CN103333341A - High-temperature-resistant hybrid silazane resin and preparation method thereof - Google Patents

High-temperature-resistant hybrid silazane resin and preparation method thereof Download PDF

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CN103333341A
CN103333341A CN2013102562047A CN201310256204A CN103333341A CN 103333341 A CN103333341 A CN 103333341A CN 2013102562047 A CN2013102562047 A CN 2013102562047A CN 201310256204 A CN201310256204 A CN 201310256204A CN 103333341 A CN103333341 A CN 103333341A
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benzene
diacetylene
preparation
reaction
temperature
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周权
陈明锋
王美贤
倪礼忠
王庚超
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East China University of Science and Technology
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Abstract

The invention relates to high-temperature-resistant hybrid silazane resin and a preparation method thereof. Diacetylene-benzene, dichlorosilane and aminophenyl acetylene are used as main raw materials of the resin, the high-temperature-resistant hybrid silazane resin (aminophenyl acetylene-terminated poly(diacetylene-benzene-silane) is prepared by a Grignard reagent method under the protection of an inert gas. The molecular weight of the polymer, the crosslinking density and the silicon or nitrogen content in the structure can be well controlled by regulating the mol ratio of the diacetylene-benzene to the dichlorosilane and the mol ratio of the dichlorosilane to the aminophenyl acetylene so as to control the polymer performance. The resin is liable to dissolve in common organic solvents, moderate in viscosity at normal temperature, good in storage stability and suitable for preparing high-performance composite material matrixes, ceramic precursors, ablation-resistant materials, high-temperature-resistant coatings and photoelectric materials and has extensive application prospect.

Description

A kind of high temperature resistant hybrid silicon azane resin and preparation method thereof
Technical field
The present invention relates to a kind of high temperature resistant hybrid silicon azane resin and preparation method thereof, particularly main chain contains a kind of hybrid inorganic-organic materials amino phenylacetylene-capped poly-(diacetylene-benzene-silane) of Siliciumatom, nitrogen-atoms and ethynyl.
Background technology
The high temperature resistant hybrid resin that contains Si, N element becomes the research focus with its excellent high strength, high-modulus and performance such as anti-oxidant.This resinoid is applicable to preparation ceramic precursor, high performance composite matrix, high temperature resistant ablator etc., in fields such as aerospace, national defence, military affairs wide application prospect is arranged.
Employing ethynyl Grignard reagents such as Luneva and aryl silicon halogenide have been feedstock production siliceous alkynes resin (Vysokomolekulyamye Soedineniya, Seriya A, 1967; 9:910-14), this resin cured matter has excellent heat resisting, and its heat resisting temperature can reach 450-550 ℃; The Chen Qi of East China University of Science etc. has synthesized methyldiphenyl ethynyl silane (MDPES) (ZL02151140.3; ZL200510110133.5), its cured article is at N 2The temperature of mass loss 5% is 615 ℃ under the condition, and the quality retention rate under 800 ℃ is 91.1%; Bill etc. are by the synthetic Si-N-C pottery (Appl.Organometal.Chem.2001 of the solid-state cracking of polysilazane and poly-silyl carbodiimide; 15:777-793), the SiC/Si that obtains 3N 4The balanced system of/C three-phase still can show good thermal stability up to 2000 ℃ the time.Studies show that, in silicon alkynes resin structure, introduce the N element, utilize the synergy of N and Si element, can further improve the heat-resisting and antioxidant property of silicon alkynes resin, it is more widely used.
The present invention is intended to prepare and contains the Si-N key in the molecular backbone chain structure, and with the high temperature resistant hybrid silicon azane resin of HC ≡ C-group end capping amino phenylacetylene-capped poly-(diacetylene-benzene-silane).On the one hand, because Si, N unit have bigger electronegativity difference, nitrogen-atoms unbound electron pair makes the Si-N key have unique stability and rigidity with the effect of the empty d track of Siliciumatom, the existence of Si-N key in the structure simultaneously, formation SiC and Si during the resin cured matter cracking 3N 4Complex phase ceramic, thus the high-temperature oxidation resistance of resin improved.On the other hand, in the structure existence of HC ≡ C-make resin can be under light, heat or lower temperature curing molding, have good processing properties.The present invention is main raw material with diacetylene-benzene, amino-benzene acetylene, dichlorosilane, adopt the Grignard reagent method to synthesize a kind of high temperature resistant hybrid silicon azane resin amino phenylacetylene-capped poly-(diacetylene-benzene-silane), this resin is soluble in all kinds of ordinary organic solvents, modest viscosity under the normal temperature, has good preservation stability, be applicable to preparation high performance composite matrix, ceramic precursor, ablation resistant material, high-temperaure coating and photoelectric material, have a extensive future.
Summary of the invention
The present invention has synthesized a kind of high temperature resistant hybrid silicon azane resin amino phenylacetylene-capped poly-(diacetylene-benzene-silane), and described resin structure formula is as follows:
Figure BSA00000916049000021
Wherein: (1), R 1, R 2Be respectively hydrogen atom, alkyl or aryl; (2), n is natural number; (3), Ar 1For
Figure BSA00000916049000022
Figure BSA00000916049000023
Or both mixtures; (4), Ar 2For
Figure BSA00000916049000024
Figure BSA00000916049000025
Figure BSA00000916049000026
Or three's mixture.
The invention provides the brand-new polymkeric substance of a kind of structure, its repeating unit contains the structure of a diacetylene-benzene-silane at least.By regulating the mol ratio of diacetylene-benzene and dichlorosilane, dichlorosilane and amino-benzene acetylene, can well control the content of silicon in the molecular weight, cross-linking density, structure of polymkeric substance or nitrogen, thereby reach the controlled purpose of polymer performance.
Another object of the present invention provides a kind of method for preparing described high temperature resistant hybrid silicon azane resin.The present invention adopts the Grignard reagent method, is main raw material with diacetylene-benzene, dichlorosilane, amino-benzene acetylene, and tetrahydrofuran (THF) (THF) is solvent, at rare gas element (as N 2) protection under, divide the preparation of four steps described resin, concrete steps are as follows:
(1), under protection of inert gas, the drips of solution of monobromethane and tetrahydrofuran (THF) is added in the mixture of magnesium powder and tetrahydrofuran (THF), reaction generates ethylmagnesium bromide.It is characterized in that: the temperature of reaction of monobromethane solution in the dropping process is 10～70 ℃, dropwises back control temperature of reaction 40～70 ℃ of reactions 0.5～4 hour.
Figure BSA00000916049000027
(2), under protection of inert gas, slowly drip the tetrahydrofuran solution of diacetylene-benzene in the ethylmagnesium bromide solution, reaction generates diacetylene phenyl magnesium bromide.It is characterized in that: the temperature of reaction of diacetylene benzole soln in the dropping process is 10～60 ℃, dropwises back control temperature of reaction 40～70 ℃ of reactions 1～4 hour.
CH 3CH 2MgBr+HC≡C-Ar 1-C≡CH→BrMgC≡C-Ar 1-C≡CMgBr
Wherein: Ar 1For
Figure BSA00000916049000031
Or two kinds mixture.
(3), under protection of inert gas, drip the tetrahydrofuran solution of dichlorosilane in the product that generates to the second step reaction, reaction generates poly-(diacetylene-benzene-silane) that two ends are chlorine atom end-blocking.It is characterized in that: the temperature of reaction of dichlorosilane solution in the dropping process is 10～50 ℃, dropwises back control temperature of reaction 40～70 ℃ of reactions 0.5～5 hour.
Figure BSA00000916049000033
Wherein: (1), R 1, R 2Be respectively hydrogen atom, alkyl or aryl; (2), n is natural number; (3), Ar 1For
Figure BSA00000916049000034
Figure BSA00000916049000035
Or both mixtures.
(4), under protection of inert gas; drip the tetrahydrofuran solution of triethylamine and amino-benzene acetylene in the product that generates to three-step reaction; after reaction finishes, handle obtaining the high temperature resistant hybrid silicon azane of final product resin amino phenylacetylene-capped poly-(diacetylene-benzene-silane).It is characterized in that: triethylamine and the temperature of reaction of amino-benzene acetylene solution in the dropping process are 10～40 ℃, dropwise back control temperature of reaction 25～45 ℃ of reactions 2～5 hours.
Wherein: (1), R 1, R 2Be respectively hydrogen atom, alkyl or aryl; (2), n is natural number; (3), Ar 1For
Figure BSA00000916049000042
Or both mixtures; (4), Ar 2For
Figure BSA00000916049000044
Figure BSA00000916049000045
Figure BSA00000916049000046
Or three's mixture.
High temperature resistant hybrid silicon azane resin of the present invention amino phenylacetylene-capped poly-(diacetylene-benzene-silane).Modest viscosity under the normal temperature is soluble in all kinds of ordinary organic solvents, can be used for preparing high temperature resistant composite matrix resin, ceramic forerunner, high-temperaure coating etc.
Specific implementation method:
Embodiment 1: prepare high temperature resistant hybrid silicon azane resin amino phenylacetylene-capped poly-(diacetylene-benzene-silane) (R wherein 1Be CH 3, R 2Be H, Ar 1For
Figure BSA00000916049000047
Ar 2For
Figure BSA00000916049000048
)
At N 2Protection under; 3.6g magnesium powder, iodine crystalline substance and 30ml tetrahydrofuran (THF) are joined in the 250ml four-hole boiling flask; drip the mixing solutions of 16.5g monobromethane and 30ml tetrahydrofuran (THF) then in the system, dropping temperature maintains 25～40 ℃, dropwises the back and react 2h under 60 ℃ of conditions.After the reactant cooling, the control temperature of reaction drips 9.6g1 at 25～30 ℃, and the mixing solutions of 4-diacetylene-benzene and 30ml tetrahydrofuran (THF) dropwises the back and react 2.5h under 60 ℃ of conditions.After the cooling of question response thing, the control temperature of reaction continues the solution that dropping 17.25g methyl hydrogen dichlorosilane and 20ml tetrahydrofuran (THF) are made at 25～30 ℃, dropwises the back and react 3h under 60 ℃ of conditions.After the question response system is cooled to room temperature, drip the mixed solution of 20ml triethylamine, 21.1g4-amino-benzene acetylene and 20ml tetrahydrofuran (THF) in the reaction system, dropwise the back and under 25～35 ℃ of conditions, react 4h.After reaction finished, suction filtration was removed the salt of generation, and underpressure distillation namely gets product after eliminating solvent.
FT-IR：3389cm -1(N-H)，3298cm -1(C≡C-H)，2157cm -1(C≡C、Si-H)，1269cm -1(Si-C)，950cm -1(Si-N)
Embodiment 2: preparation novel fire resistant hybrid silicon azane resin amino phenylacetylene-capped poly-(diacetylene-benzene-silane) (R wherein 1Be CH 3, R 2For Ar 1For
Figure BSA00000916049000052
Ar 2For
Figure BSA00000916049000053
)
At N 2Protection under; 7.2g magnesium powder, iodine crystalline substance and 50ml tetrahydrofuran (THF) are joined in the 500ml four-hole boiling flask; the mixing solutions of Dropwise 35 .7g monobromethane and 50ml tetrahydrofuran (THF) in the system then, dropping temperature maintains 25～40 ℃, dropwises the back and react 2h under 65 ℃ of conditions.After the reactant cooling, the control temperature of reaction drips 18.9g1 at 25～30 ℃, and the mixing solutions of 3-diacetylene-benzene and 60ml tetrahydrofuran (THF) dropwises the back and react 2.5h under 65 ℃ of conditions.After the cooling of question response thing, the control temperature of reaction continues the solution that dropping 31g dichloromethyl phenylsilane and 50ml tetrahydrofuran (THF) are made at 25～30 ℃, dropwises the back and react 3h under 65 ℃ of conditions.After the question response thing is cooled to room temperature, drip the mixed solution of 30ml triethylamine, 32g3-amino-benzene acetylene and 30ml tetrahydrofuran (THF) in the reaction system, dropwise the back and under 25～35 ℃ of conditions, react 4h.After reaction finished, suction filtration was removed the salt of generation, and underpressure distillation namely gets product after eliminating solvent.
FT-IR：3385cm -1(N-H)，3295cm -1(C≡C-H)，3062cm -1(Ph-H)，2160cm -1(C≡C)，1265cm -1(Si-C)，948cm -1(Si-N)
Embodiment 3: prepare high temperature resistant hybrid silicon azane resin amino phenylacetylene-capped poly-(diacetylene-benzene-silane) (R wherein 1Be CH 3, R 2Be H, Ar 1For Ar 2For
Figure BSA00000916049000055
)
At N 2Protection under; 3.6g magnesium powder, iodine crystalline substance and 30ml tetrahydrofuran (THF) are joined in the 250ml four-hole boiling flask; drip the mixing solutions of 16.5g monobromethane and 30ml tetrahydrofuran (THF) then in the system, dropping temperature maintains 25～40 ℃, dropwises the back and react 2h under 65 ℃ of conditions.After the reactant cooling, the control temperature of reaction drips 9.6g1 at 25～30 ℃, and the mixing solutions of 4-diacetylene-benzene and 30ml tetrahydrofuran (THF) dropwises the back and react 2.5h under 65 ℃ of conditions.After the cooling of question response thing, the control temperature of reaction continues the solution that dropping 18.6g methyl hydrogen dichlorosilane and 20ml tetrahydrofuran (THF) are made at 25～30 ℃, dropwises the back and react 3h under 65 ℃ of conditions.After the question response system is cooled to room temperature, drip the mixed solution of 25ml triethylamine, 23.7g3-amino-benzene acetylene and 25ml tetrahydrofuran (THF) in the reaction system, dropwise the back and under 25～35 ℃ of conditions, react 4h.After reaction finished, suction filtration was removed the salt of generation, and underpressure distillation namely gets product after eliminating solvent.
FT-IR：3379cm -1(N-H)，3292cm -1(C≡C-H)，3070cm -1(Ph-H)，2155cm -1(C＝C、Si-H)，947cm -1(Si-N)。

Claims (10)

1. a high temperature resistant hybrid silicon azane resin amino phenylacetylene-capped poly-(diacetylene-benzene-silane) is characterized in that described high temperature resistant hybrid silicon azane resin has following structure:
Figure FSA00000916048900011
Wherein: (1), R 1, R 2Be respectively hydrogen atom, alkyl or aryl; (2), n is natural number; (3), Ar 1For
Figure FSA00000916048900012
Figure FSA00000916048900013
Or both mixtures; (4), Ar 2For
Figure FSA00000916048900014
Figure FSA00000916048900015
Figure FSA00000916048900016
Or three's mixture.
2. the preparation method of the described high temperature resistant hybrid silicon azane resin of claim 1, its key step is:
(1), the first step reaction: under protection of inert gas, by the reaction generation ethylmagnesium bromide of magnesium and monobromethane;
(2), second step reaction: under protection of inert gas, the reaction product of the first step and diacetylene-benzene reaction generate diacetylene phenyl magnesium bromide;
(3), three-step reaction: under protection of inert gas, the reaction product in second step and dichlorosilane react, and generating two ends is poly-(diacetylene-silane) of chlorine atom end-blocking;
(4), four-step reaction: under protection of inert gas, the 3rd the step reaction product in the presence of triethylamine with the amino-benzene acetylene reaction, obtain the high temperature resistant hybrid silicon azane of product resin after the processing.
3. preparation method according to claim 2, it is characterized in that: the mol ratio of diacetylene-benzene and dichlorosilane is 1: (1.5～2.5); The mol ratio of dichlorosilane and amino-benzene acetylene is 1: (1～2).
4. preparation method according to claim 2, it is characterized in that: in the first step reaction process, the dropping temperature of monobromethane is 10～70 ℃, and dropwising the afterreaction temperature is 40～70 ℃, and the reaction times is 0.5～4 hour.
5. preparation method according to claim 2 is characterized in that: in the second step reaction process, the dropping temperature of diacetylene-benzene is 10～60 ℃, and dropwising the afterreaction temperature is 40～70 ℃, and the reaction times is 1～4 hour.
6. preparation method according to claim 2, it is characterized in that: in the three-step reaction process, the dropping temperature of dichlorosilane is 10～50 ℃, and dropwising the afterreaction temperature is 40～70 ℃, and the reaction times is 0.5～5 hour.
7. preparation method according to claim 2, it is characterized in that: in the four-step reaction process, the dropping temperature of triethylamine, amino-benzene acetylene is 10～40 ℃, and dropwising the afterreaction temperature is 25～45 ℃, and the reaction times is 2～5 hours.
8. preparation method according to claim 2, it is characterized in that: diacetylene-benzene is 1,3-diacetylene-benzene, 1,4-diacetylene-benzene or both mixtures.
9. preparation method according to claim 2, it is characterized in that: amino-benzene acetylene is 1,2-amino-benzene acetylene, 1,3-amino-benzene acetylene, 1,4-amino-benzene acetylene or three's mixture.
10. preparation method according to claim 2 is characterized in that: the R in the dichlorosilane 1, R 2Be respectively hydrogen atom, alkyl or aryl.
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CN103724628A (en) * 2014-01-10 2014-04-16 华东理工大学 High performance resin: acetenyl aniline terminated polycarbosilazane
CN104072780A (en) * 2014-07-21 2014-10-01 华东理工大学 Boron silicon alkyne resin and preparation method thereof
CN104130417A (en) * 2014-07-21 2014-11-05 华东理工大学 High-temperature silicon alkyne resin containing nitrogen and preparation method thereof
CN104194717A (en) * 2014-09-24 2014-12-10 中国人民解放军国防科学技术大学 Preparation method for high-temperature-resistant ceramic precursor adhesive
CN107916085A (en) * 2017-10-09 2018-04-17 珠海固瑞泰复合材料有限公司 A kind of heat-proof epoxy thermal conductive insulation glue and preparation method thereof
CN111548497A (en) * 2020-05-29 2020-08-18 华东理工大学 Silyne hybrid resin, cured product, ceramic material, composite material and preparation method

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103724628A (en) * 2014-01-10 2014-04-16 华东理工大学 High performance resin: acetenyl aniline terminated polycarbosilazane
CN103724628B (en) * 2014-01-10 2017-01-04 华东理工大学 The polycarbosilazanes of high performance resin-acetylenylaniline end-blocking
CN104072780A (en) * 2014-07-21 2014-10-01 华东理工大学 Boron silicon alkyne resin and preparation method thereof
CN104130417A (en) * 2014-07-21 2014-11-05 华东理工大学 High-temperature silicon alkyne resin containing nitrogen and preparation method thereof
CN104194717A (en) * 2014-09-24 2014-12-10 中国人民解放军国防科学技术大学 Preparation method for high-temperature-resistant ceramic precursor adhesive
CN104194717B (en) * 2014-09-24 2015-12-09 中国人民解放军国防科学技术大学 A kind of preparation method of refractory ceramics precursor binding agent
CN107916085A (en) * 2017-10-09 2018-04-17 珠海固瑞泰复合材料有限公司 A kind of heat-proof epoxy thermal conductive insulation glue and preparation method thereof
CN111548497A (en) * 2020-05-29 2020-08-18 华东理工大学 Silyne hybrid resin, cured product, ceramic material, composite material and preparation method

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