CA2477945A1 - Hydrosilylation cure of silicone resin containing colloidal silica and a process for producing the same - Google Patents

Hydrosilylation cure of silicone resin containing colloidal silica and a process for producing the same Download PDF

Info

Publication number
CA2477945A1
CA2477945A1 CA002477945A CA2477945A CA2477945A1 CA 2477945 A1 CA2477945 A1 CA 2477945A1 CA 002477945 A CA002477945 A CA 002477945A CA 2477945 A CA2477945 A CA 2477945A CA 2477945 A1 CA2477945 A1 CA 2477945A1
Authority
CA
Canada
Prior art keywords
curable composition
hydrosilylation reaction
colloidal silica
group
reaction curable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CA002477945A
Other languages
French (fr)
Other versions
CA2477945C (en
Inventor
Zhongtao Li
Frederick J. Mcgarry
Dimitris E. Katsoulis
John R. Keryk
Debora F. Bergstrom
Kermit S. Kwan
Bizhong Zhu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Massachusetts Institute of Technology
Dow Silicones Corp
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2477945A1 publication Critical patent/CA2477945A1/en
Application granted granted Critical
Publication of CA2477945C publication Critical patent/CA2477945C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/5403—Silicon-containing compounds containing no other elements than carbon or hydrogen

Abstract

A hydrosilylation reaction curable composition including a silsesquioxane polymer, a cross-linking compound, a hydrosilylation reaction catalyst and colloidal silica having a surface coating formed thereon. The curable composition is cured to form a cured resin having high fracture toughness and strength without the loss of elastic modulus and glass transition temperature.

Claims (33)

1. ~A hydrosilylation reaction curable composition comprising:
a) a silsesquioxane polymer b) a cross-linking compound;
c) a hydrosilylation reaction catalyst;
d) Colloidal silica having a surface coating formed thereon.
2. ~The hydrosilylation reaction curable composition of Claim 1 further including an optional reaction inhibitor.
3. ~The hydrosilylation reaction curable composition of Claim 1 wherein the silsesquioxane resin comprises a copolymer resin.
4. ~The hydrosilylation reaction curable composition of Claim 3 wherein the copolymer resin comprises, a copolymer resin having the empirical formula R1a R2b R3c SIO(4-a-b-c)/2, wherein: a is zero or a positive number, b is zero or a positive number, c is zero or a positive number, with the provisos that 0.8 <=
(a+b+c) <= 3.0 and component (A) has an average of at least 2 R1 groups per molecule, and each R1 is independently selected from monovalent hydrocarbon groups having aliphatic unsaturation, and each R2 and each R3 are independently selected from monovalent hydrocarbon groups and hydrogen.
5. The hydrosilylation reaction curable composition of Claim 4 wherein the silsesquioxane resin comprises (PhSiO 3/2).75 (ViMe2 SIO 1/2).25, where Ph is a phenyl group, Vi represents a vinyl group, and Me represents a methyl group.
6. The hydrosilylation reaction curable composition of Claim 1 wherein the cross-linking compound is selected from the group consisting of: 1) a silicon hydride containing hydrocarbon having the general formula: H a R1b SiR2Si R1c H d where R1 is a monovalent hydrocarbon group and R2 is a divalent hydrocarbon group and where a and d >= 1, and a+b=c+d=3, 2) a silicon hydride containing hydrocarbon having the general formula: Ha R1b SiR2Si R1c H d where R1 is a monovalent hydrocarbon group and R2 is a trivalent hydrocarbon group and where a and d >= 1, and a+b=c+d=3, 3) a silane having at least two silicon hydride functionalities, 4) a siloxane having at least two silicon hydride functionalities, or mixtures of the above.
7. The hydrosilylation reaction curable composition of Claim 6 wherein the cross-linking compound is selected from the group consisting of: p-bis(dimethylsilyl)benzene, diphenylsilane, hexamethyltrisiloxane, and 1,3,5 trisdimethylsilylbenzene.
8. The hydrosilylation reaction curable composition of Claim 1 wherein the colloidal silica comprises from 5 to 25 weight percent of the hydrosilylation reaction curable composition.
9. The hydrosilylation reaction curable composition of Claim 1 wherein the colloidal silica has a particle size of from 5 to 100 nanometers in diameter.
10. The hydrosilylation reaction curable composition of Claim 1 wherein the colloidal silica has a reactive silane or siloxane coating.
11. The hydrosilylation reaction curable composition of Claim 1 wherein the colloidal silica has a surface coating of trimethylsiloxy groups.
12. The hydrosilylation reaction curable composition of Claim 1 wherein the colloidal silica has a surface coating of trimethylsiloxy and vinyldimethylsiloxy groups.
13. The hydrosilylation reaction curable composition of Claim 12 wherein the surface coating has a molar ratio of from 0.2 to 0.9 of vinyldimethylsiloxy to trimethylsiloxy groups.
14. The hydrosilylation reaction curable composition of Claim 1 wherein the colloidal silica is dispersed in a solvent.
15. The hydrosilylation reaction curable composition of Claim 14 wherein the solvent is selected from the group consisting of toluene and xylene.
16. A process for preparing a hydrosilyation reaction curable composition comprising the steps of:
a) providing a silsesquioxane polymer;
b) providing a cross-linking compound;
c) providing colloidal silica with a surface treatment formed thereon;
d) mixing the components of a), b), c) to form a curable composition;
e) adding a hydrosilylation reaction catalyst to the curable composition of step d) f) curing the curable composition of step e) to form a cured resin having high fracture toughness and strength without the loss of elastic modulus and glass transition temperature.
17. The process of Claim 16 wherein the step of mixing is performed in a conventional mixer.
18. The process of Claim16 wherein the step of mixing is performed in a high shear rotor/stator mixer.
19. The process of Claim 16 wherein the silsesquioxane polymer is first mixed with the cross-linking compound and then mixed with the colloidal silica to form the curable composition of step e).
20. The process of Claim 16 wherein the curing step includes the steps of: 1) leaving the curable composition of step e) in a mold at room temperature overnight, 2) curing the curable composition in the mold at a temperature of 60°C
for 6 hours, 3) curing the curable composition in the mold at a temperature of 100°C for 2 hours, 4) curing the curable composition in the mold at a temperature of 160°C for 2 hours, 5) curing the curable composition in the mold at a temperature of 200°C for 3 hours, 6) curing the curable composition in the mold at a temperature of 260°C for 6 hours.
21. The process of Claim 16 wherein the silsesquioxane resin comprises a copolymer resin.
22. The process of Claim 21 wherein the copolymer resin comprises, a copolymer resin having the empirical formula R1aR2bR3cSiO(4-a-b-c)/2, wherein:
a is zero or a positive number, b is zero or a positive number, c is zero or a positive number, with the provisos that 0.8 <= (a+b+c)<= 3.0 and component (A) has an average of at least 2 R1 groups per molecule, and each R1 is independently selected from monovalent hydrocarbon groups having aliphatic unsaturation, and each R2 and each R3 independently selected monovalent hydrocarbon groups and hydrogen.
23. The process of Claim 22 wherein the silsesquioxane resin comprises (PhSiO 3/2).75 (ViMe2 SiO 1/2).25, where Ph is a phenyl group, Vi represents a vinyl group, and Me represents a methyl group.
24. The process of Claim 1 wherein the cross-linking compound is selected from the group consisting of: 1) a silicon hydride containing hydrocarbon having the general formula: H a R1b SiR2Si R1c H d where R1 is a monovalent hydrocarbon group and R2 is a divalent hydrocarbon group and where a and d >= 1, and a+b=c+d=3, 2) a silicon hydride containing hydrocarbon having the general formula: H a R1b SiR2Si R1c H d where R1 is a monovalent hydrocarbon group and is a trivalent hydrocarbon group and where a and d >= 1, and a+b=c+d=3, 3) a
25 silane having at least two silicon hydride functionalities, 4) a siloxane having at least two silicon hydride functionalities, or mixtures of the above.
25. The process of Claim 24 wherein the cross-linking resin is selected from the group consisting of: p-bis(dimethylsilyl)benzene, diphenylsilane, hexamethyltrisiloxane, and 1,3,5 trisdimethylsilylbenzene.
26. The process of Claim 16 wherein the colloidal silica comprises from 5 to weight percent of the hydrosilylation reaction curable composition.
27. The process of Claim 16 wherein the colloidal silica has a particle size of from 5 to 100 nanometers in diameter.
28. The process of Claim 16 wherein the colloidal silica has a surface coating of trimethylsiloxy groups.
29. The process of Claim 16 wherein the colloidal silica has a surface coating of trimethylsiloxy and vinyldimethylsiloxy groups.
30. The process of Claim 29 wherein the surface coating has a molar ratio of from 0.2 to 0.9 of vinyldimethylsiloxy to trimethylsiloxy groups.
31. The process of Claim 16 wherein the colloidal silica is dispersed in a solvent.
32. The process of Claim 31 wherein the solvent is selected from the group consisting of toluene and xylene.
33. The process of Claim 16 further including the step of adding an optional reaction inhibitor.
CA2477945A 2002-03-05 2003-02-20 Hydrosilylation cure of silicone resin containing colloidal silica and a process for producing the same Expired - Fee Related CA2477945C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10/091,685 US6646039B2 (en) 2002-03-05 2002-03-05 Hydrosilyation cured silicone resin containing colloidal silica and a process for producing the same
US10/091,685 2002-03-05
PCT/US2003/005355 WO2003076182A1 (en) 2002-03-05 2003-02-20 Hydrosilylation cure of silicone resin containing colloidal silica and a process for producing the same

Publications (2)

Publication Number Publication Date
CA2477945A1 true CA2477945A1 (en) 2003-09-18
CA2477945C CA2477945C (en) 2012-01-03

Family

ID=27804131

Family Applications (1)

Application Number Title Priority Date Filing Date
CA2477945A Expired - Fee Related CA2477945C (en) 2002-03-05 2003-02-20 Hydrosilylation cure of silicone resin containing colloidal silica and a process for producing the same

Country Status (10)

Country Link
US (1) US6646039B2 (en)
EP (1) EP1483112B1 (en)
JP (1) JP4601962B2 (en)
KR (1) KR100991968B1 (en)
CN (1) CN100335265C (en)
AT (1) ATE347484T1 (en)
AU (1) AU2003230561A1 (en)
CA (1) CA2477945C (en)
DE (1) DE60310206T2 (en)
WO (1) WO2003076182A1 (en)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6310146B1 (en) * 1999-07-01 2001-10-30 Dow Corning Corporation Silsesquioxane resin with high strength and fracture toughness and method for the preparation thereof
US6689859B2 (en) * 2002-03-05 2004-02-10 Dow Corning Corporation High fracture toughness hydrosilyation cured silicone resin
US6750273B2 (en) * 2002-10-02 2004-06-15 Dow Corning Corporation Filled silicone composition and cured silicone product
WO2005017058A1 (en) * 2003-08-01 2005-02-24 Dow Corning Corporation Silicone based dielectric coatings and films for photovoltaic applications
JP2005089671A (en) 2003-09-19 2005-04-07 Shin Etsu Chem Co Ltd Curable silicone resin composition
WO2006055231A1 (en) * 2004-11-19 2006-05-26 Dow Corning Corporation Silicone composition and cured silicone resin
ATE409207T1 (en) * 2004-11-19 2008-10-15 Dow Corning COMPOSITION OF ORGANOHYDROGEN POLYSILOXANE RESIN AND SILICON
US7691459B2 (en) * 2005-03-22 2010-04-06 Fujifilm Corporation Inorganic fine particle-containing composition, optical film, antireflection film and polarizing film, and polarizing plate and display device using the same
US20080221263A1 (en) * 2006-08-31 2008-09-11 Subbareddy Kanagasabapathy Coating compositions for producing transparent super-hydrophobic surfaces
US7919225B2 (en) * 2008-05-23 2011-04-05 International Business Machines Corporation Photopatternable dielectric materials for BEOL applications and methods for use
CN102272231B (en) * 2008-11-19 2013-10-30 陶氏康宁公司 Silicone composition and method for preparing same
US20130026507A1 (en) * 2009-07-06 2013-01-31 Paragon Semiconductor Lighting Technology Co., Ltd. Multichip package structure and method of manufacturing the same
TWI464920B (en) * 2012-01-19 2014-12-11 Paragon Sc Lighting Tech Co Multi-chip package structure and method of manufacturing the same
WO2014014542A2 (en) 2012-04-27 2014-01-23 Burning Bush Group High performance silicon based coating compositions
US10138381B2 (en) 2012-05-10 2018-11-27 Burning Bush Group, Llc High performance silicon based thermal coating compositions
CN107236453B (en) 2012-07-03 2019-06-11 伯宁布什集团有限公司 Silicon substrate high performance paint composition
US9006355B1 (en) * 2013-10-04 2015-04-14 Burning Bush Group, Llc High performance silicon-based compositions
WO2015194159A1 (en) * 2014-06-20 2015-12-23 東レ・ダウコーニング株式会社 Organopolysiloxane and method for producing same
JP6741678B2 (en) * 2015-03-20 2020-08-19 ダウ・東レ株式会社 Organopolysiloxane, method for producing the same, and curable silicone composition
JP6347237B2 (en) * 2015-08-21 2018-06-27 信越化学工業株式会社 Addition-curing organopolysiloxane composition and semiconductor device

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2656319B1 (en) * 1989-12-27 1992-03-20 Rhone Poulenc Chimie MAGNETISABLE COMPOSITE MICROSPHERES BASED ON A CROSSLINKED ORGANOSILICY POLYMER, THEIR PREPARATION PROCESS AND THEIR APPLICATION IN BIOLOGY.
US5110845A (en) * 1990-12-03 1992-05-05 Dow Corning Corporation Extrudable curable organosiloxane compositions
JP3024439B2 (en) * 1993-06-07 2000-03-21 信越化学工業株式会社 Organopolysiloxane composition
US5623030A (en) * 1994-12-01 1997-04-22 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Curable composition and process for producing molded articles using the same
EP0850998B1 (en) * 1996-12-31 2004-04-28 Dow Corning Corporation Method for making rubber-modified rigid silicone resins and composites produced therefrom
JP3635180B2 (en) * 1997-02-24 2005-04-06 ダウ コーニング アジア株式会社 Silylated polymethylsilsesquioxane, process for producing the same, and composition using the same
US6252030B1 (en) * 1999-03-17 2001-06-26 Dow Corning Asia, Ltd. Hydrogenated octasilsesquioxane-vinyl group-containing copolymer and method for manufacture
US6310146B1 (en) * 1999-07-01 2001-10-30 Dow Corning Corporation Silsesquioxane resin with high strength and fracture toughness and method for the preparation thereof
JP2001089662A (en) * 1999-09-22 2001-04-03 Kanegafuchi Chem Ind Co Ltd Curable composition and method of producing molding using the same
US6509423B1 (en) * 2001-08-21 2003-01-21 Dow Corning Corporation Silicone composition and cured silicone product
US6689859B2 (en) * 2002-03-05 2004-02-10 Dow Corning Corporation High fracture toughness hydrosilyation cured silicone resin

Also Published As

Publication number Publication date
DE60310206T2 (en) 2007-09-13
EP1483112B1 (en) 2006-12-06
AU2003230561A1 (en) 2003-09-22
CA2477945C (en) 2012-01-03
JP4601962B2 (en) 2010-12-22
KR100991968B1 (en) 2010-11-04
EP1483112A4 (en) 2005-03-23
WO2003076182A1 (en) 2003-09-18
CN100335265C (en) 2007-09-05
ATE347484T1 (en) 2006-12-15
US20030171476A1 (en) 2003-09-11
DE60310206D1 (en) 2007-01-18
JP2005519171A (en) 2005-06-30
US6646039B2 (en) 2003-11-11
KR20050014794A (en) 2005-02-07
CN1642732A (en) 2005-07-20
EP1483112A1 (en) 2004-12-08

Similar Documents

Publication Publication Date Title
CA2477945A1 (en) Hydrosilylation cure of silicone resin containing colloidal silica and a process for producing the same
CA2477970A1 (en) High fracture toughness hydrosilyation cured silicone resin
US7446155B2 (en) Cross-linked networks containing nanoscopic reinforcing domains
JP5426613B2 (en) Rubber-modified hard silicone resin and method for producing the same
CN100354373C (en) Self-adhesive, addition cross-linking silicone-rubber blends, method for their production, method for producing composite moulded parts and use of the latter
US4678688A (en) Method for forming a surface film of cured organosilicon polymer on a substrate surface
AU2003225538B2 (en) Elastomer-modified epoxy siloxane compositions
EP0725103B1 (en) Thermosetting silicone resins
US5747608A (en) Rubber-modified rigid silicone resins and composites produced therefrom
JPH0678433B2 (en) UV curable silicone copolymer and method for producing the same
JPS6315298B2 (en)
JP2008512559A (en) High temperature nanocomposite resin
CN113913024A (en) Addition type liquid silicone rubber, vulcanized rubber and preparation method thereof
JPH06345971A (en) One-pack curable silicone composition
JP3975305B2 (en) Epoxy resin composition and molded body
US5596060A (en) Curable polytitanosiloxane compositions and method for preparing cured polytitanosiloxanes using said compositions
JPWO2005063843A1 (en) Curable silicone composition and cured product thereof
JP5481610B2 (en) Coating composition, method for producing transparent protective film using coating composition, and organic glass having transparent protective film
WO2001005846A1 (en) Resin-reinforced uv, moisture and uv/moisture dual curable silicone compositions
JPH03766A (en) Polyorganosiloxane composition
KR20200114042A (en) Method for polymerizating alpha-olefin
JPH07224133A (en) Ultraviolet curing silicone resin composition
JP2001055512A (en) Crosslinkable silicon polymer composition, composition for antireflection film, and antireflection film
JPH0241353A (en) Resin composition for sealing semiconductor
JP3456400B2 (en) Crosslinkable silicon-based polymer composition

Legal Events

Date Code Title Description
EEER Examination request
MKLA Lapsed

Effective date: 20160222