) 3 , and —[—D 2 —SiR 4 2 ] m OSiR 4 3 ; where each R 6 is independently selected from R 4 , —OSi(R 7 ) 3 , and —[—D 2 —SiR 4 2 ] m OSiR 4 3 ; where each R 7 is independently selected from R 4 and —[—D 2 —SiR 4 2 ] m OSiR 4 3 ; where 0≤m≤100; where each D 2 is a divalent linking group; and where each R 4 is independently a substituted or unsubstituted hydrocarbyl group; or (iv) Y 1 comprises a siloxane group having the following general formula:

where 0<n≤100, s

Assignees

• Dow Silicones Corp
• Dow Global Technologies Llc

Inventors

• Vogel Erin B
• Drumright Ray E
• Cooper Richard
• Mecca Jodi M
• Lee Kangsang
• Lee Myoungbae
• Jeletic Matthew
• Ahn Dongchan

Classifications

• C08L83/08

  containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen · CPC title

• C09J143/04 Primary

  Homopolymers or copolymers of monomers containing silicon · CPC title

• C09D143/04

  Homopolymers or copolymers of monomers containing silicon · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08F30/08

  containing silicon · CPC title