Silicone-poly acrylate copolymer, sealants comprising same, and related methods

Patent metadata

Field	Value
Publication number	US-12344712-B2
Application number	US-201917416474-A
Country	US
Kind code	B2
Filing date	Dec 16, 2019
Priority date	Dec 21, 2018
Publication date	Jul 1, 2025
Grant date	Jul 1, 2025

Abstract

A silicone-polyacrylate copolymer has the formula X g [Z j Y o ] c , where each X is an independently selected silicone moiety having a particular structure, each Y is an independently selected polyacrylate moiety, each Z is an independently selected siloxane moiety, subscript c is from 1 to 150, subscript g is >1, 0≤j<2, and 0<o<2, with the proviso that j+o=2 in each moiety indicated by subscript c. Methods of preparing the silicone-polyacrylate copolymer are also disclosed. Further, a sealant is disclosed, the sealant comprising the silicone-polyacrylate copolymer and a condensation-reaction catalyst.

First claim

What is claimed is:

1. A silicone-polyacrylate copolymer having the formula X g [Z j Y o ] c , wherein each X is independently a silicone moiety having one of formulas (I) or (II):

each Y comprises an independently selected polyacrylate moiety, and each Z is an independently selected siloxane moiety having the formula [R 1 h SiO (4-h)/2 ] d ,
where 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 selected from 0 to 2; each subscript b is independently 0 or 1; subscript c is from 1 to 150; each subscript d is from 1 to 1000; each subscript e is independently 1 or 2; each subscript f is independently 0 or 1, with the proviso that within each X, when f is 1, b is 1; subscript g is >1; subscript h is independently selected from 0 to 2 in each moiety indicated by subscript d; each subscript j is independently >0 and <2; each subscript o is independently >0 and <2, with the proviso that j+o=2 in each moiety indicated by subscript c; subscript t is ≥0, and subscript u is >0; and
where each silicone moiety X is bonded to a polyacrylate moiety Y.

2. The silicone-polyacrylate copolymer of claim 1 , wherein the silicone-polyacrylate copolymer has the formula: [XA] g [Z j Y 1 o ] c , wherein each Y 1 comprises a polyacrylate moiety, wherein each silicone moiety X is bonded to a polyacrylate moiety Y 1 via A, wherein each A is independently selected from a covalent bond, -D 2 -O-D 2 -O—C(═O)—NH-D 2 -NH—C(═O)O—, D 2 -O—C(═O)—NH-D 2 -NH—C(═O)O—, -D 2 -O—C(═O)—NH—, -D 2 -NH—C(═O)—NH—, -D 2 -NR 3 —CH 2 CH 2 C(═O)O—, and -D 2 -OC(═O)—CH 2 CH 2 NR 3 —, where D 2 is a divalent group and R 3 is H or R 1 , where R 1 is defined above.

3. The silicone-polyacrylate copolymer of claim 2 , wherein the silicone-polyacrylate copolymer has the formula:

wherein each X, Y 1 , A, R 1 , subscript c, and subscript d is defined above.

4. The silicone-polyacrylate copolymer of claim 1 , wherein at least one Y further comprises at least one moiety in addition to and different from the polyacrylate moiety, and optionally, wherein the moiety is selected from an alkylaluminoxane moiety, an alkylgermoxane moiety, a polythioester moiety, a polyether moiety, a polythioether moiety, a polyester moiety, a polyacrylonitrile moiety, a polyacrylamide moiety, a polycarbonate moiety, an epoxy moiety, a polyurethane moiety, a polyurea moiety, a polyacetal moiety, a polyolefin moiety, a polyvinyl alcohol moiety, a polyvinyl ester moiety, a polyvinyl ether moiety, a polyvinyl ketone moiety, a polyisobutylene moiety, a polychloroprene moiety, a polyisoprene moiety, a polybutadiene moiety, a polyvinylidiene moiety, a polyfluorocarbon moiety, a polychlorinated hydrocarbon moiety, a polyalkyne moiety, a polyamide moiety, a polyimide moiety, a polyimidazole moiety, a polyoxazole moiety, a polyoxazine moiety, a polyoxidiazole moiety, a polythiazole moiety, a polysulfone moiety, a polysulfide moiety, a polyketone moiety, a polyetherketone moiety, a polyanhydride moiety, a polyamine moiety, a polyimine moiety, a polyphosphazene moiety, a polysaccharide moiety, a polypeptide moiety, a polyisocyante moiety, a cellulosic moiety, and combinations thereof.

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

6. A method of preparing a silicone-polyacrylate copolymer, said method comprising:
reacting a polyacrylate compound having on average more than one unsaturated group and an endcapping organosilicon compound in the presence of a hydrosilylation catalyst to give the silicone-polyacrylate copolymer;
wherein the silicone-polyacrylate copolymer is the silicone-polyacrylate copolymer of any one of claim 1 .

7. The method of claim 6 , further comprising reacting, along with the polyacrylate compound and the endcapping organosilicon compound, at least one of: (i) a chain extending organosilicon compound and (ii) a hybridizing compound having on average more than one unsaturated group.

8. The method of claim 6 , wherein the polyacrylate compound has the formula:
Y[R 4 ] i ,
wherein each R 4 is independently selected from an acrylate group and an unsaturated group having from 2 to 14 carbon atoms; subscript i is >1; and Y is a polyacrylate moiety.

9. The method of claim 7 , further comprising reacting the chain extending organosilicon compound, and wherein the chain extending organosilicon compound comprises: (i) a linear silicon hydride functional organosilicon compound; (ii) a branched silicon hydride functional organosilicon compound; or (iii) both (i) and (ii).

10. The method of claim 9 , wherein the chain extending organosilicon compound comprises the linear silicon hydride functional organosilicon compound, and wherein the linear silicon hydride functional organosilicon compound has the formula:

wherein each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group having from 1 to 18 carbon atoms; and each subscript d′ is from 1 to 999.

11. The method of claim 6 , wherein the endcapping organosilicon compound has formula (III) or (IV):

wherein each R 1 , R 2 , D 1 , subscript a, subscript b, subscript e, subscript f, subscript t, and subscript u are as defined above.

12. A method of preparing a silicone-polyacrylate copolymer, said method comprising:
reacting an organic compound having one terminal unsaturated group and one terminal hydroxyl group with an endcapping organosilicon compound in the presence of a hydrosilylation catalyst to give a hydroxyl-functional intermediate;
reacting the hydroxyl-functional intermediate with a polyisocyanate to give an isocyanate-functional intermediate; and
reacting the isocyanate-functional intermediate, a polyacrylate compound having on average more than one hydroxyl group, and optionally a polysiloxane having on average more than one hydroxyl group, to give the silicone-polyacrylate copolymer;
wherein the silicone-polyacrylate copolymer is the silicone-polyacrylate copolymer of any one of claim 1 .

13. The method of claim 12 , wherein the endcapping organosilicon compound has formula (III) or (IV):

wherein each R 1 , R 2 , D 1 , subscript a, subscript b, subscript e, subscript f, subscript t, and subscript u are as defined above.

14. A sealant, comprising:
a silicone-polyacrylate copolymer; and
a condensation reaction catalyst;
wherein the silicone-polyacrylate copolymer is the silicone-polyacrylate copolymer of claim 1 .

15. The sealant of claim 14 , further comprising: (i) a filler; (ii) a filler treating agent; (iii) a cross-linker; (iv) a surface modifier, (v) a drying agent; (vi) an extender; (vii) a biocide; (viii) a flame retardant; (ix) a plasticizer; (x) an end-blocke

Assignees

• Dow Silicones Corp
• Dow Global Technologies Llc

Inventors

• Duquesne Emmanuel
• Ferritto Michael S
• Grasmann Martin
• Harkness Brian
• Johnson William
• Krishnan Bindu
• Santos Elizabeth
• Scherzer Justin
• Young Jeanette
• Zhu Bizhong

Classifications

• C08G81/024

  Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G · CPC title

• C08L83/10

  Block- or graft-copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00) · CPC title

• C09D183/14

  in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C09D183/10 takes precedence) · CPC title

• C09D183/10

  Block or graft copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00) · CPC title

• C09K2200/0625

  Polyacrylic esters or derivatives thereof · CPC title