CN102585239A - Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof - Google Patents
Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof Download PDFInfo
- Publication number
- CN102585239A CN102585239A CN2012100033398A CN201210003339A CN102585239A CN 102585239 A CN102585239 A CN 102585239A CN 2012100033398 A CN2012100033398 A CN 2012100033398A CN 201210003339 A CN201210003339 A CN 201210003339A CN 102585239 A CN102585239 A CN 102585239A
- Authority
- CN
- China
- Prior art keywords
- polymer
- reaction
- amino
- imino
- 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.)
- Granted
Links
- HXITXNWTGFUOAU-UHFFFAOYSA-N OB(c1ccccc1)O Chemical compound OB(c1ccccc1)O HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and a preparation method thereof. The polymer is obtained by performing two-step reaction on raw materials, namely phenylboronic acid, dichlorosilane and aminophenylacetylene, and solvents, namely anhydrous diethylene glycol dimethyl ether and anhydrous tetrahydrofuran, under inert gas protection. The first-step reaction comprises the step of enabling the phenylboronic acid to react with the dichlorosilane to generate a polymer with a Si-O-B-O repeating structure unit and two ends capped by helium atoms; and the second-step reaction comprises the steps of enabling the aminophenylacetylene to react with the polymer generated in the first step and performing post-treatment to get a final product. Imino and terminal alkyne structures are introduced into the Si-O-B-O structure unit of the polymer disclosed by the invention, and by regulating the content of silicon and boron in the structure, the thermal oxidization resistance of the polymer is further improved; and by utilizing a chelating action of the imino and the Si-O-B-O structure, the hydrolysis performance of the polymer material is improved. The polymer has extensive application prospects in the fields of national defense, aviation, spaceflight and the like.
Description
Technical field
The invention belongs to one type of novel high temperature-resisting phenylboronic acid-siloxanes-imino-simple linear polymer and preparation method thereof, particularly main chain contains the class I organic-inorganic hybridized polymer materials of Siliciumatom, boron atom and amino-benzene acetylene.
Background technology
Along with the fast development of aerospace field, to the demands for higher performance of high-temperature polymer material: the temperature of lightweight, more high-strength and Nai Genggao more.Silicon-containing polymer (like polysilane, Polycarbosilane, gather nitrogen silane and polycarbosilazanes etc.) is as one type of thermoset copolymer material, because its unique physical and chemical performance and outstanding resistance toheat have obtained extensive studies and application.Wherein, Contain in the main chain-organosilicon polymer of Si-C ≡ C-reactive group; In solidification process, form the three-dimensional crosslinked network structure; Make polymer materials have performances such as very high thermostability, anti-solvent, have broad application prospects in fields such as high performance composite, photoetching material, semiconductor material, optical material and ceramic forerunners.In recent years, in polysiloxane polymer molecular backbone chain structure, introduce the element of some other types,, can make resulting polymer materials possess many special performances like B, Al, Ti, Sn etc.Wherein the introducing of B element can improve the heatproof oxidation performance ability of organosilicon material significantly, has become a research focus of high-temperature polymer material in recent years.
Japan scholar Itoh etc. are that catalyzer, phenyl silane and diacetylene-benzene are that raw material carries out the dehydrogenation polyaddition reaction with Natural manganese dioxide, have prepared in the repeating unit and have contained [Si (Ph) H-C ≡ C-C
6H
4-C ≡ C-] high temperature resistant aryne polymkeric substance (MSP resin) and can study its heatproof oxidation performance; France scholar Buvat etc. has synthesized a kind of Si-H and C ≡ C reactive group of both having contained on the basis of MSP resin; Also has the end capped phenyl aryne of ethynyl resinoid simultaneously; This resin high-temperature decomposition temperature is low than MSP, but its solidification value is lower and better in the room temperature processibility; Craig etc. have prepared a kind of line style (arylidene-siloxy-2-ethynyl) polymkeric substance through polycondensation and organolithium reagent, and it contains-and SiC ≡ C-C ≡ CH structure is a cross-linkable solidifying under 300 ℃, has very high using value; Devapal etc. with hydrochloric acid as catalyzer, diglyme as reaction solvent; Adopting boric acid and phenyl (propyl group) Trimethoxy silane (PTMOS) is raw material; Prepare the silica boron polymer of ceramicization rate at 64～75% scopes (900 ℃ of rare gas elementes) through polycondensation, research shows that this type of material is when being warming up to 500 ℃; Weightlessness basically takes place, and heat-resistant stability can be excellent; The Zhou Quan of East China University of Science etc. are the synthetic a kind of novel carborane-silane-phenylacetylene base polymkeric substance (being called for short PACS) that obtained of raw material with dimethyl dichlorosilane (DMCS), carborane, phenylacetylene and organolithium reagent; Research shows that the PACS cured product that reactive polymeric obtains under the thermal initiation effect has very high heat-resisting and heatproof oxidation performance can; Chen Qi etc. have also carried out the research work of organic and inorganic silicon alkynes hybrid material at home, and a series of phenylacetylene base silane resins have been synthesized in design, comprise methyldiphenyl ethynyl silane (MDPES) (ZL02151140.3; ZL200510110133.5), methyl three phenylacetylene base silane (MTPES) and four phenylacetylene base silanes (TPES).These three kinds of resins have good solubility in OOS, through the prepolymerization reaction viscosity of the hierarchy of control effectively, be applicable to various advanced composite material moulding processs.But the SiC that the content of inorganic elements and sinter form in the polymer materials that research obtains, B
2O
3Equal size is generally all lower, if can improve the content of the inorganic elements in the polymkeric substance, then can form successive SiC, B
2O
3Deng ceramic structure, thus the heatproof oxidation performance ability of raising material.
The present invention adopts a kind of brand-new synthetic route, and synthesized in one type of novel principal chain and contained inorganic elements boron and silicon, and with the end capped hybrid inorganic-organic polymkeric substance of amino-benzene acetylene.The present invention is that main raw material has synthesized one type of novel high temperature-resisting phenylboronic acid-siloxanes-imino-simple linear polymer with phenylo boric acid, dichlorosilane and amino-benzene acetylene.Through regulating the mol ratio of phenylo boric acid and dichlorosilane; The content of inorganic elements silicon and boron in the controlling polymers at an easy rate; Utilize the addition reaction of C ≡ C key and C ≡ C key and the Diels-Alder reaction of C ≡ C key and C ≡ C etc.; Make this hybridized polymer under heating condition, can form three-dimensional net structure, boron and the Siliciumatom in the main polymer chain at high temperature is converted into B simultaneously
2O
3, SiO
2With ceramic structures such as SiC, wherein B
2O
3At high temperature have good flowability, can repair, have the ability of self-healing, improve the heat-resisting oxidation capacity of filamentary material effectively, improved the at high temperature airborne quality retention rate of matrix material greatly coating and tiny crack.This base polymer has good high temperature resistant, heat-resisting oxidation and dielectric properties etc.; Be applicable to the ceramic precursor of preparation, high performance composite matrix, ablation resistant material, high-temperaure coating etc., extremely broad application prospect is arranged in high-end fields such as national defence, Aeronautics and Astronautics.
Summary of the invention
The present invention has synthesized one type of novel high temperature-resisting phenylboronic acid-siloxanes-imino-simple linear polymer, and described polymer architecture formula is following:
Wherein: (1) R
1, R
2Be Wasserstoffatoms, alkyl or aryl; (2) n is>=1 integer;
(3) Ar is
or three kinds mixture.
The invention provides the brand-new polymkeric substance of a kind of structure, its repeating unit contains a Si-O-B-O structure at least, and contains two ethynyl end-blockings.Through regulating phenylo boric acid and dichlorosilane, the mol ratio of phenylo boric acid and amino-benzene acetylene, the content of the molecular weight of controlling polymers, cross-linking density and silicon/boron at an easy rate, thus reach the target of polymer performance adjustable.
The present invention introduces imino-and Terminal Acetylenes based structures from Molecular Structure Design in the Si-O-B-O structural unit, obtained both siliceous, boron inorganic elements, contains the hybrid inorganic-organic materials of ethynyl again.Through the content of Si-O-B-O structure in the telomerized polymer, the content of silicon and boron in the control texture at an easy rate, thus improve the heatproof oxidation performance ability of this base polymer.Utilize the sequestering action of imino-and Si-O-B-O structure, thereby improve the hydrolysis property of this base polymer material.Cross-linking and curing reaction takes place and forms tridimensional network in said polymkeric substance under the effect of light, heat or chemical initiator.And can in air or rare gas element, further pyrolysis form ceramic structure.This base polymer is suitable for preparing ceramic precursor, high performance composite matrix, ablation resistant material, high-temperaure coating etc., and extremely broad application prospect is arranged in high-end fields such as national defence, Aeronautics and Astronautics.
Novel high temperature-resisting phenylboronic acid-siloxanes according to the invention-imino-simple linear polymer is low-viscosity (mobile) liquid to a thick solid, is soluble in all kinds of OOSs, can be used for preparing high temperature resistant composite, ceramic forerunner, high-temperaure coating etc.
Another object of the present invention provides a kind of method for preparing said novel high temperature-resisting phenylboronic acid-siloxanes-imino-simple linear polymer.The present invention is that raw material, anhydrous diethylene glycol dimethyl ether, anhydrous tetrahydro furan (THF) are made solvent with phenylo boric acid, dichlorosilane, amino-benzene acetylene, in protection of inert gas following minute two step reaction and get.The preparation method is following:
The first step reaction: under protection of inert gas, have the Si-O-B-O repeated structural unit through phenylo boric acid and dichlorosilane reaction generation, two ends are the end capped polymkeric substance of chlorine atom, and reaction formula is as follows:
Wherein: (1) R
1, R
2Be Wasserstoffatoms, alkyl or aryl; (2) n is>=1 integer;
(3) Ar is
or three kinds mixture.
The reaction of second step: under protection of inert gas, the polymer reaction that the amino-benzene acetylene and the first step generate, aftertreatment obtains final product, and reaction formula is as follows:
Wherein: (1) R
1, R
2Be Wasserstoffatoms, alkyl or aryl; (2) n is>=1 integer;
(3) Ar is
or three kinds mixture.
The present invention introduces imino-and Terminal Acetylenes based structures from Molecular Structure Design in the Si-O-B-O structural unit, obtained both siliceous, boron inorganic elements, contains the hybrid inorganic-organic materials of ethynyl again.Through the content of Si-O-B-O structure in the telomerized polymer, the content of silicon and boron in the control texture at an easy rate, thus improve the heatproof oxidation performance ability of this base polymer.Utilize the sequestering action of imino-and Si-O-B-O structure, improve the hydrolysis property of this base polymer material.This synthesis technique is simple, and reaction conditions is easy to control, and is easy to operate; Required starting material source is abundant, and product at room temperature has satisfactory stability property, and is high temperature resistant and antioxidant property is excellent, has industrial applicibility, is applicable to preparation ceramic forerunner, high performance composite matrix, ablation resistant material, high-temperaure coating etc.
Embodiment:
Further specify technical solution of the present invention in conjunction with embodiment, but it does not limit protection scope of the present invention:
Embodiment 1: preparation novel high temperature-resisting phenylboronic acid-siloxanes-imino-simple linear polymer (wherein, M
Phenylbenzene two Chlorosilane: M
Phenylo boric acid=2: 1; M
Diphenyl dichlorosilane, M
Phenylo boric acidThe mole number of representing diphenyl dichlorosilane, phenylo boric acid respectively)
Under the high pure nitrogen protective condition; 40mmol phenylo boric acid and the adding of 60ml diethylene glycol dimethyl ether are equipped with in the 250ml four-hole boiling flask of whisking appliance, TM, constant pressure funnel and reflux; Then under 20～30 ℃ of conditions, slowly drip the solution that 80mmol diphenyl dichlorosilane and 30ml diethylene glycol dimethyl ether are made into through constant pressure funnel, after dropwising; Slowly be warmed up to 165 ℃, kept back flow reaction 48 hours.After treating that back flow reaction finishes; Underpressure distillation removes the diethylene glycol dimethyl ether that desolvates; And, adding 10ml THF lysate with the product cool to room temperature, hierarchy of control temperature is at 0～10 ℃; Slowly drip the solution that 80mmol amino-benzene acetylene and 50ml diethylene glycol dimethyl ether are made into through constant pressure funnel, dropwise the back controlled temperature and under 20～30 ℃ of conditions, continues to react 3 hours.After question response finishes,, add saturated NH with the product cooling
4Cl solution fully stirs, and separatory is got upper oil phase, and repeated washing, separatory 3～5 times all are neutral until water and oil phase.Collect upper strata oily matter, underpressure distillation promptly gets product after eliminating solvent.FT-IR：3288cm
-1(C≡C-H)，3068cm
-1(Ph-H)，3374cm
-1(-NH)，1079cm
-1(Si-O)，1430cm
-1(B-Ph)，1122cm
-1(Si-Ph)；
1H-NMR(CDCl
3，TMS)δ：6.79-7.67(Ph-H)，3.05(≡CH)，3.98(-NH)；
13C-NMR(CDCl
3，TMS)δ：77.4(≡CH)，115.8-134.8(Ph)，83.9(-C≡CH)。
Embodiment 2: preparation novel high temperature-resisting phenylboronic acid-siloxanes-imino-simple linear polymer (wherein, M
Phenylbenzene two Chlorosilane: M
Phenylo boric acid=1.5: 1; M
Diphenyl dichlorosilane, M
Phenylo boric acidThe mole number of representing diphenyl dichlorosilane, phenylo boric acid respectively)
Under the high pure nitrogen protective condition; 40mmol phenylo boric acid and the adding of 60ml diethylene glycol dimethyl ether are equipped with in the 250ml four-hole boiling flask of whisking appliance, TM, constant pressure funnel and reflux; Then under 20～30 ℃ of conditions, slowly drip the solution that 60mmol diphenyl dichlorosilane and 25ml diethylene glycol dimethyl ether are made into through constant pressure funnel, after dropwising; Slowly be warmed up to 165 ℃, kept back flow reaction 48 hours.After treating that back flow reaction finishes; Underpressure distillation removes the diethylene glycol dimethyl ether that desolvates; And, adding 10ml THF lysate with the product cool to room temperature, hierarchy of control temperature is at 0～10 ℃; Slowly drip the solution that 40mmol amino-benzene acetylene and 30ml diethylene glycol dimethyl ether are made into through constant pressure funnel, dropwise the back controlled temperature and under 20～30 ℃ of conditions, continues to react 3 hours.After question response finishes,, add saturated NH with the product cooling
4C1 solution fully stirs, and separatory is got upper oil phase, repeated washing, and separatory 3～5 times all is neutral until water and oil phase.Collect upper strata oily matter, underpressure distillation promptly gets product after eliminating solvent.FT-IR：3290cm
-1(C≡C-H)，3070cm
-1(Ph-H)，3380、1185cm
-1(-NH)，1348cm
-1(B-O)，1080cm
-1(Si-O)，1437cm
-1(B-Ph)，1122cm
-1(Si-Ph)；
1H-NMR(CDCl
3，TMS)δ：6.80-7.71(Ph-H)，3.06(≡CH)，4.08(-NH)；
13C-NMR(CDCl
3，TMS)δ：77.8(≡CH)，115.3-134.8(Ph)，86.4(-C≡CH)。
Claims (7)
1. the present invention prepares a kind of novel high temperature-resisting phenylboronic acid-siloxanes-imino-simple linear polymer, it is characterized in that described novel high temperature-resisting phenylboronic acid-siloxanes-imino-simple linear polymer has following structural formula:
Wherein: (1) R
1, R
2Be Wasserstoffatoms, alkyl or aryl; (2) n is>=1 integer;
(3) Ar is
or three kinds mixture.
2. the preparation method of the described novel high temperature-resisting phenylboronic acid-siloxanes of claim 1-imino-simple linear polymer, its key step is:
(1) the first step reaction: under protection of inert gas, have the Si-O-B-O repeating unit and two ends are the end capped polymkeric substance of chlorine atom through phenylo boric acid and dichlorosilane reaction formation;
The reaction of (2) second steps: under protection of inert gas, the polymer reaction that the amino-benzene acetylene and the first step generate obtains final product through aftertreatment.
3. preparation method according to claim 2 is characterized in that: the mol ratio of phenylo boric acid and dichlorosilane is 1: (1.05～2).
4. preparation method according to claim 2 is characterized in that: in the first step reaction, the temperature of reaction of dichlorosilane solution in the dropping process is 10～40 ℃, and the temperature of reaction after dropwising is 100～200 ℃, and the reaction times is 30～50 hours.
5. preparation method according to claim 2 is characterized in that: the mol ratio of phenylo boric acid and amino-benzene acetylene is 1: (0.1～2).
6. preparation method according to claim 2 is characterized in that: in the reaction of second step, the temperature of reaction of amino-benzene acetylene solution in the dropping process is-10～30 ℃, and the reaction times after dropwising is 0.5～5 hour.
7. preparation method according to claim 2 is characterized in that: amino-benzene acetylene is the mixture of 2-amino-benzene acetylene, 3-amino-benzene acetylene, 4-amino-benzene acetylene or 2-amino-benzene acetylene, 3-amino-benzene acetylene and 4-amino-benzene acetylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210003339 CN102585239B (en) | 2012-01-06 | 2012-01-06 | Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210003339 CN102585239B (en) | 2012-01-06 | 2012-01-06 | Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102585239A true CN102585239A (en) | 2012-07-18 |
| CN102585239B CN102585239B (en) | 2013-10-09 |
Family
ID=46474523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210003339 Expired - Fee Related CN102585239B (en) | 2012-01-06 | 2012-01-06 | Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102585239B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015168804A (en) * | 2014-03-10 | 2015-09-28 | 国立大学法人北陸先端科学技術大学院大学 | Polyborosiloxane, method for producing the same, and method for producing borosilane compound |
| CN105585590A (en) * | 2015-12-02 | 2016-05-18 | 杭州师范大学 | Method for preparing hybrid cyclo-boron siloxane |
| CN105646566A (en) * | 2015-12-02 | 2016-06-08 | 杭州师范大学 | Preparation method of mixed cyclo-borosiloxane |
| CN106633075A (en) * | 2016-12-21 | 2017-05-10 | 合肥工业大学 | High-temperature-resistant polysiloxane with main chain containing conjugated structure and preparation method thereof |
| CN110078927A (en) * | 2019-05-24 | 2019-08-02 | 合肥工业大学 | A kind of heat-resisting boracic containing hydrogen silicone oil and preparation method |
| CN110982277A (en) * | 2019-12-23 | 2020-04-10 | 成都硅宝科技股份有限公司 | Single-component temperature-resistant heat-conducting silicon mud composition and preparation method thereof |
| CN112952193A (en) * | 2021-03-23 | 2021-06-11 | 中南大学 | Gel-state electrolyte, preparation method and preparation method of lithium ion battery |
| CN115417993A (en) * | 2022-08-24 | 2022-12-02 | 哈尔滨工业大学 | SiCOBN ceramic precursor and preparation method of ceramic |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544765A (en) * | 2009-05-07 | 2009-09-30 | 华东理工大学 | Novel high temperature-resisting phenylboronic acid-silane-ethynyl polymer and preparation method thereof |
| CN101831077A (en) * | 2010-05-14 | 2010-09-15 | 华东理工大学 | Phenylo boric acid-silane-ethynyl polymer and preparation method thereof |
| CN102226000A (en) * | 2011-04-21 | 2011-10-26 | 华东理工大学 | Novel boron silicon alkyne hybrid high temperature resistant resin and preparation method thereof |
-
2012
- 2012-01-06 CN CN 201210003339 patent/CN102585239B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544765A (en) * | 2009-05-07 | 2009-09-30 | 华东理工大学 | Novel high temperature-resisting phenylboronic acid-silane-ethynyl polymer and preparation method thereof |
| CN101831077A (en) * | 2010-05-14 | 2010-09-15 | 华东理工大学 | Phenylo boric acid-silane-ethynyl polymer and preparation method thereof |
| CN102226000A (en) * | 2011-04-21 | 2011-10-26 | 华东理工大学 | Novel boron silicon alkyne hybrid high temperature resistant resin and preparation method thereof |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015168804A (en) * | 2014-03-10 | 2015-09-28 | 国立大学法人北陸先端科学技術大学院大学 | Polyborosiloxane, method for producing the same, and method for producing borosilane compound |
| CN105585590A (en) * | 2015-12-02 | 2016-05-18 | 杭州师范大学 | Method for preparing hybrid cyclo-boron siloxane |
| CN105646566A (en) * | 2015-12-02 | 2016-06-08 | 杭州师范大学 | Preparation method of mixed cyclo-borosiloxane |
| CN105646566B (en) * | 2015-12-02 | 2018-01-23 | 杭州师范大学 | A kind of preparation method for mixing ring Borosiloxane |
| CN105585590B (en) * | 2015-12-02 | 2018-05-22 | 杭州师范大学 | A kind of preparation method for mixing ring Borosiloxane |
| CN106633075B (en) * | 2016-12-21 | 2019-09-27 | 合肥工业大学 | A kind of high temperature resistant polysiloxanes and preparation method thereof of the main chain containing conjugated structure |
| CN106633075A (en) * | 2016-12-21 | 2017-05-10 | 合肥工业大学 | High-temperature-resistant polysiloxane with main chain containing conjugated structure and preparation method thereof |
| CN110078927A (en) * | 2019-05-24 | 2019-08-02 | 合肥工业大学 | A kind of heat-resisting boracic containing hydrogen silicone oil and preparation method |
| CN110078927B (en) * | 2019-05-24 | 2021-04-20 | 合肥工业大学 | Heat-resistant boron-containing hydrogen-containing silicone oil and preparation method thereof |
| CN110982277A (en) * | 2019-12-23 | 2020-04-10 | 成都硅宝科技股份有限公司 | Single-component temperature-resistant heat-conducting silicon mud composition and preparation method thereof |
| CN110982277B (en) * | 2019-12-23 | 2022-02-22 | 成都硅宝科技股份有限公司 | Single-component temperature-resistant heat-conducting silicon mud composition and preparation method thereof |
| CN112952193A (en) * | 2021-03-23 | 2021-06-11 | 中南大学 | Gel-state electrolyte, preparation method and preparation method of lithium ion battery |
| CN112952193B (en) * | 2021-03-23 | 2022-04-01 | 广东聚圣科技有限公司 | Gel-state electrolyte, preparation method and preparation method of lithium ion battery |
| CN115417993A (en) * | 2022-08-24 | 2022-12-02 | 哈尔滨工业大学 | SiCOBN ceramic precursor and preparation method of ceramic |
| CN115417993B (en) * | 2022-08-24 | 2023-11-14 | 哈尔滨工业大学 | SiCOBN ceramic precursor and preparation method of ceramic |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102585239B (en) | 2013-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102585239B (en) | Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof | |
| CN101235113B (en) | Aryne resin containing polysilicone and preparation method thereof | |
| CN103613365B (en) | Method for synthesizing silicon-oxygen-carbon ceramic material by utilizing polysiloxane resin | |
| CN100577714C (en) | Clathrate silsesquioxane aryne resin containing octamethyl and method for preparing the same | |
| CN102585240B (en) | Aryne resin containing boron and silicon and preparation method thereof | |
| CN106674528B (en) | A kind of preparation method of Polycarbosilane | |
| CN103333341A (en) | High-temperature-resistant hybrid silazane resin and preparation method thereof | |
| CN101875727B (en) | Method for preparing carborane-siloxane polymer under catalysis of Lewis acid | |
| CN101857605B (en) | Novel high-temperature-resistance 1, 7-bis(alkyl hydrogen silane)-carborane/phenylethynyl silane hybrid resin and preparation method thereof | |
| CN104130417A (en) | High-temperature silicon alkyne resin containing nitrogen and preparation method thereof | |
| CN100500713C (en) | Siliceous alkynes fragrant polytriazoles resin and method for making same | |
| CN105542172A (en) | Boron-silicon-alkyne polymer containing carborane in main chain and preparation method of boron-silicon-alkyne polymer | |
| CN102226000B (en) | Novel boron silicon alkyne hybrid high temperature resistant resin and preparation method thereof | |
| CN107057070B (en) | Side-chain hydrogen-containing alkyne hybrid high-temperature-resistant polymer and preparation method thereof | |
| CN100497407C (en) | Aryne resin containing silicone | |
| CN104004194A (en) | Silicon alkyne hybrid high temperature-resistant resin and preparation method thereof | |
| CN111333844B (en) | Preparation method of high-heat-resistance silicon oxide alkyne hybrid resin | |
| CN110423352A (en) | A kind of preparation method of the high-temperature resistant silicone of structure containing carborane material | |
| CN103524746B (en) | A kind of Borazine aryne resin and preparation method thereof | |
| CN101544765B (en) | Novel high temperature-resisting phenylboronic acid-silane-ethynyl polymer and preparation method thereof | |
| CN102234375B (en) | Polyphenylacetylene silicon oxide borane and preparation method thereof | |
| CN101134816A (en) | Sesquialter siloxane polyaryne hybrid resin and preparation method and use thereof | |
| CN103724627A (en) | Synthesis of novel aminophenylacetenyl-terminated polysilazane | |
| CN102010510A (en) | Novel high-temperature resistant phenylacetylene terminated poly (acetenyl-silane) and preparation method thereof | |
| CN101139442B (en) | Organic-inorganic hybrid resin containing sesquialter siloxane and preparation method and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120718 Assignee: Shanghai Guruitai Composite Materials Technology Co.,Ltd. Assignor: East China University of Science and Technology Contract record no.: 2016310000011 Denomination of invention: Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof Granted publication date: 20131009 License type: Exclusive License Record date: 20160302 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131009 Termination date: 20170106 |