CN1535301A - Siloxane resins - Google Patents

Siloxane resins Download PDF

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Publication number
CN1535301A
CN1535301A CNA028147286A CN02814728A CN1535301A CN 1535301 A CN1535301 A CN 1535301A CN A028147286 A CNA028147286 A CN A028147286A CN 02814728 A CN02814728 A CN 02814728A CN 1535301 A CN1535301 A CN 1535301A
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China
Prior art keywords
carbon atom
silicone resin
group
resin
silane
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Pending
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CNA028147286A
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Chinese (zh)
Inventor
J・阿尔鲍夫
J·阿尔鲍夫
了刮痔
R·博伊斯沃特
佣斯基
D·布加尔斯基
呃锒
P·切瓦里尔
衿
K·艾格奇
R·金
D－L·欧
K·苏
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DuPont Toray Specialty Materials KK
Dow Silicones Corp
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Dow Corning Asia Ltd
Dow Corning Corp
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Priority claimed from US10/121,971 external-priority patent/US6596404B1/en
Application filed by Dow Corning Asia Ltd, Dow Corning Corp filed Critical Dow Corning Asia Ltd
Publication of CN1535301A publication Critical patent/CN1535301A/en
Pending legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02203—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being porous
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • 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
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    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl 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
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

Abstract

This invention pertains to a siloxane resin composition comprising R1SiO3/2 siloxane units, R2SiO3/2 siloxane units and (R3O)bSiO(4-b)/2 siloxane units wherein R1 is an alkyl group having 1 to 5 carbons, hydrogen, or mixtures thereof; R2 is a monovalent organic group having 6 to 30 carbons; R3 is a branched alkyl group having 3 to 30 carbons, b is from 1 to 3; and the siloxane resin contains from 2.5 to 85 mole percent R1SiO3/2 units, 2.5 to 50 mole percent R2SiO3/2 units and 5 to 95 mole percent (R3O)bSiO(4-b)/2 units. The siloxane resin is useful to make insoluble porous resin and insoluble porous coatings. Heating a substrate coated with the siloxane resin at a sufficient temperature effects removal of the R2 and R3O groups to form an insoluble insoluble porous coating having a porosity of 1 to 60 volume percent and a dielectric constant in the range of 1.5 to 3.0.

Description

Silicone resin
Technical field
The present invention relates to a kind of R of comprising 1SiO 3/2Siloxane unit, R 2SiO 3/2Siloxane unit and (R 3O) bSiO (4-b)/2The silicone resin composition of siloxane unit, wherein, R 1Be independently selected from alkyl with 1-5 carbon atom, hydrogen, and mix R 2Be independently selected from any monovalent organic radical group with 6-30 carbon atom and any monovalent organic radical group, R with replacement of 6-30 carbon atom 3Be independently selected from branched-chain alkyl with 3-30 carbon atom and branched-chain alkyl, and b is 1-3 with replacement of 3-30 carbon atom.The invention still further relates to insoluble porous resin and the insoluble porous coating produced by silicone resin composition.
Background technology
Semiconducter device usually has a row or multi-row interconnects patterned contact (levels), and it plays each circuit element of electrical coupling and forms unicircuit (IC).The interconnection contact is insulated coating usually or dielectric coat separates.In the past, be used for above-mentioned dielectric coat, the most frequently used material is the silica dioxide coating that utilizes chemical vapor deposition (CVD) or plasma enhanced techniques (PECVD) to form.Yet when the size of circuit element and the spacing between the said elements reduce, the high relatively specific inductivity (promptly about 4) of above-mentioned silica dioxide coating will be unsuitable for the electrical isolation that provides suitable.
For the specific inductivity that is lower than silicon-dioxide is provided, has found that and to use the dielectric coat that forms by siloxane-based resin.The example of above-mentioned coating is served as reasons and for example is described in people's such as Collins US3, the hydrogen silsesquioxane resin in 615,272 and people's such as Haluska US4,756,977 formed those.Although above-mentioned coating provides the specific inductivity that is lower than CVD or PECVD silica dioxide coating, and provide other benefit such as enhanced gap fillibility and profile pattern, the specific inductivity of above-mentioned coating also is confined to about 3 or bigger usually.
As everyone knows, the specific inductivity of insulating coating is an important factor that wherein requires to have the IC of low power consumption, cross-talk and signal delay.Because the size of IC continues to dwindle, therefore, the importance of this factor increases.What therefore, people wanted is that siloxane-based resin material and the described preparation methods of specific inductivity at the electric insulation coating layer below 3 can be provided.In addition, people also want to provide the siloxane-based resin with high anti-fragility coating and the preparation method of described resin.In addition, desirable is to process above-mentioned siloxane-based resin by standard processing technology such as spin coating coating is provided.As everyone knows, the specific inductivity of solid (solid) coating reducing and reduce with coating density.The density of porous coating is usually less than corresponding solid coating.
The US5 of Haluska, 446,088 have described structural formula HSi (OR) 3And Si (OR) 4Cohydrolysis silane to form to forming the method for the useful cohydrolysis product of coating.The R group is the organic group that comprises 1-20 carbon atom, and when being connected on the silicon by Sauerstoffatom, described group forms hydrolyzable substituting group.Especially preferred hydrolysable group is methoxyl group and oxyethyl group.The hydrolysis of water is carried out in the polar solvent that comprises acidifying oxygen.Cohydrolysis product in the solvent is applied on the base material, and solvent evaporated also is heated to 50-1000 ℃ with coating, thereby makes coating be transformed into silicon-dioxide.Haluska does not have to disclose the silane that has branched alkoxy.
People's such as Chung US6,231,989 have described a kind of method that is formed porous coating by hydrogen silsesquioxane resin.Stay mode in the coating with the solvent of at least 5% volume after the deposition, with the solution that comprises hydrogen silsesquioxane resin and solvent deposited coatings and form porous network on base material.Then, coating is exposed in the environment that comprises basic catalyst and water; Solvent evaporated from coating, thus the porous network of specific inductivity in the 1.5-2.4 scope formed.1
People's such as Smith WO98/49721 has described a kind of method that forms the nanoporous dielectric coat on base material.This method comprises the steps: organoalkoxysilane is mixed with solvent composition and nonessential water; This mixture is deposited on the base material; Base material placed sealing chamber and this chamber is evacuated to pressure be lower than normal atmosphere; Making this base material be exposed to the water vapor neutralization under pressure below atmospheric pressure is exposed in the alkaline steam then.
People's such as Mikoshiba US6,022,814 have described and have a kind ofly formed the method for silica membrane by hydrogen that has organic replacement or methyl siloxane-based resin on base material, and wherein said substituting group will be removed to the temperature range of the glass transition point of this resin at 250 ℃.The performance of the silica membrane of being reported comprises: 0.8-1.4g/cm 3Density, the mean pore size of 1-3 nanometer, 600-1500m 2The surface-area of/g and the specific inductivity of 2.0-3.0.Disclosed can comprise by oxidized useful organic substituent 250 ℃ or higher temperature: replacement with unsubstituted alkyl or alkoxyl group, for example, 3,3,3-trifluoro propyl, β-styroyl, the tertiary butyl, 2-cyanoethyl, phenmethyl, and vinyl.
People such as Mikoskiba are at J.Mat.Chem., and 1999,9, reported among the 591-598 that a kind of big aperture of dust level of setting up is with the density that reduces coating and the method for specific inductivity in the methyl silsesquioxane resin coating.To have methyl (three siloxy-silyls) unit and the unitary multipolymer of alkyl (three siloxy-silyls) and be spin-coated on the base material and and heat, thereby inflexible siloxanes matrix will be provided at 250 ℃.Then, at 450-500 ℃ coating is heated, to remove the thermally labile group, stayed the hole corresponding to the substituting group size thus, its specific inductivity is about 2.3.As the thermally labile group, to trifluoro propyl, cyanoethyl, styroyl and propyl group are studied.
Day disclosure special permission (HEI) 5-333553 of people such as Ito has described in the presence of proton acceptor, prepares the method for the silicone resin that comprises alkoxyl group and silanol functionality by the hydrolysis of diacetoxy two (tert.-butoxy) silane.In the presence of light acid, make the described resin width of cloth penetrate curing, carry out heat treated subsequently to form similar SiO 2Coating, and it can be used as the photoresist material material that IC makes.
Have found that, the branched alkoxy that will have the organic group of 6-30 carbon atom and have a 3-30 carbon atom is introduced in the silicone resin following advantage will be provided: as the stability in storage of cured resin improvement, the modulus that increases and the porosity of increase, specific inductivity remains in the scope of 1.5-3.0 simultaneously.Therefore, the object of the present invention is to provide a kind of silicone resin composition that improves stability in storage that has.Thereby another object of the present invention is to provide the preparation method of silicone resin and solidifies the method that these resins are produced insoluble porous coating, wherein, the specific inductivity of described porous coating is 1.5-3.0, and porosity is that 1-60% volume and modulus are 1.0-10GPa.The advantage of these coatings is that they can form with the processing film of routine.
Summary of the invention
The present invention relates to silicone resin composition, comprise:
(A) 2.5-85 molar part R 1SiO 3/2Siloxane unit, wherein, R 1Be independently selected from alkyl with 1-5 carbon atom, hydrogen, and mix;
(B) 2.5-50 molar part R 2SiO 3/2Siloxane unit, wherein, R 2Be independently selected from any monovalent organic radical group with 6-30 carbon atom and any monovalent organic radical group with replacement of 6-30 carbon atom; With
(C) 5-95 molar part (R 3O) bSiO (4-b)/2Siloxane unit, wherein, R 3Be independently selected from the branched-chain alkyl that has 3-30 carbon atom branched-chain alkyl and have the replacement of 3-30 carbon atom, b is 1-3.Component (A), total amount (B) and (C) is 100 molar part, and component (A), (B) and (C) sum be in the resin combination siloxane unit total amount at least 50%.
The invention still further relates to by making formula R 1SiX 3Silane or its mixture, formula R 2SiX 3Silane or its mixture, and structural formula (R 3O) cSiX (4-c)Silane or its mixture react and prepare the method for silicone resin, wherein, R 1Be independently selected from alkyl with 1-5 carbon atom, hydrogen, and mix R 2Be independently selected from any monovalent organic radical group with 6-30 carbon atom and any monovalent organic radical group, R with replacement of 6-30 carbon atom 3Be independently selected from the branched-chain alkyl with 3-30 carbon atom and the branched-chain alkyl of replacement, and c is that 1-3 and X are hydrolyzable group or hydroxyl.
The invention still further relates to method that forms insoluble porous resin and the method that on base material, forms insoluble porous coating.The specific inductivity of insoluble porous coating is in the scope of 1.5-3.0, and porosity is that 1-60% volume and modulus are at 1.0-10GPa.
Detailed Description Of The Invention
Silicone resin composition comprises:
(A) 2.5-85 molar part R 1SiO 3/2Siloxane unit, wherein, R 1Be independently selected from alkyl with 1-5 carbon atom, hydrogen, and mix;
(B) 2.5-50 molar part R 2SiO 3/2Siloxane unit, wherein, R 2Be independently selected from any monovalent organic radical group with 6-30 carbon atom and any monovalent organic radical group with replacement of 6-30 carbon atom; With
(C) 5-95 molar part (R 3O) bSiO (4-b)/2Siloxane unit, wherein, R 3Be independently selected from the branched-chain alkyl that has 3-30 carbon atom branched-chain alkyl and have the replacement of 3-30 carbon atom, b is 1-3.Component (A), total amount (B) and (C) is 100 molar part, and component (A), (B) and (C) sum be in the resin combination siloxane unit total amount at least 50%.Preferably, silicone resin comprises the component (A) of average 30-60 molar part, component of 10-25 molar part (B) and 20-50 molar part (C), wherein, component (A), (B) and total amount (C) be 100 molar part, and (A), (B) and (C) sum be in the resin combination siloxane unit total amount at least 70%.
Structure to silicone resin has no particular limits.Silicone resin can be basically fully condensation or (promptly comprise and be lower than 10% mole of Si-OR and/or be lower than 30% mole of Si-OH) of partial reaction only.The silicone resin of partial reaction is for example including, but not limited to siloxane unit, as R 1Si (X) dO (3-d/2)R 2Si (X) dO (3-d/2)And Si (X) d(OR 3) fO (4-d-f/2)R in the formula 1, R 2, and R 3As mentioned above; Each X is hydrolysable group or hydroxyl independently, and d and f are 1-2.Thereby hydrolysable group is to be connected to the alkoxyl group of formation silicon connection on the Siliciumatom or the organic group (Si-OR) of the acyloxy that silicon connects by Sauerstoffatom.Specifiable R (but being not limited to) is: have the linear alkyl of 1-6 carbon atom, and as methyl, ethyl, propyl group, butyl, amyl group, or hexyl, and acyl group with 1-6 carbon atom, as formyl radical, ethanoyl, propionyl, butyryl radicals, pentanoyl, or caproyl.Silicone resin can also comprise in addition and is lower than about 10% mole SiO 4/2The unit.
The weight-average molecular weight of silicone resin is at 400-160, and 000, preferably 5,000-100 is in 000 the scope.
R 1Can be linear alkyl with 1-5 carbon atom, hydrogen, and mix.Specifiable alkyl is including, but not limited to methyl, ethyl, propyl group, butyl, and amyl group.Preferably, R 1Be methyl, hydrogen or its mixture.
R 2The replacement or unsubstituted line style, side chain or the cyclic any monovalent organic radical group that have 6-30 carbon atom.The organic group that replaces can replace the hydrogen atom (C-H) of bond with carbon with substituting group.The R of specifiable replacement 2Group including, but not limited to: halogen such as chlorine or fluorine, ether is by structural formula CH 3O (CH 2) mO) p(CH 2) qThe polyalkylene oxide groups (m in the formula, p and q are positive integer and the positive integer that is preferably 1-9) of-expression, alkoxyl group, acyloxy, acyl group, carbalkoxy, and trialkylsiloxy.R 2Example include, but are not limited to hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, hexadecyl, triisobutyl, four isobutyl-s, trimethylsiloxy hexadecyl, octadecyl, CH 3(CH 2) 11OCH 2CH 2-, CH 3O (CH 2CH 2O) 7-9(CH 2) 3-, (CH 3) 3CCH 2(CH 3) 2C (CH 3) 3CCH 2CHCH 2-, CF 3(CF 2) 5CH 2CH 2-, styroyl, to the toluene ethyl, right-anisole ethyl and right-bromobenzene ethyl.Preferred R 2Be replacement or unsubstituted alkyl with 10-20 carbon atom.
R 3Be replacement or unsubstituted branched-chain alkyl with 3-30 carbon atom.The branched-chain alkyl that replaces can replace the hydrogen atom (C-H) of bond with carbon with substituting group.The R of the replacement that can enumerate 2Group is including, but not limited to halogen such as chlorine and fluorine, as by structural formula-(CH 2) aC (O) O (CH 2) bCH 3Described carbalkoxy is as by structural formula-(CH 2) aO (CH 2) bCH 3The alkoxy substituent of describing and as by structural formula-(CH 2) aC (O) (CH 2) bCH 3The carbonyl substituted base of describing, wherein, a0 and b0.Specifiable unsubstituted R 3Group is including, but not limited to sec.-propyl, isobutyl-, and sec-butyl, the tertiary butyl, isopentyl, neo-pentyl, tert-pentyl, the 2-methyl butyl, the 2-methyl amyl, 2-methyl hexyl, the 2-ethyl-butyl, the 2-ethyl pentyl group, the 2-ethylhexyl, or the like.Preferred R 3Be the tertiary alkyl with 4-18 carbon atom, more preferably R 3Be the tertiary butyl.
The preparation method of silicone resin comprises:
Being enough to form the time and the temperature of silicone resin, with following component (a)-(d) mix,
(a) formula R 1SiX 3Silane or silane mixture, wherein, each R 1Be independently selected from alkyl with 1-5 carbon atom, hydrogen, and mix, X is hydrolysable group or hydroxyl independently;
(b) formula R 2SiX 3Silane or silane mixture, R wherein 2Be independently selected from any monovalent organic radical group with 6-30 carbon atom and any monovalent organic radical group with replacement of 6-30 carbon atom, X is hydrolysable group or hydroxyl independently;
(c) formula (R 3O) cSiX (4-c)Silane or silane mixture, wherein, R 3Be independently selected from branched-chain alkyl with 3-30 carbon atom and the branched-chain alkyl with replacement of 3-30 carbon atom, c is 1-3, and X is hydrolysable group or hydroxyl independently; With
(d) water.
Silane (a) is formula R 1SiX 3Silane or silane mixture, each R wherein 1Be independently selected from the alkyl that has 1-5 carbon atom as mentioned above, hydrogen, and mix.Preferably, R 1Be methyl, hydrogen or its mixture.X is hydrolysable group or hydroxyl.The X that " hydrolysable group " refers to greater than 80% mole reacts (hydrolysis) with water under the reaction conditions that forms silicone resin.Thereby hydroxyl for wherein at least 70% mole be connected on the Different Silicon atom another X radical reaction condensation and formation siloxane bond (Si-O-Si) but the condensation group.Hydrolysable group is a halide group, as muriate, and amino, thus or be connected on the Siliciumatom organic group (Si-OR) that forms the acyloxy that alkoxyl group that silicon connects or silicon connects by Sauerstoffatom.When X is amino, be confined to wherein R usually 1For alkyl or comprise the component that is lower than 10% moles of hydrogen, this is because the amino stability that may damage the hydrogen-containing siloxane resin.In addition, when X was amino, to be lower than about 30% mole of use, this was because the silicone resin that obtains may comprise the SiOH greater than 30% mole usually.Specifiable R (but being not limited to) is: have the linear alkyl of 1-6 carbon atom, and as methyl, ethyl, propyl group, butyl, amyl group, or hexyl, and acyl group with 1-6 carbon atom, as formyl radical, ethanoyl, propionyl, butyryl radicals, pentanoyl, or caproyl.Preferably, silane (a) is trichlorosilane, METHYL TRICHLORO SILANE, and Trimethoxy silane, triethoxyl silane, methyltrimethoxy silane or Union carbide A-162, this is because the cause of its being easy to get property.Typically, the content of silane (a) be per 100 molar part silane (a), silane (b) and silane (c) in conjunction with total amount 2.5-85 molar part, be preferably the 30-60 molar part.
Silane (b) is formula R 2SiX 3Silane or silane mixture, wherein, as mentioned above, R 2Be independently selected from any monovalent organic radical group with 6-30 carbon atom and any monovalent organic radical group with replacement of 6-30 carbon atom.As mentioned above, X is hydrolysable group or hydroxyl independently.Preferably, silane (b) is R 2SiCl 3, R 2Si (OMe) 3And R 2Si (OEt) 3, wherein Me represents that methyl and Et represent ethyl, this is because the cause of its being easy to get property.Typically, the content of silane (b) be per 100 molar part silane (a), silane (b) and silane (c) in conjunction with total amount 2.5-50 molar part, be preferably the 10-25 molar part.
Silane (c) is formula (R 3O) cSiX (4-c)Silane or silane mixture, wherein as mentioned above, R 3Be independently selected from the branched-chain alkyl that has 3-30 carbon atom branched-chain alkyl and have the replacement of 3-30 carbon atom, c is 1-3, and X is hydrolysable group or hydroxyl independently as mentioned above.Preferably, silane (c) is two tert.-butoxy dichlorosilanes, two tert.-butoxy dihydroxyl silane, and two tert.-butoxy dimethoxy silane, two tert.-butoxy diethoxy silanes, and ditert-butyldiacetyl oxygen-base silane, this is because the cause of its being easy to get property.Typically, the content of silane (c) is that per 100 molar part silane (a), silane (b) and silane (c) are in conjunction with total amount 5-95 molar part, preferably from the 20-50 molar part.
Water is so that the amount existence that hydrolysable group X is hydrolyzed.Typically, the content of water is that every mole of X is the 0.5-2.0 mole at the silane (a) and (b) and (c), more preferably 0.8-1.2 mole.
The reaction that forms silicone resin can be carried out in the liquid state of solvent having or do not have.If the use solvent, it can comprise the functional group that does not contain the participation reaction and be any appropriate organic solvent that is used for silane (a) and (b) and solvent (c).Specifiable solvent is including, but not limited to saturated aliphatic compound such as Skellysolve A, hexane, normal heptane, octane-iso and dodecane; Alicyclic compound is as pentamethylene and hexanaphthene; Aromatic substance, as benzene, toluene, dimethylbenzene and sym-trimethylbenzene; Cyclic ethers, (THF) is with diox as tetrahydrofuran (THF); Ketone is as methyl iso-butyl ketone (MIBK) (MIBK)); The alkane that halogen replaces is as trichloroethane; Halogenated aromatics is as bromobenzene and chlorobenzene; And alcohol, as methyl alcohol, ethanol, propyl alcohol, butanols.In addition, the form that above-mentioned solvent can cosolvent two or more be used in combination.Preferred solvent is aromatic substance and cyclic ethers, toluene most preferably wherein, sym-trimethylbenzene, and tetrahydrofuran (THF).When using solvent, with solvent and silane (a), (b) and gross weight meter (c), in the scope of 40-95% weight, preferred consumption is a 70-90% weight to its consumption usually.
Can any order with component (a), (b), (c), (d) and nonessential solvent (if you are using) mix, as long as hydrolysable group (X) and water come in contact, so that react, thereby the formation silicone resin gets final product.Usually, silane is dissolved in the solvent, then water is added in this solution.When said components is mixed, usually certain reaction will take place.Yet, in order to increase speed of reaction and degree, adopted various expedites, as temperature control and/or stirring.
The temperature of reacting is unimportant, as long as it does not make silicone resin product tangible gelation take place or produce to solidify.Described temperature is logical to be at 20-150 ℃, preferred 20-100 ℃.When X is acyloxy such as acetoxyl group, preferably react 50 ℃ or following temperature.The time that forms silicone resin is depended on many factors, such as, but be not limited to: used specific silane, temperature and R 1, R 2And R 3The mol ratio of in the silicone resin product of reaction, wishing.Typically, the reaction times from several minutes to several hours.For molecular weight that increases prepared silicone resin and the stability in storage of improving silicone resin, preferably, after above-mentioned reaction or as the part of above-mentioned reaction, increase the weight of step.The reflux temperature that " increases the weight of " to refer to by being heated to solvent from 40 ℃ carries out several hours reaction, thereby increases weight-average molecular weight.Preferably, the reacting by heating mixture makes the weight-average molecular weight that heats the back silicone resin in about scope of 5,000 to 100,000.
When X is acyloxy such as acetoxyl group,, will produce corresponding acid as acetate as byproduct of reaction.Because the existence of acetate may have a negative impact to the stability of silicone resin product, any acetate therefore it is desirable to neutralize.The neutralization of by-product acetic acid can perhaps be removed by distillation and carry out by reaction mixture being contacted with neutralizing agent and carrying out.Usually, finish distillation by adding solvent such as toluene (if not existing), and under decompression and heating (promptly at the most 50 ℃) to remove acetate with the form of solvent azeotrope.If the use neutralizing agent, it must have the enough alkalescence of any residual acetate of neutralization, and insufficient alkalescence is feasible can not to make the silicone resin product catalytically rearranging but it also must have.The example of appropriate base comprises: lime carbonate, yellow soda ash, sodium bicarbonate, volatile salt, ammoniacal liquor, calcium oxide or calcium hydroxide.Neutralization can be finished by any suitable means, as stirring in the powder neutralizing agent, makes reaction mixture and any extra solvent filter then or does not hinder mobile particulate state neutralizing agent bed by its size.The step that increases the weight of recited above is carried out after neutralization and/or after removing by-product acetic acid usually.
When X is halide group, with the HX that forms as byproduct of reaction.Because the existence of HX may have a negative impact to the stability of silicone resin product, therefore, utilize neutralization known in the art or the method for removing HX to be neutralized or be removed be desirable.For example, when the HCl that produces as by product, can be removed by the gas blow-washing in reaction vessel.Perhaps, utilize method recited above that HCl is neutralized.Perhaps silicone resin liquid is washed and be removed by water.
When forming enough HX (when silane (a), (b) He (c) all comprise X, X is a halide group), can be during the formation silicone resin with silane (c) in all OR 3All remove, thereby comprised (A) and (B) siloxane unit and other SiO 4/2Unitary silicone resin composition.
If the use solvent desolvates by removing, can the recovered in solid form silicone resin.The method of removing of solvent is unimportant, and many methods all are to know in this area.For example, can adopt under vacuum and heating (being 50-120 ℃), remove the method for desolvating by distillation.Perhaps, be in the specific solvent, can carry out exchange of solvent by adding second solvent and distillating first solvent so if wish silicone resin.The silicone resin that comprises greater than 10% weight si hydrogen bonding (Si-H) stores with the solution form usually, and the silicone resin of littler Si-H content can store by solid-state form.
Can obtain insoluble porous resin by silicone resin is heated, its heat-up time and temperature are enough to make silicone resin to solidify and remove R 2And R 3The O group, and form insoluble porous resin thus." remove " and refer to greater than about 80% mole of R that is bonded on the Siliciumatom 2And R 3The O group is removed with the form of volatile hydrocarbon and hydrocarbon fragment, and this will form the space in coating, thereby forms insoluble porous resin.Heating can be carried out with single stage method or two-step approach.In two step heating methods, at first silicone resin is heated, its heat-up time and temperature are enough to be cured but the not obvious R of removing 2And R 3The O group.Usually, described temperature can keep several minutes to several hours in greater than 20 ℃ to 350 ℃ scope.Then, greater than 350 ℃ to being lower than the silicone resin skeleton or being bonded to R on the Siliciumatom as mentioned above 1The temperature range of decomposition temperature in the solidified resin is further heated (be that several minutes was to several hours heat-up time), thereby remove R from Siliciumatom 2And R 3O.Usually, this is removed step and carries out in greater than 350 ℃ to 600 ℃ temperature range, and preferred temperature range is 400-550 ℃.During curing and heating steps, greater than 90% mole the R that contains alkyl 1Group is retained on the silicone resin, and greater than 70% mole hydrogeneous R 1Group is retained on the silicone resin.The porosity of final insoluble porous resin can be by R in the silicone resin 2And R 3The molecular fraction of O group and how silicone resin is heated and control.When with similar condition under solidified only comprise the R that is incorporated in the silicone resin 2Or R 3The similar composition of O group (is R 2Or R 3Total % mole number of O leavings group is basic identical) silicone resin when comparing, comprise the R that introduces in the silicone resin 2And R 3The porosity of the formed insoluble porous resin of silicone resin of O group will increase about 10% volume usually.
In single stage method, by greater than 20 ℃ to being lower than the silicone resin skeleton or being bonded to R on the Siliciumatom as mentioned above 1Heat in the scope of the decomposition temperature of group, and carry out the curing and the R of silicone resin simultaneously 2And R 3Removing of O group, thus remove R from the solidified silicone resin 2And R 3O.Usually preferably, be cured/remove step in greater than 350-600 ℃ temperature range, most preferred temperature range is at 400-550 ℃.
Preferably, in inert atmosphere, heat, but also can use other atmosphere.At this useful inert atmosphere including, but not limited to nitrogen, helium and argon atmospher, wherein oxygen level is lower than 50ppm, preferably is lower than 15ppm.In addition, can also be in vacuum to any working pressure more than the normal atmosphere with at any effective oxidation or non-oxidized gas environment as comprising air, oxygen, oxygen plasma, ozone, ammoniacal liquor, amine, steam, N 2O heats under the atmosphere surrounding of hydrogen or the like.
Insoluble porous resin can be used as the porous material with controlled porosity and the high-temperature stability up to 600 ℃, and as the formed film of selective gas or fluid permeable, support of the catalyst, energy storage system be battery and molecular separation and isolation for example.Term " porous " refers to the porosity of insoluble porous resin in the scope of 1-60% volume.Preferred porosity is in the scope of 10-60% volume.The modulus of insoluble porous resin is in the scope of 1.0-10GPa.
Can on base material, prepare porous coating with silicone resin as follows:
(A) with the coating composition coated substrate that comprises silicone resin composition, described silicone resin composition contains:
(a) 2.5-85 molar part R 1SiO 3/2Siloxane unit, wherein, R 1Be independently selected from alkyl with 1-5 carbon atom, hydrogen, and mix;
(b) 2.5-50 molar part R 2SiO 3/2Siloxane unit, wherein, R 2Any monovalent organic radical group of the replacement of 6-30 carbon atom is rolled into a ball and had to any monovalent organic radical that is independently selected from the aforesaid 6-30 of a having carbon atom; With
(c) 5-95 molar part (R 3O) bSiO (4-b)/2Siloxane unit, wherein, R 3Be independently selected from the aforesaid 3-30 of having a carbon atom branched-chain alkyl and the branched-chain alkyl with replacement of 3-30 carbon atom, b is 1-3; Component (a), total amount (b) and (c) is 100 molar part, and component (a), (b) and (c) sum be in the resin combination siloxane unit total amount at least 50%.
(B) the heating substrates coated to be enough to make coating composition solidified temperature and
(C) further heat substrates coated to being enough to from the solidified coating composition, to remove R 2And R 3The temperature of O group forms insoluble porous coating thus on base material.Preferably, with per 100 molar part (a), (b) and (c) total amount meter, silicone resin comprises average 30-60 molar part (a), 10-25 molar part (b) and 20-50 molar part (c), and (a), (b) and (c) sum be in the resin combination siloxane unit total amount at least 70%.
Usually the form with solvent dispersion is applied to silicone resin on the base material.Operable solvent comprise do not influence gained coating or base material can dissolve or the dispersed polyorganosiloxane resin with any reagent that forms uniform liquid mixture or the mixture of reagent.Usually, described solvent can be not comprise and can participate in and the functional group of silicone resin reaction (reaction of silane mixture for example discussed above and water) such as any organic solvent of hydroxyl.
For specific application, the content of solvent dissolves silicone resin to wishing concentration for being enough to.Usually, in the weight of silicone resin and solvent, the content of solvent is 40-95% weight, preferably from 70-90% weight.If silicone resin has been retained in the solvent recited above, this solvent can use in coated substrate so, perhaps if desired, can carry out simple exchange of solvent by adding second solvent and distilling first solvent.
Silicone resin is applied to concrete grammar on the base material including, but not limited to spin coating, dip-coating, spraying, flow coat, silk screen printing or the like.Preferred applying method is spin coating.When using solvent, solvent is evaporated from coated substrate, thereby silicone resin coating is deposited on the base material.With regard to evaporation, can adopt any suitable method, as carrying out simply air-dryly in the surrounding environment, by applying vacuum, or mild heat (50 ℃ at the most), or evaporate in early days at solidified by being exposed to.When adopting spin coating, because the rotation solvent is driven away, therefore, extra drying means is minimized.
After being in application on the base material, being enough to make silicone resin to solidify and removing the R that is bonded on the Siliciumatom 2And R 3Under the temperature of O group silicone resin coating is heated, form insoluble porous coating thus." solidified coating composition " refers to coating and is insoluble to above-mentioned any solvent that silicone resin whereby is deposited in the solvent on the base material or is used for applying silicone resin basically." remove " the R on the Siliciumatom of being bonded to that refers to greater than 80% mole 2And R 3The O group is removed with the form of volatile hydrocarbon and hydrocarbon fragment, and this will produce the space in coating, thereby forms porous resin.Heating can be carried out with single stage method or two-step approach.In two step heating methods, at first at the not obvious R that removes 2And R 3Under the temperature that is enough to be cured, heat under the situation of O group.Usually, described temperature can be in greater than 20 ℃ to 350 ℃ scope.Then greater than 350 ℃ to being lower than the silicone resin skeleton or being bonded to R on the Siliciumatom as mentioned above 1In the temperature range of the decomposition of group, the solidified silicone resin coating is further heated, so that remove R from Siliciumatom 2And R 3O group (leavings group).Usually preferably, remove step in greater than 350 ℃ to 600 ℃ temperature range, most preferred temperature range is at 400-550 ℃.Solidify and heating steps during, greater than 90% mole contain alkyl R 1Group is retained on the silicone resin, and greater than 70% mole hydrogeneous R 1Group is retained on the silicone resin.
In single stage method, by greater than 20 ℃ to being lower than siloxane backbone or being bonded to R on the Siliciumatom as mentioned above 1Heat under the decomposition temperature of group and carry out the curing of silicone resin simultaneously and remove R 2And R 3The O group, thus from the solidified coating composition, remove R 2And R 3The O group.Usually preferably, solidify/remove step and carry out in greater than 350 ℃ to 600 ℃ temperature range, most preferred temperature range is at 400-550 ℃.By control R 2And R 3The O group in silicone resin molecular fraction and how silicone resin is heated the porosity of the final insoluble porous resin of may command.
Preferably, in inert atmosphere, heat, but also can use other atmosphere.Inert atmosphere is including, but not limited to nitrogen as used herein, helium and argon atmospher, and wherein oxygen level is lower than 50ppm, preferably is lower than 15ppm.In addition, can also be in vacuum to effective atmosphere pressure any more than the normal atmosphere and at any effective oxidation or non-oxidized gas environment as comprising air, oxygen, oxygen plasma, ozone, ammoniacal liquor, amine, steam, N 2O heats in the atmosphere surrounding of hydrogen or the like.
By aforesaid method, on base material, formed thin (less than 5 microns) insoluble porous coating.Preferably, the thickness of described insoluble porous coating is the 0.3-2.5 micron, and preferred thickness is the 0.5-1.2 micron.This coating will make the irregular surface of the various base materials cunning that flattens, and have excellent bond performance.
In the present invention, can adopt any heating means usually, as utilize quartz tube furnace, the heating means of convection oven or divergence or micro-wave energy.Similarly, rate of heating is unimportant usually, but the most practical and preferably as quickly as possible coated substrate is heated.
The insoluble porous coating of Sheng Chaning can be produced on any base material in the present invention.Yet, particularly coating is used for electronic substrate." electronic substrate " refers to and comprises silicon-based devices and the gallium-arsenide base device that is used to make semiconductor element, comprises focal plane arrays (FPA), photoelectronic device, photocell, Optical devices, similar transistorized device, the 3-D device, the silicon device on isolator, superlattice device or the like.
If desired, extra coating can be applied on the insoluble porous coating.These additional coatings can comprise for example silica dioxide coating, contain silicon coating, siliceous carbon coating, siliceous nitrogen coating, contain silica nitrogen coating, coating like siliceous nitrogen carbon coating and/or the diamond that produces by deposition (being CVD, PECVD or the like) amorphous Si C:H, diamond, silicon nitride.The applying method of described coating is well known in the art.The applying method of additional coatings is unimportant, and described coating is passed through for example thermal chemical vapor deposition (TCVD) of chemical vapour deposition technique usually, photo chemical vapor deposition, plasma body enhanced chemical vapour deposition (PECVD), electron cyclotron resonace (ECR) and injection vapour deposition apply.In addition, extra coating also can for example sputter or electron beam evaporation apply by the physical vapour deposition technology.These methods comprise the form with heat or plasma body thereby energy are applied to the reaction that causes hope on the volatile matter, perhaps with energy accumulating on solid sample, thereby deposit.
The insoluble porous coating that forms by described method especially can be used as the coating on electron device such as the unicircuit.For the layer insulation coating, the specific inductivity of the insoluble porous coating that makes by described method is in the scope of 1.5-3, more preferably in the scope of 1.5-2.5.The porosity that term " porous " refers to insoluble porous coating is the 1-60% volume.Preferred porosity is in the scope of 10-60% volume.The modulus of insoluble porous coating is in the scope of 1.0-10GPa.
Embodiment
Provide following indefiniteness embodiment, so that make those skilled in the art can more easily understand the present invention.In an embodiment, weight is with gram (g) expression.Molecular weight is represented with weight-average molecular weight (Mw) and number-average molecular weight (Mn) by gel permeation chromatography measurement.Utilize 29Si nucleus magnetic resonance (NMR) is analyzed silicone resin composition.Utilize QuantaChrome Autosorb 1MP system to carry out nitrogen absorption porosity measurement.Before placing sample cell, the solidified silicone resin is ground to form fine powder, carry out several hours the degassing, and be loaded in the analytical equipment.By Brunauer-Emmett-Teller method meter area.Suppose that the hole fills up adsorptive, near consistent relative pressure (P/P 0=0.995) under, measures total pore volume according to the quantity of steam in the suction port.Utilize the helium specific gravity flask to measure skeletal density.Skeletal density is represented the true density of silicone resin entity structure, does not comprise any internal voids, crack or hole in measurement.Calculate the percentage porosity according to skeletal density and total pore volume.Utilize the oval photometer of Woollam M-88 beam split to measure specific refractory power (RI) and coat-thickness.
In the following example, Me represents methyl, and tBu represents the tertiary butyl, and AcO represents acetoxyl group, and Et represents ethyl.In tabulating down, n.m. represents not measure specific performance properties.
Embodiment 1
Present embodiment is illustrated the formation of silicone resin composition, wherein R 1Be hydrogen, R 2For having the organic group of 8-22 carbon atom, and R 3Be the tertiary butyl.Under argon atmospher, with the described consumption of table 1, with HSi (OEt) 3(A), (AcO) 2Si (OtBu) 2(B) and R 2Si (OMe) 3(C) adding 75 in the flask restrains in the tetrahydrofuran (THF)s (THF).Then deionized water (D) is added in the flask, and mixture was stirred 1 hour in room temperature.In mixture, add 75 gram toluene then.Utilize rotatory evaporator to remove and desolvate, to obtain viscosity oily silicone resin, existing side by side soon, it is dissolved in the 150 gram toluene.By under reduced pressure being heated to 38 ℃, to remove by-product acetic acid with the form of methylbenzene azeotropic thing.Once more with resin dissolves in toluene, and in backflow toluene azeotropic drying and heating 1 hour.R 2Si (OMe) 3(C) list in the table 2.The analysis and the molecular weight of resin structure are listed in the table 3.
The synthetic general introduction of table 1. resin
Embodiment number (A) (g) (B) (g) (C) (g) (D) (g) Toluene in the reflow step (g) Yield (g) Outward appearance
????1-1 ?25.3 ?40.0 ?19.3 ?14.4 ????250 ??43.6 Oily
????1-2 ?22.5 ?40.0 ?25.7 ?14.4 ????250 ??46.7 Oily
????1-3 ?36.5 ?20.0 ?25.6 ?16.4 ????250 ??44.4 Oily
????1-4 ?12.4 ?10.0 ?10.3 ?6.7 ????110 ??19.6 The wax shape
????1-5 ?29.0 ?40.8 ?10.3 ?14.0 ????120 ??37.0 The wax shape
????1-6 ?40.0 ?25.0 ?11.8 ?13.2 ????250 ??41.0 Oily
????1-7 ?40.0 ?25.0 ?25.5 ?15.1 ????250 ??47.4 Oily
????1-8 ?40.0 ?25.0 ?21.3 ?14.8 ????250 ??49.2 Oily
????1-9 ?40.0 ?25.0 ?16.0 ?13.1 ????250 ??42.9 Oily
Table 2
Embodiment number (C) R in 2Group
????1-1 ????CH 3(CH 2) 17-
????1-2 ????CH 3(CH 2) 17-
????1-3 ????CH 3(CH 2) 17-
????1-4 ????CH 3(CH 2) 17-
????1-5 ????CH 3(CH 2) 17-
????1-6 ????CH 3O(CH 2CH 2O) 7-9(CH 2) 3-
????1-7 ????CH 3(CH 2) 11OCH 2CH 2-
????1-8 ????(CH 3) 3CCH 2(CH 3) 2C(CH 3) 3CCH 2CHCH 2-
????1-9 ????CF 3(CF 2) 5CH 2CH 2-
Table 3. (HSiO 3/2) f(R 2SiO 3/2) g((tBuO) bSiO 4-b/2) hThe analysis of resin
Embodiment F/g/h mol ratio based on reactant The f/g/h mol ratio ( 29SiNMR) ?Mn ??Mw
??1-1 ????0.45/0.15/0.40 ????0.46/0.13/0.41 ?9360 ??72,100
??1-2 ????0.40/0.20/0.40 ????0.41/0.19/0.40 ?5660 ??80,200
??1-3 ????0.65/0.20/0.15 ????n.m. ?n.m. ＞100,00
??1-4 ????0.55/0.20/0.25 ????0.54/0.18/0.24 ?8270 ??35,900
??1-5 ????0.50/0.10/0.40 ????n.m. ?n.m. ??n.m.
??1-6 ????0.48/0.09/0.43 ????0.42/0.04/0.54 ?n.m. ??n.m.
??1-7 ????0.43/0.18/0.39 ????0.43/0.14/0.43 ?2880 ??72,200
??1-8 ????0.43/0.18/.0.39 ????0.55/0.23/0.22 ?1450 ??19,700
??1-9 ????0.48/0.083/0.44 ????0.47/0.05/0.48 ?9040 ??158,100
Embodiment 2a.
Present embodiment is illustrated the formation of silicone resin composition, wherein R 1Be hydrogen, R 2Be octadecyl and R 3Be the tertiary butyl.Exempt from the flask of UV/ light with protective reaction in the aluminium foil covering, under nitrogen atmosphere, by mixing 256.0g (1.51mol) SiCl 4, 228.0g (1.46mol) Si (OMe) 4And 13.5g (101.3mmol) AlCl 3And prepare (MeO) 2SiCl 2Under nitrogen atmosphere, in room temperature mixture was stirred 17 days, continue the protection of UV/ light simultaneously.Under vacuum, from reaction mixture, distill out unreacted chlorosilane, and be collected in the Schlenk pipe that is dipped in the liquid nitrogen.Thereby the product that stays distills to provide at 760mmHg and has 29SiNMR feature and comprise and be rich in Cl 2Si (OMe) 2Some cuts of following cut:
(b.p.95 ℃, 70mHg) 87.0g comprises 44.0 weight %Cl to cut 1 3Si (OMe), 43.2 weight %Cl 2Si (OMe) 2With 12.8 weight %ClSi (OMe) 3
(b.p.102 ℃, 70mmHg) 119.0g comprises 8.5 weight %Cl to cut 2 3Si (OMe), 58.7 weight %Cl 2Si (OMe) 2With 32.8 weight %ClSi (OMe) 3
Embodiment 2b
Under nitrogen, prepare (MeO) by the above-mentioned cut 2 of 119.0 grams being added in potassium tert.-butoxide/THF solution of 1.5 liters of (1.5 moles, excessive) 1M in 0 ℃ 2Si (OtBu) 2Then, 500 milliliters of anhydrous THF are added in this reaction mixture, reflux simultaneously and stir 4 hours (65 ℃).Under the vacuum of 100mmHg, in 20 ℃ of evaporating solvents.With pentane/diethyl ether mixture reaction product is washed several times, filter and distillation (92 ℃ 75mmHg), are passed through thereby provide 79.5 grams 29SiNMR, 13CNMR is that GC and GC-MS characterize, comprise 90.3 weight % (MeO) 2Si (OtBu) 2, 3.8 weight % (MeO) 3Si (OtBu) and 5.9 weight % (MeO) Si (OtBu) 3Colourless liquid.
Embodiment 2c
Under nitrogen, 5.48g reaction product, the 8.70 gram CH of embodiment 2b will be derived from 3(CH 2) 17Si (OMe) 3With 7.62 gram HSi (OEt) 3Mixture be added among the MIBK of 40ml, drop to then and comprise 80ml MIBK, in the mixture of 40ml toluene and 60ml deionized water.In 120 ℃ reaction mixture refluxed is spent the night.After the cooling, reaction mixture is divided into two-phase, water/insolubles and organic phase.Separate organic phase from water/insoluble substance mutually, and utilize Dean Stark water trap to carry out drying.Utilize the rotatory evaporator evaporating solvent, obtain 7.2 gram waxy solids, it confirms as (CH by 29SiNMR 3SiO 3/2) 0.55(CH 3(CH 2) 17SiO 3/2) 0.24((tBuO) bSiO 4-b/2) 0.21, Mn be 3030 and Mw be 4410.
Embodiment 3
Present embodiment is illustrated in the formation of silicone resin composition under the condition that is similar to embodiment 1, wherein R 1Be hydrogen, R 2Be styroyl and the R that replaces 3Be the tertiary butyl.With the described consumption of table 4, under argon atmospher, with HSi (OEt) 3(A), (AcO) 2Si (OtBu) 2(B) and right-ZC 6H 4CH 2CH 2Si (OEt) 3(C) be added in 37 grams tetrahydrofuran (THF)s (THF) in flask.Then, (D) is added in this solution with deionized water, and at room temperature this mixture stirred and spend the night.50 gram toluene are added in this reaction mixture.At 35-40 ℃, utilize rotatory evaporator to remove and desolvate, thereby obtain viscous liquid, immediately it is dissolved in then in the 80 gram toluene.As removing residual acetic acid with methylbenzene azeotropic thing (the azeotrope boiling point is 38 ℃).Viscous liquid is added in the 120 gram toluene, and the content that makes viscous liquid is 10% weight (in the gross weight of toluene and viscous liquid), then reflux 30 minutes and carry out azeotropic drying and refluxed 1 hour.Solution filtered and remove by evaporation desolvate, thereby obtain final resin product.The general introduction of resin synthetic is shown in Table 4.Resin analysis is shown in Table 5.
The synthetic general introduction of table 4. resin
Embodiment number ??(A) ??(g) ???(B) ???(g) (C) right-ZC 6H 4CH 2CH 2Si(OEt) 3????(g) ????(D) ????(g) Yield (g)
????3-1 ??5.6 ????5 ????9.6(Z＝Me) ????3.1 ????9.0
????3-2 ??5.6 ????5 ????10.2(Z＝MeO) ????3.1 ????9.6
????3-3 ??5.6 ????5 ????11.8(Z＝Br) ????3.1 ????10.8
????3-4 ??5.6 ????5 ????9.2(Z＝H) ????6.7 ????8.8
Table 5. (HSiO 3/2) f(ZC 6H 4CH 2CH 2) SiO 3/2) g((tBuO) bSiO 4-b/2) hThe analysis of resin
Embodiment F/g/h mol ratio based on reactant Based on 29The f/g/h mol ratio of SiNMR ????Mn ????Mw
????3-1 ????0.25/0.5/0.25 ????0.27/0.5/0.23 ????580 ????1,400
????3-2 ????0.25/0.5/0.25 ????0.21/0.51/0.28 ????480 ????930
????3-3 ????0.25/0.5/0.25 ????0.25/0.47/0.28 ????n.m. ????460
????3-4 ????0.25/0.5/0.25 ????0.24/0.53/0.23 ????n.m. ????600
Embodiment 4
Present embodiment is illustrated the formation of insoluble porous resin, wherein R 1Be hydrogen, R 2Be organic group and R with 8-22 carbon atom 3Be the tertiary butyl.Be metered into the resin (2-3 gram) of embodiment 1 and embodiment 2 preparations in the alumina crucible and be transferred in the quartz tube furnace.(＜2666Pa=also uses the argon backfill to＜20mmHg with stove evacuation.With 50-60 ℃/minute speed, sample is heated to the temperature that is shown in table 6, and, in the argon gas purge, is cooled to room temperature then under this temperature, keeping 2 hours.The solidify material that is obtained is transparent or slight opaque thick film.By the pyrolytical condition of nitrogen absorptiometry, the charing yield, TGA (thermogravimetric analysis) yield and porosity data are listed in table 6 and 7.Charing yield and thermogravimetric analysis yield are represented with the weight percentage that is kept after analyzing under specified temperature.
The analysis of table 6. cured resin
Embodiment number The resin-like Article Number 450 ℃ of charing yield (weight %) 450 ℃ of TGA yield (weight %) 500 ℃ of TGA yield (weight %) Pore volume cm3/g Surface-area, BET m 2/g
?4-1 ??1-1 ????51.9 ????73.8 ????56.4 ??0.701 ????1213
?4-2 ??1-2 ????53.0 ????75.2 ????53.2 ??0.678 ????1123
?4-3 ??1-3 ????53.9 ????77.5 ????57.9 ??0.623 ????1007
?4-4 ??1-4 ????61.8 ????80.2 ????58.2 ??0.349 ????534
?4-5 ??1-5 ????60.8 ????70.8 ????62.6 ??0.515 ????882
?4-6 ??1-6 ????48.5 ????49.8 ????48.3 ??0.297 ????528
?4-7 ??1-7 ????52.1 ????52.5 ????46.4 ??0.430 ????723
?4-8 ??1-8 ????40.1 ????38.8 ????36.2 ??0.452 ????770
?4-9 ??1-9 ????60.6 ????54.3 ????52.7 ??0.246 ????417
?4-10 ??2c ????n.m. ????n.m. ????n.m. ??0.457 ????752
The analysis of table 7. cured resin
Embodiment number The resin-like Article Number Skeletal density G/cm 3 Pore volume cm 3/g Porosity weight % Surface-area, BET m 2/g
????4-1 ????1-1 ????1.669 ??0.701 ??53.9 ????1213
????4-2 ????1-2 ????1.638 ??0.678 ??52.6 ????1123
????4-3 ????1-3 ????1.337 ??0.623 ??45.4 ????1007
????4-4 ????1-4 ????1.346 ??0.349 ??32.0 ????534
????4-5 ????1-5 ????1.751 ??0.515 ??47.4 ????882
Embodiment 5
Present embodiment is illustrated in and forms insoluble porous coating, wherein R on the base material 1Be hydrogen, R 2Be organic group and R with 8-22 carbon atom 3Be the tertiary butyl.The resin (2-3 gram) of embodiment 1,2 and 3 preparations is dissolved among the MIBK, thereby forms the clear solution that comprises 25 weight % resins.Solution is filtered pass through 1.0 microns injecting type membrane filter, pass through 0.2 micron injecting type membrane filter then, thereby remove any macrobead.By 20 seconds of spin coating under 2000rpm, solution is applied on the silicon chip.The silicon chip of coating is put into quartz tube furnace, and this stove is carried out purge with nitrogen.Rapidly described stove is heated to 450 ℃ (50-60 ℃/minute), and, when keeping, is cooled to room temperature then with the nitrogen purge 450 ℃ of insulations 2 hours.Before carrying out performance measurement, the silicon chip that is coated with is stored under the nitrogen atmosphere.The performance of film is listed in the table 8.
The film performance of table 8. resin on silicon chip (450 ℃)
Embodiment number The resin-like Article Number ????Dk Modulus GPa Hardness GPa The thickness dust ????RI
????5-1 ????1-1 ????2.30 ????3.4 ????0.53 ????9396 ????1.186
????5-2 ????1-2 ????1.97 ????2.1 ????0.36 ????11795 ????1.173
????5-3 ????1-3 ????1.70 ????1.8 ????0.31 ????15020 ????1.178
????5-4 ????1-4 ????2.55 ????4.7 ????0.80 ????4921 ????1.288
????5-5 ????1-5 ????2.25 ????4.4 ????0.36 ????14,532 ????1.165
????5-6 ????1-6 ????2.67 ????6.9 ????0.63 ????7478 ????1.233
????5-7 ????1-7 ????2.58 ????6.3 ????0.56 ????5737 ????1.231
????5-8 ????1-8 ????2.72 ????8.0 ????0.66 ????4048 ????1.235
????5-9 ????1-9 ????2.82 ????10.5 ????0.94 ????4244 ????1.266
????5-10 ????2c ????2.18 ????2.0 ????0.39 ????3295 ????1.249
????5-11 ????3-1 ????2.56 ????3.7 ????0.52 ????7697 ????1.339
????5-12 ????3-2 ????2.89 ????6.0 ????0.94 ????7355 ????1.400
????5-13 ????3-3 ????n.m. ????5.9 ????0.81 ????6674 ????1.433
????5-14 ????3-4 ????2.47 ????5.1 ????0.80 ????7372 ????1.342
Embodiment 6
Present embodiment is illustrated in and forms insoluble porous coating, wherein R under the various solidification values on base material 1Be hydrogen, R 2Be organic group and R with 8-22 carbon atom 3Be the tertiary butyl.The resin (2-3 gram) of embodiment 1 preparation is dissolved among the MIBK, thereby forms the clear solution that comprises 25 weight % resins.Solution is filtered pass through 1.0 microns injecting type membrane filter, pass through 0.2 micron injecting type membrane filter then, thereby remove any macrobead.By 20 seconds of spin coating under 2000rpm, solution is applied on the silicon chip.The silicon chip of coating is put into quartz tube furnace, and this stove is carried out purge with nitrogen.Divide stove is heated to 250 ℃, the temperature of 390 ℃ and 450 ℃, and kept respectively 1 hour in each temperature, in maintenance nitrogen purge, be cooled to room temperature then.Before carrying out performance measurement, the silicon chip that is coated with is stored under the nitrogen atmosphere.The performance of film is listed in the table 9.
The film performance of table 9. resin on silicon chip
Embodiment number The resin-like Article Number ????Dk Modulus GPa Hardness GPa The thickness dust ??RI?Tyger
????6-1 ????1-1 ????2.17 ????2.3 ????0.24 ????11,580 ????1.215
????6-2 ????1-3 ????1.80 ????1.2 ????0.14 ????11,749 ????1.206
Embodiment 7
Present embodiment is illustrated the formation of silicone resin composition, and wherein R1 is a methyl, and R2 is that octadecyl and R3 are the tertiary butyl.With the described consumption of table 9, under argon atmospher, with MeSi (OMe) 3(A), (AcO) 2Si (OtBu) 2(B) and CH 3(CH 2) 17Si (OMe) 3(C) be added in 75 grams tetrahydrofuran (THF)s (THF) in flask.Then, (D) is added in this solution with deionized water, and at room temperature this mixture stirred 1 hour.75 gram toluene are added in this reaction mixture.Utilize rotatory evaporator to desolvate, thereby obtain the product of viscous oil, immediately it is dissolved in then in the 150 gram toluene by evaporating to remove.By being heated to 38 ℃, under reduced pressure, to remove residual acetic acid with the form of methylbenzene azeotropic thing.Once more with resin dissolves in 250 gram toluene, and carry out azeotropic drying and refluxed 1 hour.Solution filtered and remove by evaporation desolvate, thereby obtain final resin product.The general introduction of resin synthetic is shown in Table 10.The molecular weight information of resin is shown in Table 11.
The general introduction of table 10. resin synthetic
Embodiment number ????(A) ????(g) ????(B) ????(g) ??(C) ??(g) ??(D) ??(g) Yield (g) Outward appearance
????7-1 ????9.3 ????10.2 ??12.8 ??6.1 ??12.4 The wax shape
????7-2 ????14.9 ????40 ??10.28 ??11.2 ??34.4 Oily
????7-3 ????23.4 ????40.1 ??12.8 ??14.4 ??40.1 Oily
????7-4 ????21.0 ????40.0 ??19.3 ??14.4 ??45.4 The wax shape
????7-5 ????27.8 ????29.9 ??12.8 ??15.0 ??40.0 Oily
Table 11 (MeSiO 3/2) f(CH 3(CH 2) 17SiO 3/2) g((tBuO) bSiO 4-b/2) hResin analysis
Embodiment F/g/h mol ratio based on reactant ????Mn ????Mw
????7-1 ????0.55/0.20/0.25 ????6730 ????22,600
????7-2 ????0.40/0.10/0.50 ????2790 ????18,300
????7-3 ????0.50/0.10/0.40 ????1560 ????9800
????7-4 ????0.45/0.15/0.40 ????1830 ????10,100
????7-5 ????0.60/0.10/0.30 ????2470 ????8320
Embodiment 8
Present embodiment is illustrated the formation of insoluble porous resin, wherein R 1Be methyl, R 2Be octadecyl and R 3Be the tertiary butyl.Be metered into the resin (2-3 gram) of embodiment 7 preparation in the alumina crucible and be transferred in the quartz tube furnace.With stove evacuation to (＜2666Pa=also uses the argon backfill less than＜20mmHg.With 50-60 ℃/minute speed, sample is heated to the temperature that is shown in table 12, and under this temperature, kept 2 hours, in the argon gas purge, be cooled to room temperature then.The solidify material that is obtained is transparent or slight opaque thick film.By the pyrolytical condition of nitrogen absorptiometry, the charing yield, TGA yield and porosity data are listed in table 12 and 13.
The porosity of table 12. cured resin and charing yield
Embodiment number The resin-like Article Number 450 ℃ of charing yield (weight %) 450 ℃ of TGA yield (weight %) 500 ℃ of TGA yield (weight %) Pore volume cm 3/g Surface-area, BET m 2/g
??8-1 ??7-1 ????47.0 ????78.7 ????492 ??0.515 ????719
??8-2 ??7-2 ????55.1 ????59.5 ????51.4 ??0.451 ????731
??8-3 ??7-3 ????52.7 ????60.7 ????52.5 ??0.523 ????874
??8-4 ??7-4 ????51.9 ????60.8 ????48.5 ??0.464 ????749
??8-5 ??7-5 ????58.1 ????64.9 ????55.8 ??0.436 ????711
The analysis of table 13. cured resin
Embodiment number The resin-like Article Number Skeletal density G/cm 3 Pore volume cm 3/g Porosity weight % Surface-area, BET m 2/g
????8-1 ????7-1 ????1.380 ??0.515 ??41.5 ????719
????8-2 ????7-2 ????1.591 ??0.451 ??41.8 ????731
????8-3 ????7-3 ????1.429 ??0.523 ??42.8 ????874
????8-4 ????7-4 ????1.508 ??0.464 ??41.2 ????749
????8-5 ????7-5 ????1.447 ??0.436 ??38.7 ????711
Embodiment 9
Present embodiment is illustrated in and forms insoluble porous coating, wherein R on the base material 1Be methyl, R 2Be octadecyl and R 3Be the tertiary butyl.The resin (2-3 gram) of embodiment 7 preparations is dissolved among the MIBK, thereby forms the clear solution that comprises 25 weight % resins.Solution is filtered pass through 1.0 microns injecting type membrane filter, pass through 0.2 micron injecting type membrane filter then, thereby remove any macrobead.By 20 seconds of spin coating under 2000rpm, solution is applied on the silicon chip.The silicon chip of coating is put into quartz tube furnace, and this stove is carried out purge with nitrogen.Rapidly described stove is heated to 450 ℃ (50-60 ℃/minute), and, when keeping, is cooled to room temperature then with the nitrogen purge 450 ℃ of insulations 2 hours.Before carrying out performance measurement, the silicon chip that is coated with is stored under the nitrogen atmosphere.The modulus of film and specific inductivity (Dk) are listed in the table 14.
The film performance of table 14. resin on silicon chip (450 ℃)
Embodiment number The resin-like Article Number ??Dk Modulus GPa Hardness GPa The thickness dust ????RI
????9-1 ????7-1 ??2.43 ????4.7 ????0.69 ????4921 ????1.295
????9-2 ????7-2 ??2.19 ????3.2 ????0.47 ????7960 ????1.242
????9-3 ????7-3 ??2.24 ????4.8 ????1.04 ????7030 ????1.266
????9-4 ????7-4 ??2.02 ????3.3 ????0.80 ????7248 ????1.242
????9-5 ????7-5 ??2.13 ????3.7 ????0.86 ????7622 ????1.274
Embodiment 10
Under argon shield, with tetrahydrofuran (THF)/toluene (3: 2 w/w) solvent of measuring vol, Cl 2Si (OtBu) 2, HSi (OEt) 3And RSi (OMe) 3Be added in the reaction flask, form a clear solution.Then, deionized water is added in this reaction mixture lentamente.Under the situation that does not have heating, this material was stirred 1 hour then, and remove the HCl by product by successive argon purge.Vacuum (1 mmhg) evaporation of volatile substances at room temperature again, and remaining oily product is dissolved in the toluene.In backflow toluene, this product solution is carried out azeotropic drying and increased the weight of 30 minutes.This solution is filtered pass through 1.0 microns syringe filter.Vacuum evaporating solvent under 25 ℃ and 1mmHg has obtained final product.Prescription, synthesis condition and yield are summarized in the table 15.Molecular weight information and composition are shown in Table 16.
The general introduction of table 15. resin synthetic
Sample The theoretical composition HSi(OEt) 3????g Cl 2Si(OtBu) 2????g ?RSi(OMe) 3????g THF/ toluene/H 2O ????g Toluene increases the weight of g Yield, the gram outward appearance
10-1 T H 0.36 Q 0.46T R 0.18 9.0 ????17.3 (MeO) 3Si- (CH 2) 17CH 3????10.0 ?60/40/4.0 ?90.0 20.0, the wax shape
10-2 T H 0.50 Q 0.33T R 0.17 9.0 ????9.0 (MeO) 3Si-four isobutyl-s 6.6 ?60/40/4.0 ?120.4 11.7, solid
Q comprises Q (OtBu) b
Table 16. material characterizes
Sample The theoretical composition ????Mw ????Mn
??10-1 ??T H 0.36 Q 0.46T R 0.18 ????-- ????--
??10-2 ??T H 0.50Q 0.33T R 0.17 ????4,790 ????188,800
Embodiment 11
In typical method, with Cl 2Si (OtBu) 2, RSiCl 3And HSiCl 3Mixture be dissolved among the 40ml MIBK and under 0 ℃ of nitrogen atmosphere, be added drop-wise in the mixture that the HCl water by 80mlMIBK and 60ml 0.5M in the 500ml flask forms.At 25 ℃ reaction mixture is spent the night.Remove and anhydrate and insoluble substance, and utilize Dean Stark water trap to make the organic phase drying.Utilize revolution evaporator evaporation solvent, obtain 4.0 gram white solids.The general introduction of resin synthetic is shown in Table 17.Molecular weight information and composition are shown in Table 18.
The general introduction of table 17. resin synthetic
Sample The theoretical composition HSiCl 3????g ?Cl 2Si(OtBu) 2????g ????RSiCl 3????g Yield, the gram outward appearance
??11-1 T H 0.5Q 0.25T R 0.25 ????7.8 ????7.0 ?CH 3(CH 2) 17SiCl 3??11.2 4, solid
??11-2 T H 0.4Q 0.375TR 0.225 ????6.2 ????10.6 ?CH 3(CH 2) 17SiCl 3??10.0 9, solid
??11-3 T H 0.5Q 0.25T R 0.25 ????7.8 ????7.0 ?Cl 3Si-three isobutylenes 8.7 7.9, the wax shape
Q comprises Q (OtBu) b
Table 18. material property
Sample The R group Theoretical resin is formed Resin by NMR is formed Mw ?Mn
?11-2 ?CH 3(CH 2) 17 TH 0.4Q 0.375TR 0.225 ?T C18 0.31Q 0.08T R 0.61 14200 ?3790
?11-3 Three isobutylenes T H 0.5Q 0.25T R 0.25 ?T C12 0.42Q 0.06T H 0.53 1870 ?1380
Embodiment 12
Be metered into the five equilibrium resin sample of embodiment 11 preparation in the alumina crucible and be transferred in the quartz tube furnace.Stove evacuation extremely＜20 is held in the palm and uses the argon backfill.Under the argon purge, the speed with 10 ℃/minute is heated to design temperature with sample, and keeps 2 hours under this temperature, is cooled to room temperature then.The final solidify material that is obtained is transparent or slight opaque thick self-support film.Pyrolytical condition, charing yield and porosity information by the nitrogen absorptiometry are listed in the table 19.
The porosity of table 19. resin and charing yield (450 ℃ of pyrolysis)
Sample The R group Resin is formed, NMR Pore volume cc/g Surface-area, BET m 2/g
??11-1 ??CH 3(CH 2) 17 ?T R 0.18Q 0.22T H 0.60 ????0.54 ????925
??11-2 ??CH 3(CH 2) 17 ?T C18 0.31Q 0.08T H 0.61 ????0.48 ????724
??11-3 Three isobutylenes ?T C12 0.42Q 0.06T H 0.53 ????0.44 ????746
Q comprises Q (OtBu) b
Embodiment 13
With the five equilibrium resin dissolves of embodiment 11 preparation in hexone (MIBK), thereby form the clear solution that comprises 25 weight %.Make solution filter injecting type membrane filter in proper order, thereby remove any macrobead by 1.0 microns and 0.2 micron.This solution is administered on the silicon chip, and utilizes Karl Suss RC8 or Headway spin coater to be spin-coated on the silicon chip, then 20 seconds of 2000rpm spin coating.By the thickness in conjunction with the may command spin-coated thin film of strength of solution and spin speed, its thickness from 2000 to 20,000 dusts.
Pack into resin molding in the QTF stove and under nitrogen atmosphere, be heated to 450 ℃ rapidly.At 450 ℃ film was heated 2 hours, be cooled to room temperature then.Before carrying out performance measurement, the silicon chip of all coatings is stored under the nitrogen atmosphere.By T H aT R bQ cThe modulus and the specific inductivity of the film that resin obtains are listed in the table 20.
Table 20.T H aT R bQ cThe film performance of resin
Sample The R group Resin is formed, NMR After fixing thickness, (dust) ????RI ????dk Modulus (GPa)
?11-1 CH 3(CH 2) 17Si ?T R 0.18Q 0.22T H 0.60 ????7773 ??1.201 ??1.82 ??2.3
?11-2 CH 3(CH 2) 17 ?T C18 0.31Q 0.08T H 0.61 ????1679 ??-- ??1.82 ??--
?11-3 Three isobutylenes ?T C12 0.42Q 0.06T H 0.53 ????4792 ??1.285 ??2.19 ??--
?11-3 Three isobutylenes ?T C12 0.42Q 0.06T H 0.53 ????3844 ??1.358 ??1.72 ??3.3
Q comprises Q (OtBu) b
Comparative Examples 1
Present embodiment is illustrated the formation of silicone resin composition, wherein R 1Be hydrogen, R 2Do not exist and R 3Be the tertiary butyl.With the described consumption of table 13, under argon atmospher, with HSi (OEt) 3(A) and (AcO) 2Si (OtBu) 2(B) be added in 72 grams tetrahydrofuran (THF)s (THF) in flask.Then, (D) is added in the flask with deionized water, and at room temperature this mixture stirred 1 hour.Then, 75 gram toluene are added in this mixture.Utilize rotatory evaporator to remove and desolvate, thereby obtain viscosity buttery silicone resin, immediately it is dissolved in then in the 150 gram toluene by evaporation.By being heated to 38 ℃, under reduced pressure, to remove by-product acetic acid with the form of methylbenzene azeotropic thing.Once more with resin dissolves in 110 the gram toluene in, and in backflow toluene, carry out azeotropic drying and the heating 1 hour.Solution filtered and remove by evaporation desolvate, thereby obtain silicone resin product.The general introduction of resin synthetic is shown in Table 21.The molecular weight information of resin is shown in Table 22.
The general introduction of table 21. resin synthetic
Comparative Examples number ????(A) ????(g) ????(B) ????(g) ????(D) ????(g) Yield (g) Outward appearance
????C1-1 ????5.67 ????40.2 ????6.1 ????23.7 Gluey
????C1-2 ????11.23 ????30.0 ????6.65 ????18.7 Gluey
????C1-3 ????26.2 ????20.0 ????10.0 ????19.2 Gluey
Table 22. (HSiO 3/2) f((tBuO) bSiO 4-b/2) hThe analysis of resin
Comparative Examples number F/h mol ratio based on reactant Based on 29The f/g mol ratio of SiNMR ????Mn ????Mw
????C1-1 ????0.20/0.80 ????0.21/0.79 ????3,040 ????6,300
????C1-2 ????0.40/0.60 ????0.43/0.57 ????6,750 ????25,800
????C1-3 ????0.70/0.30 ????n.m. ????n.m. ????n.m.
Be metered into resin sample (2-3 gram) in the alumina crucible and be transferred in the quartz tube furnace.Stove evacuation is extremely also used the argon backfill less than 20mmHg (less than 2666Pa).With 50-60 ℃/minute speed, sample is heated to 450 ℃, and under this temperature, is incubated 1 hour, then, under argon cleaning, be cooled to room temperature.The final solidify material that obtains is transparent or slight opaque thick film.Pyrolysis temperature, charing yield and porosity data are listed in the table 23.The charing yield is represented with the weight percentage that is kept after analyzing under specified temperature.
The porosity of table 23. cured resin and charing yield
The resin-like Article Number Skeletal density g/cm 3 Charing yield weight % Pore volume cm 3/g Porosity % Surface-area, BET m 2/g
????C1-1 ????1.970 ????45.8 ??0.313 ????38.1 ????550
????C1-2 ????1.982 ????51.4 ??0.317 ????38.6 ????559
????C1-3 ????1.787 ????65.0 ??0.224 ????28.6 ????392
Resin sample (2-3 gram) is dissolved among the MIBK, thereby forms the clear solution that comprises 25 weight % resins.Solution is filtered pass through 1.0 microns injecting type membrane filter, pass through 0.2 micron injecting type membrane filter then, thereby remove any macrobead.By 20 seconds of spin coating under 2000rpm, solution is applied on the silicon chip.The silicon chip of coating is put into quartz tube furnace, and this stove is carried out purge with nitrogen.Stove is heated to 450 ℃ temperature (50-60 ℃/minute) and under this temperature, is incubated 2 hours, when keeping, be cooled to room temperature then with the nitrogen purge.Before carrying out performance measurement, the silicon chip that is coated with is stored under the nitrogen atmosphere.The modulus of film and specific inductivity (Dk) are listed in the table 24.
The film performance of table 24. resin on silicon chip
The resin-like Article Number ????Dk Modulus GPa Hardness GPa The thickness dust ????RI
????C1-1 ??24.3 ????18.6 ????0.88 ????4,180 ????1.321
????C1-2 ??14.9 ????16.1 ????0.77 ????4,120 ????1.355
????C1-3 ??6.34 ????10.8 ????1.06 ????6,590 ????1.290
Present embodiment is illustrated, and compares with 2 with embodiment 1, wherein R 1Be hydrogen, R 2Do not exist and R 3For the silicone resin of the tertiary butyl has good modulus, but Dk is high as can not to accept.In addition, present embodiment also shows: when with comprise R 2And R 3The embodiment 1 of group is when 2 compare, and porosity is lower.
Comparative Examples 2
Present embodiment is illustrated the formation of silicone resin composition, wherein R 1Be methyl, R 2Do not exist and R 3Be the tertiary butyl.With the described consumption of table 17, under argon atmospher, with MeSi (OMe) 3(A), (AcO) 2Si (OtBu) 2(B) and THF be added in the flask.AcO represents acetoxyl group, and Me represents methyl, and tBu represents the tertiary butyl.Then, deionized water is added in the flask, and at room temperature this mixture was stirred 1 hour.75 gram toluene are added in this reaction mixture.Utilize rotatory evaporator to remove and desolvate, thereby obtain viscosity oily product, immediately it is dissolved in then in the 150 gram toluene by evaporation.Under reduced pressure, to remove residual acetic acid with the form of methylbenzene azeotropic thing (the azeotrope boiling point is 38 ℃).Once more with resin dissolves in 110 gram toluene, and carry out azeotropic drying and refluxed 1 hour.Solution filtered and remove by evaporation desolvate, thereby obtain final resin product.The general introduction of resin synthetic is shown in Table 25.The molecular weight information of resin is shown in Table 26.
The general introduction of table 25. resin synthetic
Comparative Examples number ????(A) ????(g) ????(B) ????(g) ??THF ????(g) ????H 2O ????(g) Yield (g) Outward appearance
????C2-1 ????18.6 ????40.0 ????72.0 ????11.1 ????23.6 Solid
????C2-2 ????27.9 ????40.0 ????80.0 ????14.5 ????26.0 Solid
????C2-3 ????43.5 ????40.3 ????90.0 ????20.0 ????40.0 Solid
????C2-4 ????92.9 ????39.9 ????120.3 ????28.3 ????67.3 The wax shape
Table 26. (MeSiO 3/2) f((tBuO) bSiO 4-b/2) hResin analysis
Comparative Examples number F/h mol ratio based on reactant Based on 29The f/g mol ratio of SiNMR ??Mn ????Mw
??C2-1 ????0.50/0.50 ????0.44/0.56 ?2,990 ????17,700
??C2-2 ????0.60/0.40 ????0.55/0.44 ?2,010 ????46,000
??C2-3 ????0.70/0.30 ????0.69/0.31 ?n.m. ??＞100,000
??C2-4 ????0.85/0.15 ????0.83/0.17 ?3,400 ????32,100
Be metered into resin sample (2-3 gram) in the alumina crucible and be transferred in the quartz tube furnace.Stove evacuation is extremely also used the argon backfill less than 20mmHg (less than 2666Pa).With 10 ℃/minute speed, sample is heated to 450 ℃, and under this temperature, is incubated 1 hour, under the argon flushing, be cooled to room temperature then.The final solidify material that obtains is transparent or slight opaque thick film.Pyrolysis temperature, charing yield and porosity data are listed in the table 27.The charing yield is represented with the weight percentage that is kept after analyzing under specified temperature.
The porosity of table 27. cured resin and charing yield
The resin-like Article Number Skeletal density g/cm 3 Charing yield weight % Pore volume cm 3/g Porosity % Surface-area, BET m 2/g
????C2-1 ??1.693 ????60.5 ????0.271 ??31.4 ????461
????C2-2 ??1.624 ????72.5 ????0.280 ??31.3 ????481
????C2-3 ??1.505 ????78.0 ????0.249 ??27.2 ????425
????C2-4 ??1.398 ????76.5 ????0.125 ??14.9 ????168
Resin sample (2-3 gram) is dissolved among the MIBK, thereby forms the clear solution that comprises 25 weight % resins.Solution is filtered pass through 1.0 microns injecting type membrane filter, pass through 0.2 micron injecting type membrane filter then, thereby remove any macrobead.By 20 seconds of spin coating under 2000rpm, solution is applied on the silicon chip.The silicon chip of coating is put into quartz tube furnace, and this stove is carried out purge with nitrogen.Stove is heated to the temperature shown in the table 21 (50-60 ℃/minute), and under this temperature, is incubated 2 hours, when keeping the nitrogen purge, be cooled to room temperature then.Before carrying out performance measurement, the silicon chip that is coated with is stored under the nitrogen atmosphere.The modulus of film and specific inductivity (Dk) are listed in the table 28.
The film performance of table 28. resin on silicon chip
The resin-like Article Number Temperature ℃ ????Dk Modulus GPa Hardness GPa The thickness dust ????RI
????C2-1 ??450 ????2.32 ????7.9 ????0.91 ????6,300 ????1.273
????C2-1 ??425 ????2.36 ????9.0 ????1.11 ????6,728 ????1.276
????C2-1 ??400 ????2.48 ????8.7 ????0.95 ????6,826 ????1.271
????C2-2 ??450 ????2.16 ????3.5 ????0.51 ????6,199 ????1.252
????C2-2 ??425 ????2.48 ????5.5 ????0.65 ????6,374 ????1.307
????C2-2 ??400 ????2.55 ????4.8 ????0.53 ????6,333 ????1.338
????C2-3 ??450 ????2.61 ????7.4 ????1.11 ????8,551 ????1.347
????C2-3 ??425 ????2.52 ????6.9 ????1.08 ????9,025 ????1.350
????C2-3 ??400 ????2.38 ????7.4 ????1.19 ????9,413 ????1.336
????C2-4 ??450 ????2.88 ????7.8 ????1.4 ????10,500 ????1.368
????C2-4 ??425 ????2.71 ????6.0 ????1.19 ????10,525 ????1.383
????C2-4 ??400 ????2.63 ????7.1 ????1.25 ????10,892 ????1.375
Present embodiment is illustrated: when comparing with the embodiment 7 that comprises R2 and R3 group, and R wherein 1Be methyl, R 2Do not exist and R 3For the silicone resin of the tertiary butyl have fine Dk and porosity lower.
Comparative Examples 3
Present embodiment is illustrated the formation of silicone resin composition, wherein R 1Be hydrogen, R 2Be octadecyl and R 3Do not exist.At 110 ℃, 1.2 * 10 -5Weight part platinum (is and 1,3-divinyl-1,1,3, the form of 3-tetramethyl disiloxane title complex) under the existence, makes the hydrogen silicon half silicone resin (weight-average molecular weight 70 that is dissolved in the toluene, 000, by people's such as Collins US3, method described in 615,272 preparation) two kinds of solution reacted 2 hours with the 1-octadecylene.Reacted every kind of resin solution sample (2 gram) is placed porcelain crucible, under nitrogen atmosphere,, under nitrogen atmosphere, heated 1 hour then in 500 ℃ in 350 ℃ of heating 0.5 hour.With toluene every kind of resin solution sample is diluted to 17% weight, is applied on the silicon chip and as described in embodiment 5 by spin coating and is cured, then Measuring Dielectric Constant.Table 29 shows the parts by weight of per 1 weight part hydrogen silsesquioxane resin solvent for use and 1-octadecylene, the porosity of each sample and specific inductivity.Sample C3-3 is the toluene solution of hydrogen silsesquioxane resin, and it does not react with the 1-octadecylene.
Table 29. (HSiO 3/2) f(CH 3(CH 2) 17SiO 3/2) gResin analysis
Comparative Examples number The weight part of toluene The weight part of octadecylene F/g mol ratio based on reactant Porosity % Dk
?C3-1 ?2.22 ?1.60 ?0.66/0.34 ?27.1 ?2.1
?C3-2 ?2.72 ?1.10 ?0.77/0.23 ?27.9 ?2.2
?C3-3 ?4.72 ?0 ?1.0/0 ?0 ?3.0
Present embodiment is illustrated: when with comprise R 2And R 3The embodiment 1 of O group compares with 2, wherein R 1Be hydrogen, R 2Be octadecyl R 3Non-existent silicone resin has good Dk, and porosity is lower.

Claims (26)

1. silicone resin composition comprises:
(A) 2.5-85 molar part R 1SiO 3/2Siloxane unit, wherein, R 1Be independently selected from alkyl with 1-5 carbon atom, hydrogen, and mix;
(B) 2.5-50 molar part R 2SiO 3/2Siloxane unit, wherein, R 2Be independently selected from any monovalent organic radical group with 6-30 carbon atom and any monovalent organic radical group with replacement of 6-30 carbon atom; With
(C) 5-95 molar part (R 3O) bSiO (4-b)/2Siloxane unit, wherein, R3 is independently selected from the branched-chain alkyl that has 3-30 carbon atom branched-chain alkyl and have the replacement of 3-30 carbon atom, and b is 1-3; Component (A), total amount (B) and (C) is 100 molar part, and component (A), (B) and (C) sum be in the resin combination siloxane unit total amount at least 50%.
2. the described silicone resin composition of claim 1, wherein, silicone resin comprises the component (A) of average 30-60 molar part, component of 10-25 molar part (B) and 20-50 molar part (C), wherein, component (A), total amount (B) and (C) is 100 molar part, and (A), sum (B) and (C) be in the resin combination siloxane unit total amount at least 70%.
3. the described silicone resin composition of claim 1, wherein, R 1Be selected from methyl, hydrogen, and mix R 2Be replacement or unsubstituted alkyl with 10-20 carbon atom, and R 3For having the tertiary alkyl of 4-18 carbon atom.
4. the described silicone resin composition of claim 1, wherein, R3 is the tertiary butyl.
5. the described silicone resin composition of claim 1, wherein, described resin also comprises at least a following siloxane unit: the R that is selected from addition 1Si (X) dO (3-d/2), R 2Si (X) dO (3-d/2), Si (X) d(OR 3) fO (4-d-f/2), SiO 4/2And composition thereof, wherein, R 1, R 2, and R 3As top definition; Each X is hydrolysable group or hydroxyl independently, and d and f are 1-2.
6. one kind comprises R 1SiO 3/2Siloxane unit, R 2SiO 3/2Siloxane unit and (R 3O) bSiO (4-b)/2The preparation method of the silicone resin of siloxane unit, this method comprises:
Being enough to form the time and the temperature of silicone resin, with following component (a)-(d) mix:
(a) 2.5-85 molar part formula R 1SiX 3Silane or silane mixture, wherein, each R 1Be independently selected from alkyl with 1-5 carbon atom, hydrogen, and mix, X is hydrolysable group or hydroxyl independently;
(b) 2.5-50 molar part formula R 2SiX 3Silane or silane mixture, R wherein 2Be independently selected from any monovalent organic radical group with 6-30 carbon atom and any monovalent organic radical group with replacement of 6-30 carbon atom, X is hydrolysable group or hydroxyl independently; (c) 5-95 molar part formula (R 3O) cSiX (4-c)Silane or silane mixture, wherein, R 3Be independently selected from branched-chain alkyl with 3-30 carbon atom and have the branched-chain alkyl of the replacement of 3-30 carbon atom, c is the 1-3 that comprises end value, and X is hydrolysable group or hydroxyl independently, and silane (a) is 100 molar part with (c) total amount (b); With
(d) water.
7. the described method of claim 6 also comprises solvent in addition.
8. the described method of claim 6, wherein, R 1Be selected from methyl, hydrogen, and mix R 2Be replacement or unsubstituted alkyl with 10-20 carbon atom, and R 3For having the tertiary alkyl of 4-18 carbon atom.
9. the described method of claim 6, wherein, R 3It is the tertiary butyl.
10. the described method of claim 6, wherein, based on silane (a), every mole of X in silane (b) and the silane (c), water-content is the 0.5-2.0 mole.
11. the method for claim 6, wherein, based on silane (a), every mole of X in silane (b) and the silane (c), water-content is the 0.8-1.8 mole.
12. the described method of claim 6, wherein, X is the chlorine atom.
13. pass through the product of the method preparation of claim 12.
14. the formation method of an insoluble porous resin comprises:
(A) to be enough to make the silicone resin solidified temperature and time of claim 1, heat described silicone resin,
(B) to be enough to from the curing silicone resin, removing R 2And R 3The temperature and time of O group is the described silicone resin of heating further, forms insoluble porous resin thus.
15. the method for claim 12, wherein, the heating of step (A) from greater than 20 ℃ to 350 ℃ and heating in step (B) from greater than 350 ℃ to 600 ℃.
16. the method for claim 12, wherein, the curing of silicone resin and from the curing silicone resin, remove R 3The O group was finished in a step.
17. the method for claim 12, wherein, the porosity of insoluble porous resin is the 1-60% volume, and modulus is 1.0-10GPa.
18. a method that forms insoluble porous coating on base material comprises the steps:
(A) with the coating composition coated substrate that comprises silicone resin composition, described silicone resin composition comprises:
(a) 2.5-85 molar part R 1SiO 3/2Siloxane unit, wherein, R 1Be selected from alkyl with 1-5 carbon atom, hydrogen, and mix,
(b) 2.5-50 molar part R 2SiO 3/2Siloxane unit, wherein, R 2Be selected from any monovalent organic radical group with 6-30 carbon atom and have 6-30 carbon atom replacement any monovalent organic radical group and
(c) 5-95 molar part (R 3O) bSiO (4-b)/2Siloxane unit, wherein, R 3Be selected from the branched-chain alkyl that has 3-30 carbon atom branched-chain alkyl and have the replacement of 3-30 carbon atom, b is 1-3, component (a), and total amount (b) and (c) is 100 molar part, and component (a), (b) and (c) sum be in the resin combination siloxane unit total amount at least 50%;
(B) the heating substrates coated to be enough to make coating composition solidified temperature and
(C) further heat substrates coated to being enough to from cure coating compositions, to remove R 2And R 3The temperature of O group forms insoluble porous coating thus on base material.
19. the method for claim 18, wherein, the heating in the step (B) from greater than 20 ℃ to 350 ℃ and further heating in step (C) from greater than 350 ℃ to 600 ℃.
20. the method for claim 18, wherein, described curing and in remove R 2And R 3The O group is finished in a step in greater than 20 ℃ to 600 ℃ scope.
21. the method for claim 18 wherein, is removed R 2And R 3The O group carries out in greater than 350 ℃ to 600 ℃ temperature range.
22. the method for claim 18, wherein, the porosity of insoluble porous coating is the 1-60% volume, and specific inductivity is in the 1.5-3.0 scope, and modulus is 1.0-10GPa.
23. electronic substrate that has by the insoluble porous coating of the method for claim 18 preparation.
24. a method that forms insoluble porous coating on base material comprises the steps:
(A) product with preparation in the claim 12 is coated with base material;
(B) be enough to make under the coating composition solidified temperature substrates coated heated and
(C) further heat substrates coated to from the solidified coating composition, removing any R 2The temperature of group forms insoluble porous coating thus on base material.
25. the method for claim 24 wherein, is carried out described curing and is removed step in a step in greater than 20 ℃ to 600 ℃ temperature range.
26. electronic substrate that has by the insoluble porous coating of the method for claim 24 preparation.
CNA028147286A 2001-07-26 2002-06-18 Siloxane resins Pending CN1535301A (en)

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CN101501139B (en) * 2006-08-04 2011-08-17 陶氏康宁公司 Silicone resin and silicone composition
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KR100683428B1 (en) * 1999-10-25 2007-02-20 다우 코닝 코포레이션 Silicone resin compositions having good solution solubility and stability
KR101191098B1 (en) * 2004-12-17 2012-10-15 다우 코닝 코포레이션 Siloxane resin coating
CA2920646A1 (en) 2016-02-12 2017-08-12 Seastar Chemicals Inc. Organometallic compound and method
JP6923199B2 (en) * 2017-11-07 2021-08-18 国立研究開発法人産業技術総合研究所 Manufacturing method of halosilane

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EP1095958B1 (en) * 1999-10-25 2006-02-08 Dow Corning Corporation Soluble silicone resin compositions

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CN101501139B (en) * 2006-08-04 2011-08-17 陶氏康宁公司 Silicone resin and silicone composition
CN111006182A (en) * 2018-10-04 2020-04-14 Zkw集团有限责任公司 Projection arrangement for a light module of a motor vehicle headlight and method for producing a projection arrangement

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