CN103724628A - High performance resin: acetenyl aniline terminated polycarbosilazane - Google Patents
High performance resin: acetenyl aniline terminated polycarbosilazane Download PDFInfo
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- CN103724628A CN103724628A CN201410011167.8A CN201410011167A CN103724628A CN 103724628 A CN103724628 A CN 103724628A CN 201410011167 A CN201410011167 A CN 201410011167A CN 103724628 A CN103724628 A CN 103724628A
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- acetylenylaniline
- polycarbosilazanes
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- blocking
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Abstract
The invention discloses a preparation method of high performance resin: acetenyl aniline terminated polycarbosilazane. The structural formula of the acetenyl aniline terminated polycarbosilazane prepared by adopting the method disclosed by the invention is shown as a formula I in the specification, wherein phenylenediamine is of para-position, meta-position and ortho-position structures; acetenyl aniline is of para-position, meta-position and ortho-position structures; R1 and R2 respectively are methyl and phenyl. The acetenyl aniline terminated polycarbosilazane is viscous deep yellow liquid, the acetenyl is contained at the tail end of the molecular structure and the activity of terminal alkynyl is high, so that the liquid can be cross-linked and solidified at a certain temperature to obtain a solidified substance which is tight, compact and excellent in heat resistance; plenty of benzene rings are contained in the main chain structure, so that small molecules can be prevented from escaping; the benzene rings are conjugated with carbon-carbon triple bond, so that the heat resistance of the resin is further increased; the resin is high in viscosity and large in molecular weight and is very easily dissolved in various solvents; the resin is high performance resin and can be used for preparing high temperature resisting coatings, high performance composite resin matrixes, and high temperature resisting polymers and preparing ceramic precursors containing Si3N4 and SiC.
Description
Technical field
The present invention relates to a kind of performance resins---the polycarbosilazanes of acetylenylaniline end-blocking, belongs to the synthetic field of organic high molecular polymer.
Background technology
In the non-oxygen pottery of high-performance, silicon nitride (Si
3n
4) ceramic owing to thering is the characteristics such as good mechanical behavior under high temperature, thermostability, resistance to oxidation, high rigidity, low density and being subject to people's extensive concern with the good chemical consistency of metal.Along with the high speed development of the top science technology such as aerospace, the demand of new high-performance load material has further been promoted to the researchdevelopment of high performance structure ceramic.Scientists is inspired for SiC pottery by gathering silicon-carbon alkane presoma cracking by Yajima, has just started with polysilazane cracking for Si
3n
4the research work of pottery, and obtain certain achievement.With respect to silicon carbide ceramics presoma, the research of Study of Silicon-nitride Preceramics is started late also less.
The class organic polymer that it is main chain containing Si-N key in molecular structure that polysilazane (polysilazane, PSZ) refers to.After this polymer cracking, can generate Si
3n
4or Si-C-N pottery.Different from Polycarbosilane is that silazane more easily exists with the form of trimerization or four poly-cyclosilazanes, so general synthetic polysilazane majority contains trimerization or four poly-cyclosilazane structures.
Research discovery, in polysilazane, leading-in end alkynyl and phenyl ring can significantly improve thermotolerance and the ceramic rate of material.The existence of the carbon-carbon triple bond of high reaction activity makes it can be solidified into fine and close thermosetting resin, in some polycarbosilazanes, contains aromatic ring, forms conjugated system with carbon-carbon triple bond, further improves the resistance to elevated temperatures of resin.Wang Rui etc. have synthesized the silazane of end ethynyl by the aminolysis reaction of dichlorosilane, in product, existing curable crosslinked ethynyl, has again phenyl ring, and therefore cured article has very high thermotolerance.
Summary of the invention
The invention provides a kind of performance resins---the polycarbosilazanes of acetylenylaniline end-blocking, on molecular backbone chain, there are Si-N key and a large amount of phenyl ring, and with HC ≡ C-group end capping.The ethynyl is here end alkynyl radical, active large, can be at lower temperature crosslinking curing.Main polymer chain contains a large amount of phenyl ring, can stop micromolecular effusion on the one hand, and phenyl ring and carbon carbon triple bond form conjugated system on the other hand, all can make its resistance to elevated temperatures and ceramic rate obtain one and significantly improve.Owing to there being Si-N key, at high temperature surface meeting of polymkeric substance ceramic, forms SiC, Si
3n
4complex phase ceramic, plays the provide protection of heat insulation oxygen barrier to inner layer material, at high temperature have higher quality retention rate.It can be for the preparation of high temperature resistant composite, ablation resistant material, ceramic forerunner and high-temperaure coating etc.
The structural formula of the performance resins of synthesized of the present invention---the polycarbosilazanes of acetylenylaniline end-blocking is shown in formula I:
Wherein, the structure of phenylenediamine is contraposition, a position and ortho position; The structure of acetylenylaniline is contraposition, a position; R
1, R
2be respectively methyl, aryl; N is 50 ~ 180.
The present invention is take phenylenediamine, alkyl dichlorosilane, acetylenylaniline as raw material, and triethylamine is acid binding agent, and organic solvent is that carbonatoms is one or more in 6 ~ 12 alkane, tetrahydrofuran (THF), ether, synthesizes the polycarbosilazanes of acetylenylaniline end-blocking.Concrete steps are as follows:
(1) under inert atmosphere, phenylenediamine mixes 1:3 ~ 7 in molar ratio with organic solvent, adds triethylamine, is uniformly mixed; By alkyl dichlorosilane (structural formula is suc as formula shown in II) and the organic solvent solution that mix 1:2 ~ 8 in molar ratio, be dropwise added drop-wise in above-mentioned mixing solutions, after dropwising, at-10 ~ 25 ℃, react 3 ~ 10 hours, obtain the polycarbosilazanes of silicon chlorine key end-blocking.
Wherein, the structure of phenylenediamine is contraposition, a position and ortho position; The structure of acetylenylaniline is contraposition, a position; R
1, R
2be respectively methyl, aryl; N is 50 ~ 180.
(2) under inert atmosphere, acetylenylaniline mixes 1:2 ~ 8 in molar ratio with organic solvent, is dropwise added drop-wise in the first step product solution, reacts 5 ~ 15 hours at-10 ~ 25 ℃, obtains the polycarbosilazanes of acetylenylaniline end-blocking.
(3) reaction finishes rear suction filtration, takes off a layer clear filtrate, is placed in Rotary Evaporators except desolventizing, obtains thick liquid, is product.
The present invention is by phenylenediamine and alkyl dichlorosilane generation aminolysis reaction, Si-N key and HC ≡ C-group is incorporated in the middle of polymkeric substance, and with phenylenediamine, be that main polymer chain structure is introduced a large amount of phenyl ring and increased its thermotolerance.The aminolysis reaction of chlorosilane is easier to carry out, easily-controlled reaction conditions, and technical process is simple, and operation is simple.The polycarbosilazanes of gained performance resins---acetylenylaniline end-blocking is thick liquid.Its hot setting thing has good resistance to elevated temperatures and has higher ceramic rate.It can be for the preparation of high temperature resistant composite, ablation resistant material, ceramic forerunner and high-temperaure coating etc.
specific implementation method
Embodiment 1: between Ursol D preparation, (wherein phenylenediamine is contraposition to the polycarbosilazanes of acetylenylaniline end-blocking; Acetylenylaniline be between position; R
1for methyl; R
2for methyl)
Under inert atmosphere, in the four-hole boiling flask of 500ml, add Ursol D 0.06mol, tetrahydrofuran (THF) 0.48mol and triethylamine 0.24mol.℃ left and right, ice bath control temperature-30, adds dimethyldichlorosilane(DMCS) 0.12mol and tetrahydrofuran (THF) 0.60mol mixing solutions in constant pressure funnel, be dropwise added drop-wise in four-hole bottle, strengthens stirring dynamics simultaneously.Can observe and in solution, have a large amount of triethylamine hydrochloride white precipitates.After dropwising, at 20 ℃, react 4 hours.After the first step reaction finishes, add ice bath control temperature-30 ℃ of left and right, by constant pressure funnel, to reaction system, dropwise drip the mixed solution of m-aminophenyl acetylene 0.12mol and tetrahydrofuran (THF) 0.60mol.After dropwising, at 20 ℃, react 6 hours.After reaction finishes, by suspension suction filtration for several times, get filtrate, tetrahydrofuran (THF) is steamed to remove and collect 22.17g viscous deep yellow liquid, obtain product.Productive rate is 90.65%.
As shown in Figure 1, its solidification value peak is at 265.0 ℃ for DSC result.
The DSC figure of the polycarbosilazanes of acetylenylaniline end-blocking between the preparation of Fig. 1 Ursol D
Thermotolerance to this polycarbosilazanes cured article is studied, and as shown in Figure 2, in nitrogen atmosphere, temperature during mass loss 5% is 241.84 ℃ to test result, and the quality retention rate at 1000 ℃ is 47.82%.
The TGA figure of the polycarbosilazanes of acetylenylaniline end-blocking between the preparation of Fig. 2 Ursol D
Embodiment 2: O-Phenylene Diamine is prepared polycarbosilazanes to acetylenylaniline end-blocking, and (wherein phenylenediamine is ortho position; Acetylenylaniline is contraposition; R
1for methyl; R
2for phenyl)
Operate with the device identical with example 1.Under inert atmosphere, in the four-hole boiling flask of 500ml, add O-Phenylene Diamine 0.06mol, tetrahydrofuran (THF) 0.48mol and triethylamine 0.18mol.℃ left and right, ice bath control temperature-30, adds dichloromethyl phenylsilane 0.09mol and tetrahydrofuran (THF) 0.60mol mixing solutions, and is dropwise added drop-wise in four-hole bottle in constant pressure funnel, strengthen stirring dynamics simultaneously.Can observe and in solution, have a large amount of triethylamine hydrochloride white precipitates.After dropwising, at 20 ℃, react 4 hours.After the first step reaction finishes, add ice bath control temperature-30 ℃ of left and right, by constant pressure funnel, to reaction system, dropwise drip the mixed solution of p-aminophenyl acetylene 0.06mol and tetrahydrofuran (THF) 0.60mol.After dropwising, at 20 ℃, react 6 hours.After reaction finishes, by suspension suction filtration for several times, get filtrate, tetrahydrofuran (THF) is steamed to remove and collect 24.93g thickness light yellow liquid, obtain product.Productive rate is 85.95%.
As shown in Figure 3, its solidification value peak is at 270.1 ℃ for DSC result.
Thermotolerance to this polycarbosilazanes cured article is studied, and as shown in Figure 4, in nitrogen atmosphere, temperature during mass loss 5% is 317.90 ℃ to test result, and the quality retention rate at 1000 ℃ is 56.15%.
Fig. 3 O-Phenylene Diamine is prepared the DSC figure of the polycarbosilazanes to acetylenylaniline end-blocking
Fig. 4 O-Phenylene Diamine is prepared the TGA figure of the polycarbosilazanes to acetylenylaniline end-blocking
Embodiment 3: mphenylenediamine prepare polycarbosilazanes to acetylenylaniline end-blocking (wherein phenylenediamine be between position; Acetylenylaniline is contraposition; R
1for phenyl; R
2for phenyl)
Operate with the device identical with example 1,2.Under inert atmosphere, in the four-hole boiling flask of 500ml, add mphenylenediamine 0.06mol, tetrahydrofuran (THF) 0.48mol and triethylamine 0.22mol.℃ left and right, ice bath control temperature-30, adds diphenyl dichlorosilane 0.11mol and tetrahydrofuran (THF) 0.60mol mixing solutions, and is dropwise added drop-wise in four-hole bottle in constant pressure funnel, strengthen stirring dynamics simultaneously.Can observe and in solution, have a large amount of triethylamine hydrochloride white precipitates.After dropwising, at 20 ℃, react 4 hours.After the first step reaction finishes, add ice bath control temperature-30 ℃ of left and right, by constant pressure funnel, to reaction system, dropwise drip the mixed solution of p-aminophenyl acetylene 0.10mol and tetrahydrofuran (THF) 0.60mol.After dropwising, at 20 ℃, react 6 hours.After reaction finishes, by suspension suction filtration for several times, get filtrate, tetrahydrofuran (THF) is steamed to remove and collect 19.31g thickness light yellow liquid, obtain product.Productive rate is 91.32%.
As shown in Figure 5, its solidification value peak is at 256.8 ℃ for DSC result.
Fig. 5 mphenylenediamine is prepared the DSC figure of the polycarbosilazanes to acetylenylaniline end-blocking
Thermotolerance to this polycarbosilazanes cured article is studied, and as shown in Figure 6, in nitrogen atmosphere, temperature during mass loss 5% is 443.35 ℃ to test result, and the quality retention rate at 1000 ℃ is 58.29%.
Fig. 6 mphenylenediamine is prepared the TGA figure of the polycarbosilazanes to acetylenylaniline end-blocking.
Claims (3)
1. performance resins a---polycarbosilazanes for acetylenylaniline end-blocking, is characterized in that it has following molecular structure:
Wherein, the structure of phenylenediamine is contraposition, a position and ortho position; The structure of acetylenylaniline is contraposition, a position; R
1, R
2be respectively methyl, phenyl; N is 50 ~ 180.
2. performance resins claimed in claim 1---the polycarbosilazanes of acetylenylaniline end-blocking, its preparation method carries out in the steps below:
Under inert atmosphere, phenylenediamine mixes 1:3 ~ 7 in molar ratio with organic solvent, adds triethylamine, is uniformly mixed; By alkyl dichlorosilane and the organic solvent solution that mix 1:2 ~ 8 in molar ratio, be dropwise added drop-wise in above-mentioned mixing solutions, after dropwising, at-10 ~ 25 ℃, react 3 ~ 10 hours, obtain the polycarbosilazanes of silicon chlorine key end-blocking, its structure is suc as formula shown in II:
Wherein, the structure of phenylenediamine is contraposition, a position and ortho position; The structure of acetylenylaniline is contraposition, a position; R
1, R
2be respectively methyl, phenyl; N is 50 ~ 180;
Acetylenylaniline mixes 1:2 ~ 8 in molar ratio with organic solvent, is dropwise added drop-wise in the first step product solution, reacts 5 ~ 15 hours at-10 ~ 25 ℃, obtains the polycarbosilazanes of acetylenylaniline end-blocking.
3. performance resins according to claim 2---the polycarbosilazanes of acetylenylaniline end-blocking, described organic solvent is that carbonatoms is one or more in 6 ~ 12 alkane, tetrahydrofuran (THF), ether.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333341A (en) * | 2013-06-25 | 2013-10-02 | 华东理工大学 | High-temperature-resistant hybrid silazane resin and preparation method thereof |
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| CN103333341A (en) * | 2013-06-25 | 2013-10-02 | 华东理工大学 | High-temperature-resistant hybrid silazane resin and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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