US4624998A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Silicone-modified epoxy resins having improved impact resistance
Assignee: Dow Silicones Corp
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Filing: 1985-12-30
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Granted: 1986-11-25
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Expires: 2005-12-30
Abstract
Abstract This invention relates to a dispersion of a functional silicone modifier in a curable epoxy resin wherein emulsification of said silicone is aided by a siloxane-polyoxyalkylene copolymer. The silicone modifier comprises an alpha,omega-functional polydimethylsiloxane having carboxyl, amine or epoxide endgroups. A method of using the dispersion to improve the impact resistance of the resin, when the latter is cured, is described.
Inventors
- 👤 Joseph W. Keil
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 17:54
CPC Classifications
C; C08; C08L; C08L63/00
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
435 words
A dispersion comprising: a. from about 78 to 94.5 percent by weight of a curable epoxy resin; b. from about 5 to 20 percent by weight of an alpha,omega-functional polydimethylsiloxane having an average degree of polymerization between 30 and 400 and having endblocking groups containing carboxyl, amine or epoxide functionality; and c. from about 0.5 to 2.0 percent by weight of a dispersing agent capable of maintaining (b) dispersed in (a), said dispersing agent being a siloxane copolymer selected from the group consisting of 1. copolymers consisting essentially of SiO 2 units, (CH 3 ) 3 SiO 1/2 units and D(CH 3 ) 2 SiO 1/2 units in which D is a polyoxyethylene polymer having a molecular weight between 1000 and 5000, or a polyoxyethylene-polyoxypropylene copolymer having a molecular weight between 1000 and 6000 wherein the polyoxypropylene portion constitutes up to 100 mole percent of the copolymer, said D being attached to the silicon atom via a silicon-carbon bond, and the ratio of the SiO 2 units to the total (CH 3 ) 3 SiO 1/2 and D(CH 3 ) 2 SiO 1/2 units is in the range of 1:0.4 to 1:1.2, 2. copolymers which are reaction products derived from heating a mixture of a siloxane resin copolymer consisting essentially of SiO 2 units and (CH 3 ) 3 SiO 1/2 units in which the ratio of SiO 2 units to (CH 3 ) 3 SiO 1/2 units is in the range of 1:0.4 to 1:1.2, and a hydroxylated polyoxyethylene polymer having a molecular weight in the range of 1000 to 5000 or a hydroxylated polyoxyethylene-polyoxypropylene copolymer having a molecular weight in the range of 1000 to 6000 wherein the polyoxypropylene portion constitutes up to 100 mole percent of the copolymer, 3. polydimethylsiloxane-organic copolymer in which the polydimethylsiloxane portion has a molecular weight between 1500 and 2000 and the organic portion consists essentially of a polyoxyethylene polymer having a molecular weight between 1000 and 2000, or a polyoxyethylene-polyoxypropylene copolymer having a molecular weight between 1500 and 4000 wherein said polyoxypropylene portion constitutes up to 100 mole percent of organic portion of the copolymer, said organic portion being attached to silicon atoms via silicon-carbon bonds, and 4. polydimethylsiloxane-organic copolymers which are the reaction products produced by heating a mixture of a polydimethylsiloxane containing silicon bonded hydrogen atoms having a molecular weight between 1500 and 2000 and a hydroxylated polyoxyethylene having a molecular weight between 1000 and 2000, or a hydroxylated polyoxyethylene-polyoxypropylene copolymer having a molecular weight between 1500 and 4000 wherein said polyoxypropylene constitutes up to 100 mole percent of the organic portion of the copolymer.
Claim 2
Dependent Claim
435 words
A dispersion comprising: a. from about 78 to 94.5 percent by weight of a curable epoxy resin; b. from about 5 to 20 percent by weight of an alpha,omega-functional polydimethylsiloxane having an average degree of polymerization between 30 and 400 and having endblocking groups containing carboxyl, amine or epoxide functionality; and c. from about 0.5 to 2.0 percent by weight of a dispersing agent capable of maintaining (b) dispersed in (a), said dispersing agent being a siloxane copolymer selected from the group consisting of 1. copolymers consisting essentially of SiO 2 units, (CH 3 ) 3 SiO 1/2 units and D(CH 3 ) 2 SiO 1/2 units in which D is a polyoxyethylene polymer having a molecular weight between 1000 and 5000, or a polyoxyethylene-polyoxypropylene copolymer having a molecular weight between 1000 and 6000 wherein the polyoxypropylene portion constitutes up to 100 mole percent of the copolymer, said D being attached to the silicon atom via a silicon-carbon bond, and the ratio of the SiO 2 units to the total (CH 3 ) 3 SiO 1/2 and D(CH 3 ) 2 SiO 1/2 units is in the range of 1:0.4 to 1:1.2, 2. copolymers which are reaction products derived from heating a mixture of a siloxane resin copolymer consisting essentially of SiO 2 units and (CH 3 ) 3 SiO 1/2 units in which the ratio of SiO 2 units to (CH 3 ) 3 SiO 1/2 units is in the range of 1:0.4 to 1:1.2, and a hydroxylated polyoxyethylene polymer having a molecular weight in the range of 1000 to 5000 or a hydroxylated polyoxyethylene-polyoxypropylene copolymer having a molecular weight in the range of 1000 to 6000 wherein the polyoxypropylene portion constitutes up to 100 mole percent of the copolymer, 3. polydimethylsiloxane-organic copolymer in which the polydimethylsiloxane portion has a molecular weight between 1500 and 2000 and the organic portion consists essentially of a polyoxyethylene polymer having a molecular weight between 1000 and 2000, or a polyoxyethylene-polyoxypropylene copolymer having a molecular weight between 1500 and 4000 wherein said polyoxypropylene portion constitutes up to 100 mole percent of organic portion of the copolymer, said organic portion being attached to silicon atoms via silicon-carbon bonds, and 4. polydimethylsiloxane-organic copolymers which are the reaction products produced by heating a mixture of a polydimethylsiloxane containing silicon bonded hydrogen atoms having a molecular weight between 1500 and 2000 and a hydroxylated polyoxyethylene having a molecular weight between 1000 and 2000, or a hydroxylated polyoxyethylene-polyoxypropylene copolymer having a molecular weight between 1500 and 4000 wherein said polyoxypropylene constitutes up to 100 mole percent of the organic portion of the copolymer.
Claim 3
Dependent Claim
24 words
The dispersion of claim 1, wherein said endblocking group of component (b) is represented by a formula selected from the group consisting of ##STR7##
Claim 4
Dependent Claim
15 words
The dispersion of claim 1, wherein the dispersing agent (c) is the copolymeric product (1).
Claim 5
Dependent Claim
15 words
The dispersion of claim 1, wherein the dispersing agent (c) is the copolymeric product (2).
Claim 6
Dependent Claim
15 words
The dispersion of claim 1, wherein the dispersing agent (c) is the copolymeric product (3).
Claim 7
Dependent Claim
15 words
The dispersion of claim 1, wherein the dispersing agent (c) is the copolymeric product (4).
Claim 8
Dependent Claim
28 words
The dispersion of claim 4, wherein said alpha,omega-functional polydimethylsiloxane has an average degree of polymerization from 30 to 300 and constitutes from 5 to 10% of the dispersion.
Claim 9
Dependent Claim
22 words
The dispersion of claim 7, wherein said alpha,omega-functional polydimethylsiloxane is endblocked with groups represented by the formula --C 10 H 20 COOH.
Claim 10
Dependent Claim
18 words
The dispersion of claim 7, wherein said alpha,omega-functional polydimethylsiloxane is endblocked with groups represented by the formula ##STR8##
Claim 11
Dependent Claim
26 words
The dispersion of claim 7, wherein said alpha,omega-functional polydimethylsiloxane is endblocked with groups represented by the formula --CH 2 CH 2 CH 2 --NH 2 .
Claim 12
Dependent Claim
19 words
The dispersion of claim 7, wherein said alpha,omega-functional polydimethylsiloxane is endblocked with groups represented by the the formula ##STR9##
Claim 13
Dependent Claim
18 words
The dispersion of claim 7, wherein said alpha,omega-functional polydimethylsiloxane is endblocked with groups represented by the formula ##STR10##
Claim 14
Independent Claim
458 words
A method for improving the impact resistance of a curable epoxy resin, comprising: (A) emulsifying in an epoxy resin from about 5 to 20 percent by weight of an alpha,omega-functional polydimethylsiloxane having an average degree of polymerization between 30 and 400 and having endblocking groups containing carboxyl, amine or epoxide functionally, using as dispersing agent from about 0.5 to 2.0 percent by weight of a copolymer selected from the group consisting of 1. copolymers consisting essentially of SiO 2 units, (CH 3 ) 3 SiO 1/2 units and D(CH 3 ) 2 SiO 1/2 units in which D is a polyoxyethylene polymer having a molecular weight between 1000 and 5000, or a polyoxyethylene-polyoxypropylene copolymer having a molecular weight between 1000 and 6000 wherein the polyoxypropylene portion constitutes up to 100 mole percent of the copolymer, said D being attached to the silicon atom via a silicon-carbon bond, and the ratio of the SiO 2 units to the total (CH 3 ) 3 SiO 1/2 and D(CH 3 ) 2 SiO 1/2 units is in the range of 1:0.4 to 1:1.2. 2. copolymers which are reaction products derived from heating a mixture of a siloxane resin copolymer consisting essentially of SiO 2 units and (CH 3 ) 3 SiO 1/2 units in which the ratio of SiO 2 units to (CH 3 ) 3 SiO 1/2 units is in the range of 1:0.4 to 1:1.2, and a hydroxylated polyoxyethylene polymer having a molecular weight in the range of 1000 to 5000 or a hydroxylated polyoxyethylene-polyoxypropylene copolymer having molecular weight in the range of 1000 to 6000 wherein the polyoxypropylene portion constitutes up to 100 mole percent of the copolymer, 3. polydimethylsiloxane-organic copolymer in which the polydimethylsiloxane portion has a molecular weight between 1500 and 2000 and the organic portion consists essentially of a polyoxyethylene polymer having a molecular weight between 1000 and 2000, or a polyoxyethylene-polyoxypropylene copolymer having a molecular weight between 1500 and 4000 wherein said polyoxypropylene portion constitutes up to 100 mole percent of organic portion of the copolymer, said organic portion being attached to silicon atoms via silicon-carbon bonds, and 4. polydimethylsiloxane-organic copolymers which are the reaction products produced by heating a mixture of a polydimethylsiloxane containing silicon bonded hydrogen atoms having a molecular weight between 1500 and 2000 and a hydroxylated polyoxyethylene having a molecular weight between 1000 and 2000, or a hydroxylated polyoxyethylene-polyoxypropylene copolymer haing a molecular weight between 1500 and 4000 wherein said polyoxypropylene constitutes up to 100 mole percent of the organic portion of the copolymer to form a homogeneous dispersion; (B) mixing said dispersion with an appropriate amount of a cure agent for the epoxy resin to produce a uniform mixture therebetween; and (C) curing the mixture obtained in step B.
Claim 15
Independent Claim
458 words
A method for improving the impact resistance of a curable epoxy resin, comprising: (A) emulsifying in an epoxy resin from about 5 to 20 percent by weight of an alpha,omega-functional polydimethylsiloxane having an average degree of polymerization between 30 and 400 and having endblocking groups containing carboxyl, amine or epoxide functionally, using as dispersing agent from about 0.5 to 2.0 percent by weight of a copolymer selected from the group consisting of 1. copolymers consisting essentially of SiO 2 units, (CH 3 ) 3 SiO 1/2 units and D(CH 3 ) 2 SiO 1/2 units in which D is a polyoxyethylene polymer having a molecular weight between 1000 and 5000, or a polyoxyethylene-polyoxypropylene copolymer having a molecular weight between 1000 and 6000 wherein the polyoxypropylene portion constitutes up to 100 mole percent of the copolymer, said D being attached to the silicon atom via a silicon-carbon bond, and the ratio of the SiO 2 units to the total (CH 3 ) 3 SiO 1/2 and D(CH 3 ) 2 SiO 1/2 units is in the range of 1:0.4 to 1:1.2. 2. copolymers which are reaction products derived from heating a mixture of a siloxane resin copolymer consisting essentially of SiO 2 units and (CH 3 ) 3 SiO 1/2 units in which the ratio of SiO 2 units to (CH 3 ) 3 SiO 1/2 units is in the range of 1:0.4 to 1:1.2, and a hydroxylated polyoxyethylene polymer having a molecular weight in the range of 1000 to 5000 or a hydroxylated polyoxyethylene-polyoxypropylene copolymer having molecular weight in the range of 1000 to 6000 wherein the polyoxypropylene portion constitutes up to 100 mole percent of the copolymer, 3. polydimethylsiloxane-organic copolymer in which the polydimethylsiloxane portion has a molecular weight between 1500 and 2000 and the organic portion consists essentially of a polyoxyethylene polymer having a molecular weight between 1000 and 2000, or a polyoxyethylene-polyoxypropylene copolymer having a molecular weight between 1500 and 4000 wherein said polyoxypropylene portion constitutes up to 100 mole percent of organic portion of the copolymer, said organic portion being attached to silicon atoms via silicon-carbon bonds, and 4. polydimethylsiloxane-organic copolymers which are the reaction products produced by heating a mixture of a polydimethylsiloxane containing silicon bonded hydrogen atoms having a molecular weight between 1500 and 2000 and a hydroxylated polyoxyethylene having a molecular weight between 1000 and 2000, or a hydroxylated polyoxyethylene-polyoxypropylene copolymer haing a molecular weight between 1500 and 4000 wherein said polyoxypropylene constitutes up to 100 mole percent of the organic portion of the copolymer to form a homogeneous dispersion; (B) mixing said dispersion with an appropriate amount of a cure agent for the epoxy resin to produce a uniform mixture therebetween; and (C) curing the mixture obtained in step B.
Claim 16
Dependent Claim
24 words
The method of claim 13, wherein said endblocking group of component (b) is represented by a formula selected from the group consisting of ##STR11##
Claim 17
Dependent Claim
14 words
The method of claim 13, wherein said dispersing agent is the copolymeric product 2.
Claim 18
Dependent Claim
31 words
The method of claim 15, wherein said alpha,omega-functional polydimethylsiloxane has a degree of polymerization from 30 to 300 and constitutes from 5 to 10 percent of the dispersion of step A.
Claim 19
Dependent Claim
15 words
An article of manufacture, comprising a cured epoxy composite prepared in accordance with claim 13.
Claim 20
Dependent Claim
15 words
An article of manufacture, comprising a cured epoxy composite prepared in accordance with claim 14.
Claim 21
Dependent Claim
15 words
An article of manufacture, comprising a cured epoxy composite prepared in accordance with claim 15.
Claim 22
Dependent Claim
15 words
An article of manufacture, comprising a cured epoxy composite prepared in accordance with claim 16.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1989-11-24 | 1990-05-26 | 1990-11-25 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1993-11-24 | 1994-05-26 | 1994-11-25 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1997-11-24 | 1998-05-26 | 1998-11-25 | $7700.00 | Window Closed / Lapsed |