Silicone acrylate compositions and methods of preparing the same

Patent metadata

Field	Value
Publication number	US-10463737-B2
Application number	US-201615532362-A
Country	US
Kind code	B2
Filing date	Jan 29, 2016
Priority date	Jan 29, 2015
Publication date	Nov 5, 2019
Grant date	Nov 5, 2019

Abstract

Silicone acrylate copolymer composition, namely, silicone resin-acrylate copolymers and methods of preparing the same. The silicone acrylate composition may include a silicone resin coupled with an acrylate polymer via a linking group. The silicone acrylate composition may be formed by preparing an acrylate or a (meth)acrylate functional resin and carrying out acrylate polymerization in the presence of a functionalized resin. A silane-functional acrylate polymer may be prepared, followed by a reaction to couple a resin to the silane-functional acrylate polymer. The resulting copolymer may then be used as desired, e.g., added to a silicone and acrylate mixture to create a non-separating blend.

First claim

The invention claimed is:

1. A silicone acrylate having a general formula:

wherein
each R 1 is independently selected from hydrogen or methyl;
each R 2 and R 3 is independently selected from hydrogen alkyls, branched alkyls, methyl, ethyl, propyl, n-butyl, iso-butyl, tert-butyl, hexyl, 2-ethylhexyl, iso-octyl, iso-nonyl, iso-pentyl, tridecyl, stearyl, lauryl, and; and
each R 4 is a silane having the general formula:

wherein R 5 is selected from —(CH 2 ) 3 —NH—C(═O)—O—CH 2 —CH 2 —, —(CH 2 ) 3 —NH—CH 2 —CH(OH)—CH 2 —, and —OCH 2 —CH 2 —, and each R 6 , R 7 , and R 8 is independently selected from C1-C12 alkyl, phenyl, and —(CH 2 ) n —CH═CH 2 where n is from 0 to 6, or

and wherein each R is a silsesquioxane having the general formula:
[(R 9 ) 2 R 10 SiO 1/2 ] a [SiO 4/2 ] q [R 11 SiO 3/2 ] t [(R 12 ) 3 SiO 1/2 ] m ,
wherein R 9 is C1-12 alkyl, R 10 is —(CH 2 ) z —, where z is 3, R 11 is selected from phenyl, C1-C12 alkyl, —OH, isopropoxy, and —(CH 2 ) n —CH═CH 2 , where n is between 0 and 6, and R 12 is selected from C1-C12 alkyl, wherein a is from 1 to 5 per R unit, q is from 1 to 300, t is 0, m is from 4-300, and the ratio of m/q is between 10/90 to 90/10,

wherein the silicone acrylate includes between 0-99% w/w x groups, between 0-99% w/w y groups, 0% w/w s groups, and between 1-80% w/w r groups, where the % w/w of at least one of the x groups and the y groups is not zero.

2. A thermodynamically stable silicone acrylate blend comprising:
(a) a silicone acrylate composition having a general formula:

wherein
each R 1 is independently selected from hydrogen or methyl,
each R 2 and R 3 is independently selected from, hydrogen alkyls, branched alkyls, methyl, ethyl, propyl, n-butyl, iso-butyl, tert-butyl, hexyl, 2-ethylhexyl, iso-octyl, iso-nonyl, iso-pentyl, tridecyl, stearyl, lauryl, and,
each R 4 is a silane having the general formula

wherein R 5 is selected from —(CH 2 ) 3 —NH—C(═O)—O—CH 2 —CH 2 —, —(CH 2 ) 3 —NH—CH 2 —CH(OH)—CH 2 —, and —OCH 2 —CH 2 —, and
each R 6 , R 7 , and R 8 is independently selected from C1-C12 alkyl, phenyl, and —(CH 2 ) n —CH═CH 2 where n is from 0 to 6, or

wherein each R is a silsesquioxane having the general formula:
[(R 9 ) 2 R 10 SiO 1/2 ] a [SiO 4/2 ] q [R 11 SiO 3/2 ] t [(R 12 ) 3 SiO 1/2 ] m ,

wherein R 9 is C1-12 alkyl,
R 10 is —(CH 2 ) z —, where z is 3,
R 11 is selected from phenyl, C1-C12 alkyl, —OH, isopropoxy, and —(CH 2 ) n —CH═CH 2 where n is between 0 and 6, and
R 12 is selected from C1-C12 alkyl,
wherein a is from 1 to 5 per R unit, q is from 1 to 300, t is 0, m is from 4-300, and the ratio of m/q is between 10/90 to 90/10,
wherein the composition includes between 0-99% w/w x groups, between 0-99% w/w y groups, 0% w/w s groups, and between 1-80% w/w r groups, where the % w/w of at least one of the x groups and the y groups is not zero;

(b) a silicone pressure sensitive adhesive; and
(c) an acrylic polymer that is different from the silicone acrylate composition of (a),
wherein the silicone acrylate blend composition lacks covalent bonds between the composition, the silicone pressure sensitive adhesive, and the acrylic polymer.

3. The silicone acrylate blend composition of claim 2 , wherein the silicone pressure sensitive adhesive is selected from amine-compatible silicone adhesives and any combination thereof.

4. The silicone acrylate blend composition of claim 2 , wherein the pressure sensitive adhesive has the general formula:
[SiO 4/2 ] g [R 13 SiO 3/2 ] h [(R 14 ) 3 SiO 1/2 ] i [(R 14 ) 3 SiO 2/2 ] d ,
wherein R 13 is —OH, isopropoxy, or the combination thereof, and R 14 is C1-C12 alkyl wherein g is between 5-50 mol %, h is between 0.1-20 mol %, i is between 5-50 mol %, and d is between 5-90%, and wherein the weight ratio of (g+h+i)/d is between 10/90 to 90/10.

5. The silicone acrylate blend composition of claim 2 , wherein the silicone pressure sensitive adhesive is (a) silanol-functional.

6. The silicone acrylate blend composition of claim 2 , wherein the acrylic polymer is an acrylic polymer compound derived from methacrylic monomer, aliphatic acrylates, aliphatic methacrylates, cycloaliphatic acrylates, cycloaliphatic methacrylates, acrylamides, methacrylamides, hydroxy-functional (meth)acrylates, carboxy-functional (meth)acrylates, and any combination thereof, each having up to 20 carbon atoms in the alkyl radical.

7. The silicone acrylate blend composition of claim 6 , wherein the acrylic polymer is derived from aliphatic acrylates selected from methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, iso-octyl acrylate, iso-nonyl acrylate, iso-pentyl acrylate, tridecyl acrylate, stearyl acrylate, lauryl acrylate, and any combination thereof.

8. The silicone acrylate blend composition of claim 6 , wherein the acrylic polymer is derived from aliphatic methacrylates selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, iso-octyl methacrylate, iso-nonyl methacrylate, iso-pentyl methacrylate, tridecyl methacrylate, stearyl methacrylate, lauryl methacrylate, and any combination thereof.

9. A transdermal drug delivery system, comprising:
a silicone acrylate having a general formula:

wherein
each R 1 is independently selected from hydrogen or methyl,
each R 2 and R 3 is independently selected from hydrogen alkyls, branched alkyls, methyl, ethyl, propyl, n-butyl, iso-butyl, tert-butyl, hexyl, 2-ethylhexyl, iso-octyl, iso-nonyl, iso-pentyl, tridecyl, stearyl, lauryl, and,
each R 4 is a silane having the general formula

wherein R 5 is selected from —(CH 2 ) 3 —NH—C(═O)—O—CH 2 —CH 2 —, —(CH 2 ) 3 —NH—CH 2 —CH(OH)—CH 2 —, —(CH 2 ) 3 — and —OCH 2 —CH 2 —, and
each R 6 , R 7 , and R 8 is independently selected from C1-C12 alkyl, phenyl, and —(CH 2 ) n —CH═CH 2 where n is from 0 to 6, or

wherein each R is a silsesquioxane having the general formula:
[(R 9 ) 2 R 10 SiO 1/2 ] a [SiO 4/2 ] q [R 11 SiO 3/2 ] t [(R 12 ) 3 SiO 1/2 ] m ,

wherein R 9 is C1-12 alkyl,
R 10 is —(CH 2 ) z —, where z is 3,
R 11 is selected from phenyl, C1-C12 alkyl, —OH, isopropoxy, and —(CH 2 ) n —CH═CH 2 where n is between 0 and 6, and
R 12 is selected from C1-C12

Assignees

• Dow Corning

Inventors

• Huber Robert O
• Loubert Gary Lee
• Schalau Ii Gerald K
• Toth Simon

Classifications

• C09J151/00

  Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds (based on ABS polymers C09J155/02); Adhesives based on derivatives of such polymers · CPC title

• A61K47/24 Primary

  containing atoms other than carbon, hydrogen, oxygen, halogen, nitrogen or sulfur, e.g. cyclomethicone or phospholipids · CPC title

• A61K9/7061

  Polyacrylates · CPC title

• C08F275/00 Primary

  Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00 · CPC title

• C08F130/08

  containing silicon · CPC title