CN101348568B - Accurate structure POSS hybridization low dielectric material preparation - Google Patents
Accurate structure POSS hybridization low dielectric material preparation Download PDFInfo
- Publication number
- CN101348568B CN101348568B CN 200810041996 CN200810041996A CN101348568B CN 101348568 B CN101348568 B CN 101348568B CN 200810041996 CN200810041996 CN 200810041996 CN 200810041996 A CN200810041996 A CN 200810041996A CN 101348568 B CN101348568 B CN 101348568B
- Authority
- CN
- China
- Prior art keywords
- poss
- low dielectric
- dielectric material
- hybridization
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 CCCCCNO*=*(*)ON(C)C Chemical compound CCCCCNO*=*(*)ON(C)C 0.000 description 1
- LNKZBMIHRCNPID-UHFFFAOYSA-N Cc(cc1)ccc1Oc1cc(Oc2ccc(C)cc2)ccc1 Chemical compound Cc(cc1)ccc1Oc1cc(Oc2ccc(C)cc2)ccc1 LNKZBMIHRCNPID-UHFFFAOYSA-N 0.000 description 1
- YWYHGNUFMPSTTR-UHFFFAOYSA-N Cc(cc1)ccc1Oc1ccc(C)cc1 Chemical compound Cc(cc1)ccc1Oc1ccc(C)cc1 YWYHGNUFMPSTTR-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a preparation method for a finely structured POSS hybridization low dielectric material. The method takes a POSS monomer containing an active group and dual functional group organic micromolecules capable of having a click chemical reaction as the precursor of the finely structured hybridization low dielectric material, and makes use of an environmentally friendly click chemical synthesis method to connect the finely structured POSS molecules and the organic micromolecules onto the low dielectric material structure orderly. Through changing the composition, structure and performance of the organic molecular chain connected with POSS, the method realizes the adjustment and control of the structure, porosity, thermal property, mechanical property and dielectric constant of the finely structured hybridization low dielectric material.
Description
Technical field
The invention belongs to the dielectric materials preparation field, particularly relate to a kind of preparation method of accurate structure POSS hybridization low dielectric material.
Background technology
Be accompanied by the develop rapidly of circuit, device and element, the especially in recent years appearance of high density integrated circuit, also more and more higher to the requirement of electronic package material.Electronic package material is the important support of Electronic Encapsulating Technology.Concerning integrated antenna package, electronic package material refers to the sealing member of unicircuit.Not only chip had mechanical support and Environmental Role by encapsulation; make it avoid pollution and the erosion of steam, impurity and various chemical atmospheres in the atmosphere; thereby make integrated circuit (IC) chip can play consistently the normal electrical airway dysfunction, and the thermal characteristics and even the reliability that encapsulate device and circuit play a part very important.Electronic package material mainly contains plastic cement, ceramic packaging material and Materials for Metal Packaging.Because rear both poor processability, be difficult to satisfy the Electronic Encapsulating Technology that develops rapidly, its application is confined to the air-tight packaging in space flight, aviation and the military field, and, quality low owing to price as the plastic encapsulant of non-air-tight packaging is light, excellent performance is widely used in civil area.Present Electronic Encapsulating Technology requires plastic cement to have following performance: thermostability is high, and mechanical property is good, and dielectric properties are excellent, good flame resistance, radio frequency stability height, and machine-shaping property is good, and water-intake rate is low, and (CTE) is low for thermal expansivity, and thermal conductivity is high.
Plastic cement generally is comprised of matrix resin, filler and additive etc.Matrix resin is the plastic cement important component, plays bonding, insulate and gives the machine-shaping property of material excellence.Current mainly containing: Resins, epoxy (ER), silicone based (silicone plastics), polyimide (PI) and polyphenylene sulfide (PPS) etc.
CN200510021278.8 discloses a kind of polyphenylene sulfide electronic packaging material, contains the high purity polyphenylene sulfide, through the mineral filler of coupling agent surface-treated, toughner and rheological modifier.CN200710027674.0 discloses a kind of composite epoxy type electron packaging material and preparation method thereof, and the gained composite epoxy type electron packaging material has thermotolerance height, water-absorbent is low and environmental protection flame retardant is good advantage.CN200410026436.4 discloses a kind of modifying epoxy resin by organosilicon and preparation method thereof and by the preparation method of its electronic package material of making and this electronic package material thereof, has got the Electronic Packaging epoxide resin material of more excellent performance.CN01103521.8 discloses the synthetic technology of the solvable polyarylether of a kind of low-k, and this kind polyarylether has lower specific inductivity (2.7～2.8) and solubility property preferably.CN200410083960.5 discloses a kind of preparation method of Nano film of multiporous polyimide in low dielectric constant.Adopt sol-gel method to prepare polyimide/nano-silica hybrid films, laminated film is immersed in the etching liquid, then through washing and dry, the nanofoam films of preparation polyimide.02807986.8 disclose a kind of low-k organic dielectric based on cagelike structure, it has the first main chain with aromatics part and the first reactive group, with the second main chain with aromatics part and the second reactive group, wherein the first and second main chains do not have additional crosslink agent by the first and second reactive groups are crosslinked in crosslinking reaction, and the cagelike structure that wherein contains at least 10 atoms be covalently bound to the first and second main chains one of at least on.
Along with the update of electronic package material and technology, people are pursuing the high performance while of product, more pay attention to its characteristics such as nontoxic, green, environmental friendliness.Existing a lot of relevant proposal and rules requires restriction and forbids using in the electron trade some damage to the environment and healthy material now.Matrix resin is the main part of electronic package material, therefore, synthetic make new advances have toughness reinforcing, heat conduction, heat-resisting, a hydrophobic and low dielectric resin of flame retardant properties, be that exploitation is nontoxic, green, the key of environmentally friendly electronic package material.
Cage modle multiaspect oligomeric silsesquioxane (Polyhedral oligomeric silsesquioxane, abbreviation POSS) the about 1～3nm of size of molecule, 1.5), and the microvoid structure with the about 0.5nm intrinsic in aperture the similar (Si: O=1: to silicon-dioxide of its cagelike structure.POSS molecular thermodynamics stable in properties, density are low, and mechanical property is excellent.Eight (or ten of its cagelike structure, or 12) but the different organo-functional group of individual summit keyed jointing, become POSS organic functional monomer, it is the multi-functional hybrid molecule of a class, can be by the chemical bond grafting at high molecular side chain or directly enter main chain and cross-linked network, preparation copolymerization or crosslinked hydridization polymer.In addition, POSS itself has good flame retardant resistance, no matter be connected to high molecular side chain or main chain, still directly enter cross-linked network, because the nanometer size effect (size of molecule about 1～3nm), in the situation of being heated, can hinder the motion of molecule segment, improve the high molecular thermodynamic stability of hydridization.And the multiaspect micropore SiO in the POSS molecule
2Have rigid structure, can effectively reduce the thermal expansivity of material, improve thermal conductivity.
CN200710110427.7 discloses and has contained low dielectric resin of oligomeric silsesquioxane and preparation method thereof.This resin is after other thermosetting resins such as silesquioxane compound, bismaleimides, cyanate and/or Resins, epoxy, allylic cpd etc. of containing reactive functional groups mix by melting or solution methods, to prepare through pre-polymerization.This resin cured matter has lower specific inductivity, preferably resistance toheat.But the material structure of this method preparation is difficult to accurately control, can cause the unstable of material property.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of accurate structure POSS hybridization low dielectric material, this method is take the POSS monomer that comprises active group and the double-functional group organic molecule that can the click chemical reaction presoma as the preparation of precision architecture hybridization low dielectric material, utilize eco-friendly click chemistry synthetic method, the POSS molecule of precision architecture and organic molecule are connected in the dielectric materials structure in an orderly manner.
The preparation method of accurate structure POSS hybridization low dielectric material of the present invention comprises step:
In solution system, and in the presence of light trigger or catalyzer, POSS and double-functional group organic precursor react 0.5～10h under illumination or heating (20～60 ℃) condition, generate accurate structure POSS hybridization low dielectric material, the wherein SiO among the POSS
1.5With the mass ratio of double-functional group organic precursor be 5～80: 90～20, the ratio of preferred mass is 20～60: 80～40.
The solvent of described solution system is one or more in water, methyl alcohol, ethanol, hexanaphthene, benzene,toluene,xylene, dioxane, tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), the methylene dichloride, and the mass ratio of itself and presoma POSS is 100～2: in 1 scope.
Described catalyzer is that the generation click chemistry is necessary, such as benzoin dimethylether, CuSO
45H
2O or CdCl
2Deng.
Described POSS contains the active group oligomeric silsesquioxane, and general formula can be expressed as R
xR '
y(SiO
1.5) n, wherein n is 8,10 or 12,2≤x≤n, x+y=n; Wherein R be the active group that can click chemical reaction comprise thiazolinyl, sulfydryl, nitrine, alkynyl, amido, epoxy group(ing) or-OSiR
1R
2R
3(R wherein
1And R
2Can independently be hydrogen atom, halogen atom, hydroxyl, C at the same time or separately
1-20Alkyl, alkenyl, aryl, alicyclic radical, alkoxyl group, wherein R
3Be necessary for a kind of in thiazolinyl, sulfydryl, nitrine, alkynyl, amido, the epoxy group(ing)) etc.; R ' can be hydrogen atom, halogen atom, hydroxyl, C
1-20Alkyl, alkenyl, alkynyl, aryl, alicyclic radical, alkoxyl group or-OSiR
1R
2R
3(R wherein
1, R
2, R
3Independent at the same time or separately is hydrogen atom, halogen atom, hydroxyl, C
1-20Alkyl, alkenyl, alkynyl, aryl, alicyclic radical, alkoxyl group) etc.
Described double-functional group organic precursor general formula R '-R-R ', wherein R ' comprises thiazolinyl, sulfydryl, nitrine, alkynyl, amido, epoxy group(ing) etc. for the functional group at two ends, R can be C
1-20Alkyl, alkenyl, alkynyl, aryl, alicyclic radical, alkoxyl group, amine ester group, hydroxyl, carbonyl, acid amides etc. by chemical bond and organic segment.
In the described accurate structure POSS hybridization low dielectric material, specific inductivity is lower than 2.7, POSS and connects uniform sequentially in low dielectric hybrid material, thermal expansivity 60～120 μ m/m ℃, has good hydrophobicity.
Beneficial effect:
(1) the click chemistry reaction of adopting, reaction conditions is gentle, environmental friendliness and efficiently controlled, and insensitive to water and oxygen, such as ethylene linkage and sulfydryl under the effect of trace light trigger, the addition reaction that occurs by illumination;
(2) utilize carbon heteroatoms binding reaction fast uniform sequential being connected in the hybrid material molecule of POSS;
(3) by changing composition, structure and the performance of the organic molecule chain that connects POSS, realization is to the regulation and control of precision architecture hybridization low dielectric material structure, porosity, thermal characteristics, mechanical property and specific inductivity, and the dielectric materials of preparation is mainly used in the fields such as electronic package material, low dielectric coat.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Both arms vinyl POSS's is synthetic: the preparation of (1) both arms vinyl POSS intermediate: with the trimethoxy-benzene base silane of 120g, and the NaOH of 16g and the H of 10～20g
2O places 1000mL that four neck flasks of constant pressure funnel, condensing reflux pipe and thermometer are housed, (reactive material and 2-propyl alcohol mass ratio make the above-mentioned substance dissolving at 1:4～1:40) to add the 2-propyl alcohol again, under the nitrogen protection, magnetic agitation reflux 4h, stopped heating leaves standstill 8h under the reaction mixture room temperature, filters, the washing of 2-propyl alcohol, vacuum-drying obtains white solid a; (2) 22.60g (0.02mol) solid a and 8.00g (0.08mol) triethylamine are placed be furnished with the condensing reflux pipe; in the four neck flasks of constant pressure funnel and thermometer; the THF that adds 200～300mL; magnetic agitation 1h; the methyl ethylene dichlorosilane that under nitrogen protection and magnetic agitation condition, dropwise adds 8.40g (0.06mol) with constant pressure funnel; continue to stir 2h; add the water of 100～200mL to reaction mixture; the sodium-chlor that dissolving generates and the complete methyl ethylene dichlorosilane of hydrolysis unreacted; standing demix; get organic layer and use successively alkene hydrochloric acid; saturated sodium bicarbonate solution and deionized water wash obtain product.React as follows:
Synthesizing of difunctional sulfydryl monomer: with thioglycolic acid 9.21g (0.10mol), the diamine monomer quality is respectively 10.01g, 14.62g and 20.51g (being 0.05mol) is dissolved in the benzene solvent, and (reactive material and benzene mass ratio are at 1:4～1:40), place the 150mL round-bottomed flask, 110 ℃ of heating reflux reaction 10h.Obtain solid product, purify with ethyl alcohol recrystallization.Product numbering: M
1～M
3, synthesis step is as follows:
Both arms vinyl POSS: the mol ratio of difunctional sulfydryl monomer=1:1, namely the above-mentioned vinyl POSS of 24.44g (0.02mol) respectively with 6.97g (0.02mol) M
1, 8.57g (0.02mol) M
2, 11.17g (0.02mol) M
3(reactive material and THF mass ratio are in 1:5～1:100) jointly to be dissolved in tetrahydrofuran (THF) with the trace benzoin dimethylether, join in the round-bottomed flask that agitator 250mL is housed, under the illumination condition, reaction 2～10h, occur to click chemical reaction, react as follows.Obtain the straight chain type POSS hybridization low dielectric material of precision architecture, the length of regulating organic segment, its specific inductivity (test frequency 1M) is 2.25～2.03, has low thermal expansivity 83～91 μ m/m ℃.
Embodiment 2
Sulfydryl POSS's is synthetic: with γ mercaptopropyitrimethoxy silane 196.30g (1.0mol); it is 3.0 that methyl alcohol 800mL, distilled water 55mL and an amount of concentrated hydrochloric acid are regulated pH value; join agitator is housed; in the there-necked flask of the 1500mL of thermometer and reflux condensing tube; under nitrogen protection, 60 ℃ of reactions of constant temperature 48h.Then stopped heating is cooled to room temperature, filter reaction and separate out the product that obtains, with hexanaphthene with product cleaning.
Synthesizing of diene monomers: get the 1000mL flask, add 20.00g (0.144mol) P-hydroxybenzoic acid, pour again 300mL ethanol and 200mL water into.Other claims 10g NaOH and 2g KI, is dissolved in 100mLH
2Among the O, with NaOH, KI solution dropwise adds in the ethanol-water solution, after adding about 1～2h, adds 13mL (0.153mol, excessive) bromopropylene, 65～70 ℃ of backflow 70h.Stopped reaction adds the acidifying of 30mL concentrated hydrochloric acid, and rotary evaporation gets a large amount of white precipitates, and suction filtration is collected solid, and ethyl alcohol recrystallization gets white needle-like crystals.Take by weighing 4.00g (0.024mol) to the allyloxy phenylformic acid in the 150mL there-necked flask, add 60mL dry toluene dissolving, add 6mL (0.11mol, excessive) thionyl chloride, meet CaCl on the prolong
2Drying tube, 60 ℃ of lower stirring reaction 4h.Underpressure distillation goes out excessive SOCl
2And solvent toluene, get weak yellow liquid.Connect the synthetic reaction of previous step acyl chlorides, in three-necked flask, add 60mL THF, 0.62mL (0.011mol) ethylene glycol (or butyleneglycol 1.0mL, 0.011mol), other adds the 8mL triethylamine and makes acid binding agent.Back flow reaction 24h.Cross the neutral alumina chromatographic column after the reaction solution rotary evaporation is concentrated.Eluent adopts the proportioning of sherwood oil: ethyl acetate=1:1, collects top phosphor dot component.Rotary evaporation gets light yellow solid, uses a small amount of ethyl alcohol recrystallization, obtains needle-like crystal.Diene monomers product numbering: M
1～M
4(n=2,4,6,8), synthesis step is as follows:
Press sulfydryl POSS: diene mol ratio=1:4, namely the above-mentioned sulfydryl POSS of 10.18g (0.01mol) respectively with 15.29g (0.04mol) M
1, 16.41g (0.04mol) M
2, 17.53g (0.04mol) M
3, 18.65g (0.04mol) M
4(reactive material and THF mass ratio join in the round-bottomed flask that agitator 250mL is housed in 1:4～1:80), and under the illumination condition, reaction 2～10h occurs to click chemical reaction, reacts as follows jointly to be dissolved in tetrahydrofuran (THF) with the trace benzoin dimethylether.Obtain the network-type POSS hybridization low dielectric material of precision architecture, the length of regulating organic segment, its specific inductivity (test frequency 1M) is 2.35～2.11, has low thermal expansivity 65～84 μ m/m ℃.
Embodiment 3
Both arms azido-POSS's is synthetic, and its synthetic method was divided into for 3 steps, and (1) is identical with the synthesis step (1) of both arms vinyl POSS among the embodiment 1; (2) the 3-propyl group dimethyl dichlorosilane (DMCS) that only the methyl ethylene dichlorosilane in the synthesis step (2) of both arms vinyl POSS among the embodiment 1 is replaced with 11.40g (0.06mol) gets final product; (3) the material b with 26.44g (0.02mol) is dissolved among the THF of 150mL, adds to be dissolved with 3.90g (0.06mol) NaN again
3The aqueous solution of 20mL, stir 2～6h under the room temperature, obtain both arms azido-POSS through purification.React as follows:
Synthesizing of difunctional alkynes monomer: place 250mL with the round-bottomed flask of prolong the acetylenic acid of 8.00g (0.10mol) and the thionyl chloride of 23.80g (0.20mol), heated and stirred, 65 ℃ of reaction 4h, underpressure distillation goes out excessive SOCl
2, will be dissolved in again in the methylene dichloride that (diamine monomer and methylene dichloride mass ratio are in that 1:5～1:40) quality is respectively 10.01g, and 14.62g and 20.51g (being 0.05mol) diamine monomer adds wherein, heating reflux reaction 3h.Obtain solid product, purify with ethyl alcohol recrystallization.Product numbering: M
1～M
3, synthesis step is as follows:
Both arms azido-POSS: the mol ratio of difunctional alkynes monomer=1:1, namely the above-mentioned both arms azido-of 25.60g (0.02mol) POSS respectively with 6.97g (0.02mol) M
1, 8.57g (0.02mol) M
2, 11.17g (0.02mol) M
3With an amount of CuSO
45H
2O is dissolved in water/tetrahydrofuran solvent jointly, and (ratio of mixture is 1:50, and reactive material and THF mass ratio add in the round-bottomed flask of 250mL in 1:2～1:50), and under the stirring at room condition, reaction 2～10h occurs to click chemical reaction, reacts as follows.What obtain precision architecture contains 1,3,5-triazole straight chain type POSS hybridization low dielectric material, the length of regulating organic segment, and its specific inductivity (test frequency 1M) is 2.58～1.96, has low thermal expansivity 76～85 μ m/m ℃.
Embodiment 4
Both arms contain the synthetic of epoxy group(ing) function POSS: the vinyl among the embodiment 1 synthetic both arms vinyl POSS is namely obtained both arms through the metachloroperbenzoic acid oxidation contain epoxy group(ing) function POSS, be specially as follows.The both arms vinyl POSS of 12.44g (0.01mol) and the metachloroperbenzoic acid (m-CPBA) of 10.12g (0.04mol) are joined in the three-necked flask of 250mL, the methylene dichloride that adds again 150mL, 40 ℃ of backflow 48h, 0 ℃ of placement of reaction solution is spent the night, separate out white precipitate, the washing recrystallization obtains both arms and contains epoxy group(ing) function POSS.React as follows:
Both arms contain epoxy group(ing) function POSS: the mol ratio of diamine monomer=1:1, namely the above-mentioned both arms of 12.53g (0.01mol) are contained epoxy group(ing) function POSS and quality is respectively 2.00g, 2.92g and the diamine monomer of 4.10g (being 0.05mol) is dissolved in dichloromethane solvent, and (reactive material and methylene dichloride mass ratio add an amount of CdCl in 1:4～1:50)
2, occur to click chemical reaction, react as follows.Obtain precision architecture straight chain type POSS hybridization low dielectric material, the length of regulating flexible organic segment, its specific inductivity (test frequency 1M) is 2.41～2.18, has low thermal expansivity 102～115 μ m/m ℃.
Claims (2)
1. the preparation method of an accurate structure POSS hybridization low dielectric material comprises step:
In solution system, and in the presence of the catalyzer of necessity, POSS and double-functional group organic precursor react 0.5～10h under illumination or 20～60 ℃ of heating conditions, generate accurate structure POSS hybridization low dielectric material; Wherein catalyzer is benzoin dimethylether, CuSO
45H
2O or CdCl
2
Described POSS contains the active group oligomeric silsesquioxane, is both arms vinyl POSS, and its general formula is expressed as R
xR '
y(SiO
1.5)
n, wherein n is 8,10 or 12, x=2, x+y=n; Wherein R is vinyl, and R ' is hydrogen atom, halogen atom, hydroxyl, C
1-20Alkyl, alkenyl, alkynyl, aryl, alicyclic radical, alkoxyl group or-OSiR
1R
2R
3, R wherein
1, R
2, R
3Independent at the same time or separately is hydrogen atom, halogen atom, hydroxyl, C
1-20Alkyl, alkenyl, alkynyl, aryl, alicyclic radical, alkoxyl group;
Described double-functional group organic precursor is difunctional sulfydryl monomer, and its general formula is R '-R-R ', and wherein R ' is the functional group at two ends, and R ' is sulfydryl, and R is C
1-20Alkyl, alkenyl, alkynyl, aryl, alicyclic radical, amine ester group, carbonyl or acid amides are by organic segment of chemical bonding;
Both arms vinyl POSS wherein: the mol ratio of difunctional sulfydryl monomer=1:1.
2. the preparation method of accurate structure POSS hybridization low dielectric material according to claim 1, it is characterized in that: the solvent of described solution system is one or more in water, methyl alcohol, ethanol, hexanaphthene, benzene,toluene,xylene, dioxane, tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), the methylene dichloride, and the mass ratio of itself and presoma POSS is in 100～2:1 scope.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810041996 CN101348568B (en) | 2008-08-22 | 2008-08-22 | Accurate structure POSS hybridization low dielectric material preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810041996 CN101348568B (en) | 2008-08-22 | 2008-08-22 | Accurate structure POSS hybridization low dielectric material preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101348568A CN101348568A (en) | 2009-01-21 |
| CN101348568B true CN101348568B (en) | 2013-01-02 |
Family
ID=40267557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810041996 Expired - Fee Related CN101348568B (en) | 2008-08-22 | 2008-08-22 | Accurate structure POSS hybridization low dielectric material preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101348568B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580711B (en) * | 2009-06-05 | 2013-06-26 | 东华大学 | Star-structure organic inorganic hybridization green light material and preparation and application thereof |
| CN103665863B (en) * | 2012-09-13 | 2016-01-20 | 北京化工大学 | Containing the compositions of thermosetting resin of double-tower type epoxy silsesquioxane |
| CN103923116A (en) * | 2014-04-03 | 2014-07-16 | 东华大学 | Method for grafting polyamino and polyhydroxyl substance by use of epoxy POSS |
| CN104841389B (en) * | 2015-04-16 | 2017-01-25 | 同济大学 | Preparation method of organic/inorganic hybrid material POSS-PDMAEMA two-phase adsorbed organic dye |
| CN105778153B (en) * | 2016-03-30 | 2018-07-20 | 南昌航空大学 | A kind of preparation method of cage type polysilsesquioxane grafting carbon fiber reinforcement |
| EP3677586A4 (en) * | 2017-08-28 | 2021-04-21 | Hitachi Chemical Co., Ltd. | Method for manufacturing silsesquioxane compound |
| CN108384012B (en) * | 2018-03-16 | 2020-12-01 | 深圳市山德实业有限公司 | Polyeugenol-phenyl silsesquioxane and preparation method thereof |
| CN110358091B (en) * | 2018-03-26 | 2021-01-22 | 北京化工大学 | Preparation method of epoxidized phenyl silicone rubber |
| CN109233294B (en) * | 2018-08-28 | 2020-04-24 | 淮阴工学院 | Organic silicon micro-porous ultralow dielectric film and preparation method thereof |
| CN110218328B (en) * | 2019-06-19 | 2021-08-31 | 陕西天策新材料科技有限公司 | Method for synthesizing epoxy cage-type silsesquioxane |
| CN111430782B (en) * | 2020-05-08 | 2021-11-12 | 深圳市元鼎智能创新有限公司 | Silicon aerogel modified lithium ion battery diaphragm and preparation method thereof |
| CN112080041B (en) * | 2020-09-23 | 2023-08-15 | 极塑材料科技(东莞)有限公司 | Preparation method of POSS grafted tannin modified diatomite flame-retardant modified composite material |
| CN114068066B (en) * | 2021-12-23 | 2022-04-19 | 西安宏星电子浆料科技股份有限公司 | High-weather-resistance encapsulation dielectric paste for thick film circuit |
| CN114940760A (en) * | 2022-06-29 | 2022-08-26 | 深圳职业技术学院 | Polyimide film and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1666861A (en) * | 2005-04-01 | 2005-09-14 | 安徽大学 | Porous silicon oxide membrane with low dielectric constant and its preparation method |
| KR20060051694A (en) * | 2004-09-27 | 2006-05-19 | 신닛테츠가가쿠 가부시키가이샤 | Silicone resin composition and molded product thereof |
| CN1803809A (en) * | 2005-12-13 | 2006-07-19 | 浙江大学 | Synthesis method of multi-amino polyhedral oligomeric silsesquioxanes |
| JP2006276501A (en) * | 2005-03-29 | 2006-10-12 | Seiko Epson Corp | Alignment layer, forming method of alignment layer, substrate for electron device, liquid crystal panel, and electronic equipment |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100533538B1 (en) * | 2002-12-03 | 2005-12-05 | 삼성전자주식회사 | Compsoition for Preparing Porous Interlayer Dielectric Thin Film, Containing Novel Pore-Generating Material |
-
2008
- 2008-08-22 CN CN 200810041996 patent/CN101348568B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060051694A (en) * | 2004-09-27 | 2006-05-19 | 신닛테츠가가쿠 가부시키가이샤 | Silicone resin composition and molded product thereof |
| JP2006276501A (en) * | 2005-03-29 | 2006-10-12 | Seiko Epson Corp | Alignment layer, forming method of alignment layer, substrate for electron device, liquid crystal panel, and electronic equipment |
| CN1666861A (en) * | 2005-04-01 | 2005-09-14 | 安徽大学 | Porous silicon oxide membrane with low dielectric constant and its preparation method |
| CN1803809A (en) * | 2005-12-13 | 2006-07-19 | 浙江大学 | Synthesis method of multi-amino polyhedral oligomeric silsesquioxanes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101348568A (en) | 2009-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101348568B (en) | Accurate structure POSS hybridization low dielectric material preparation | |
| JP6664398B2 (en) | Thermosetting alkoxysilyl compound having two or more alkoxysilyl groups, composition containing the same, cured product, use thereof, and method for producing alkoxysilyl compound | |
| CN105254828B (en) | The preparation method of eight phenolic hydroxyl group polyhedral oligomeric silsesquioxane hybrid phenol-formaldehyde resins | |
| CN109749087A (en) | A kind of semiclosed caged trifunctional epoxy ether POSS and preparation method thereof | |
| CN112898586B (en) | Preparation method of epoxy group-containing hyperbranched organic silicon resin and compound thereof | |
| CN104448838B (en) | High-fluidity click light-cured heat conduction heteropolysilicon rubber and preparation method thereof | |
| CN104788647A (en) | Phosphorous-containing epoxy resin amine curing agent and preparation method thereof | |
| CN104072779A (en) | Silica aryne resin containing carborane unit in main chain framework and preparation method thereof | |
| Fujiwara et al. | A simple preparation method of epoxy resin/silica nanocomposite for T g loss material | |
| CN114437493B (en) | High-thermal-conductivity elastomer and preparation method thereof | |
| WO2022156832A2 (en) | Preparation method for high-insulativity low-temperature electronic packaging material | |
| CN101591421A (en) | Silicon framework hyperbranched epoxy resin and preparation method and with the high temperature-resisting solvent-free insulated paint of its composition | |
| CN102875777B (en) | Novel epoxy hardener and preparation method thereof | |
| CN108659226A (en) | A kind of normal-butyl blocks the preparation method and applications of poly bis phenyl methyl silazane | |
| CN105778096A (en) | Manufacturing method and application of benzocyclobutenyl containing silicon resin | |
| CN108864014A (en) | A kind of alicyclic dianhydride compound of the naphthalene structure containing perhydrogenating and preparation method thereof and purposes | |
| CN109735203A (en) | A kind of semiclosed caged trifunctional epoxy ether POSS combination material, coating and preparation method | |
| CN104277069B (en) | Synthesis and application of new nano hybrid | |
| CN108864432A (en) | A kind of preparation method and applications of the poly bis phenyl methyl silazane of methyl blocking | |
| CN105837826A (en) | Hydrogen-containing silicon resin and preparation method and application thereof | |
| CN106279242A (en) | A kind of three-functionality-degree acrylate monomer of silicone-containing structure and preparation method thereof | |
| CN108641672A (en) | A kind of anti-oxidant LED packaging plastics of high transparency | |
| CN110372861A (en) | The preparation method of modification dicyclopentadiene type ethylene rhodanate resin with agent of low hygroscopicity | |
| CN108715738A (en) | A kind of high temperature resistant LED high transparency organic silica gels | |
| JP3574712B2 (en) | Low hygroscopic glycidyloxy group-containing aromatic polyamide resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xu Hongyao Inventor after: Zhang Chao Inventor after: Guang Shanyi Inventor after: Lin Naibo Inventor before: Xu Hongyao Inventor before: Zhang Chao Inventor before: Guang Shanyi |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: XU HONGYAO ZHANG CHAO GUANG SHANYI TO: XU HONGYAO ZHANG CHAO GUANG SHANYI LIN NAIBO |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130102 Termination date: 20150822 |
|
| EXPY | Termination of patent right or utility model |