Granted Patent B2

US 12,503,554 · App. 17/905,028 · Granted Dec 23, 2025

Inventors: Nanguo Liu (Midland, MI); Zachary Wenzlick (Midland, MI)

Assignee: Dow Silicones Corporation

C08G77/06C08G77/20C08G77/34

Abstract

Claims (57)

1 . A method for preparing a (meth)acrylate functional silicone, where the method comprises:

1) combining, under conditions to form a crude hydrolysis product, starting materials comprising

A) an alkoxysilyl-functional (meth)acrylate monomer,

B) water, and

C) an acid catalyst;

2) refining the crude hydrolysis, thereby forming a refined hydrolysis product;

3) combining, under conditions to form a condensation product, the refined hydrolysis product and starting materials comprising

D) a polydiorganosiloxane selected from the group consisting of

D1) an unsaturated polydiorganosiloxane having, per molecule, at least one silicon bonded aliphatically unsaturated group;

D2) a hydroxyl-functional polydiorganosiloxane having, per molecule, at least two silicon bonded hydroxyl groups, and

D3) a combination of D1) and D2);

E) a condensation reaction catalyst;

optionally F) a polydialkylsiloxane;

optionally G) a solvent; and

H) a free radical scavenger; thereby making a condensation reaction product comprising the (meth)acrylate functional silicone and a condensation by-product;

4) refining the condensation reaction product during and/or after step 3);

optionally 5) neutralizing the condensation reaction product; and

optionally 6) recovering the (meth)acrylate functional silicone, where the (meth)acrylate functional silicone comprises unit formula

(R 1 2 R 3 SiO 1/2 ) 2 (R 1 2 SiO 2/2 ) m (R 1 R 2 SiO 2/2 ) n , where

each R 1 is a monovalent hydrocarbon group free of aliphatic unsaturation,

each R 2 is a (meth)acryloxyalkyl functional group,

each R 3 is an aliphatically unsaturated monovalent hydrocarbon group, and

a quantity (m+n) is 500 to 10,000, and a ratio m/n is 1/1 to 500/1.

2 . The method of claim 1 , where starting material A) has formula R 2 R 1 Si(OR 1 ) 2 , where each R 1 is an independently selected monovalent hydrocarbon group free of aliphatic unsaturation, and each R 2 is an independently selected (meth)acryloxyalkyl functional group.

3 . The method of claim 1 , where starting material C) comprises HCl.

4 . The method of claim 1 , where starting material D-1) comprises unit formula D1-1):

(R 3 R 1 2 SiO 1/2 ) b (R 1 2 SiO 2/2 ) c (R 3 R 1 SiO 2/2 ) d (R 1 3 SiO 1/2 ) e (R′OR 1 2 SiO 1/2 ) f (R′OR 1 SiO 2/2 ) g , where each R 3 is an independently selected aliphatically unsaturated hydrocarbon group, each R 1 is an independently selected monovalent hydrocarbon group free of aliphatic unsaturation, each R′ is independently selected from the group consisting of H and R 1 , subscript b is 0, 1, or 2, subscript c≥1, subscript d≥0, subscript e is 0, 1, or 2, subscript f is 0, 1, or 2, and subscript g≥0, with the provisos that a quantity (b+d)≥1, a quantity (b+e+f)=2, and a quantity (b+c+d+e+f+g) is at least 3.

5 . The method of claim 1 , where starting material D-2) comprises unit formula D-2) comprises unit formula D-2-1):

(R 1 2 SiO 2/2 ) h (R 1 3 SiO 1/2 ) i (HOR 1 2 SiO 1/2 ) j , where each R 1 is an independently selected monovalent hydrocarbon group free of aliphatic unsaturation, subscript j is 1 or 2, subscript i is 0 or 1, a quantity (j+i)=2, subscript h≥1, and a quantity (h+i+j) is at least 3.

6 . The method of claim 1 , where starting material E) is a phosphonitrile halide.

7 . The method of claim 1 , where step 2) comprises filtration, stripping, and/or distillation.

8 . The method of claim 1 , where step 4) comprises filtration, stripping, and/or distillation.

9 . The method of claim 1 , where step 5) is present and step 5) comprises adding a neutralizing agent comprising an alkyl amine, such as trihexylamine or trioctylamine.

10 . The method of claim 1 , where step 6) is present, and step 6) comprises filtration, stripping, and/or distillation.

11 . The method of claim 2 , where each monovalent hydrocarbon group for R 1 is an alkyl group.

12 . The method of claim 2 , where each (meth)acryloxyalkyl functional group for R 2 is independently selected from the group consisting of acryloxypropyl and methacryloxypropyl.

13 . The method of claim 4 , where each aliphatically unsaturated monovalent hydrocarbon group for R 3 is an independently selected alkenyl group.

14 . A method for preparing a (meth)acrylate functional silicone, where the method comprises:

1) combining, under conditions to form a crude hydrolysis product, starting materials comprising

A) an alkoxysilyl-functional (meth)acrylate monomer,

B) water, and

C) an acid catalyst;

2) refining the crude hydrolysis, thereby forming a refined hydrolysis product;

3) combining, under conditions to form a condensation product, the refined hydrolysis product and starting materials comprising

D) a polydiorganosiloxane selected from the group consisting of

D1) an unsaturated polydiorganosiloxane having, per molecule, at least one silicon bonded aliphatically unsaturated group; and

a combination of D1) and D2), wherein

D2) is a hydroxyl-functional polydiorganosiloxane having, per molecule, at least two silicon bonded hydroxyl groups;

where starting material D-1) comprises unit formula D1-1): (R 3 R 1 2 SiO 1/2 ) b (R 1 2 SiO 2/2 ) c (R 3 R 1 SiO 2/2 ) d (R 1 3 SiO 1/2 ) e (R′OR 1 2 SiO 1/2 ) f (R′OR 1 SiO 2/2 ) g , where each R 3 is an independently selected aliphatically unsaturated hydrocarbon group, each R 1 is an independently selected monovalent hydrocarbon group free of aliphatic unsaturation, each R′ is independently selected from the group consisting of H and R 1 , subscript b is 0, 1, or 2, subscript c≥1, subscript d≥0, subscript e is 0, 1, or 2, subscript f is 0, 1, or 2, and subscript g≥0, with the provisos that a quantity (b+d)≥1, a quantity (b+e+f)=2, and a quantity (b+c+d+e+f+g) is at least 3;

E) a condensation reaction catalyst;

optionally F) a polydialkylsiloxane;

optionally G) a solvent; and

H) a free radical scavenger; thereby making a condensation reaction product comprising the (meth)acrylate functional silicone and a condensation by-product;

4) refining the condensation reaction product during and/or after step 3);

optionally 5) neutralizing the condensation reaction product; and

optionally 6) recovering the (meth)acrylate functional silicone.

15 . The method of claim 14 , where each aliphatically unsaturated monovalent hydrocarbon group for R 3 is an independently selected alkenyl group.

Assignments (1)

Continuity (2)

References Cited (94)