CN103724628B - The polycarbosilazanes of high performance resin-acetylenylaniline end-blocking - Google Patents
The polycarbosilazanes of high performance resin-acetylenylaniline end-blocking Download PDFInfo
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- CN103724628B CN103724628B CN201410011167.8A CN201410011167A CN103724628B CN 103724628 B CN103724628 B CN 103724628B CN 201410011167 A CN201410011167 A CN 201410011167A CN 103724628 B CN103724628 B CN 103724628B
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Abstract
The invention discloses the preparation method of the polycarbosilazanes of a kind of high performance resin acetylenylaniline end-blocking.The structural formula of the polycarbosilazanes of this acetylenylaniline end-blocking obtained by invention is as shown in formula I, and wherein, the structure of phenylenediamine is para-position, meta and ortho position；The structure of acetylenylaniline is para-position, meta and ortho position；R1、R2It is respectively methyl, phenyl.The polycarbosilazanes of the acetylenylaniline end-blocking of this invention is viscous deep yellow liquid.Molecular structure end contains acetenyl, and end alkynyl radical activity is high, so cross-linkable solidifying at a certain temperature, obtains the solidfied material of tight densification, excellent heat resistance.Containing a large amount of phenyl ring in backbone structure, the effusion of little molecule can be stoped, and be conjugated with carbon-carbon triple bond, then improve the thermostability of resin.This resin viscosity is big, and molecular weight is big, is highly soluble in various solvent, can be used for preparing high-temperaure coating, high-performance composite materials resin matrix, heat-resistant polymer and preparation containing Si3N4, the ceramic presoma of SiC, be a kind of high performance resin.
Description
Technical field
The present invention relates to the polycarbosilazanes of a kind of high performance resin-acetylenylaniline end-blocking, belong to organic polymer and gather
Compound synthesis field.
Background technology
In high-performance non-oxygen pottery, silicon nitride (Si3N4) pottery is owing to having good mechanical behavior under high temperature, thermally-stabilised
The characteristic such as property, resistance to oxidation, high rigidity, low-density and with the good chemical compatibility of metal and by people's extensive concern.With
The high speed development of the most advanced branches of science technology such as Aero-Space, the demand of new high-performance load material is further promoted height
The research and development of performance structure pottery.Scientists is inspired, just by poly-silicon-carbon alkane presoma cracking preparation SiC ceramic by Yajima
Start to prepare Si with polysilazane cracking3N4The research work of pottery, and obtain certain achievement.Before silicon carbide ceramics
Driving body, the research of Study of Silicon-nitride Preceramics is started late the most less.
Polysilazane (polysilazane, PSZ) refers to that in molecular structure, the N key Han Si is an organic high score of class of main chain
Son.Si can be generated after this polymer cracking3N4Or Si C N pottery.Silazane is more easy to trimerization unlike Polycarbosilane
Or four presented in polycyclic silazane, so the polysilazane majority of general synthesis contains trimerization or four polycyclic silazane knot
Structure.
Research finds, in polysilazane, leading-in end alkynyl and phenyl ring can be greatly improved thermostability and the ceramic of material
Rate.The existence of the carbon-carbon triple bond of high reaction activity makes it can be solidified into the thermosetting resin of densification, in some polycarbosilazanes
Containing aromatic ring, form conjugated system with carbon-carbon triple bond, improve the resistance to elevated temperatures of resin further.Wang Rui etc. pass through dichlorosilane
Aminolysis reaction synthesized the silazane of end acetenyl, the acetenyl of existing curable crosslinking in product, have again a phenyl ring, therefore solid
Compound has the highest thermostability.
Summary of the invention
The present invention provides the polycarbosilazanes of a kind of high performance resin-acetylenylaniline end-blocking, has on molecular backbone
Si-N key and a large amount of phenyl ring, and with HC ≡ C-group end capping.Here acetenyl is end alkynyl radical, and activity is big, can be relatively low
At a temperature of crosslinking curing.Main polymer chain is contained within a large amount of phenyl ring, on the one hand can stop the effusion of little molecule, on the other hand phenyl ring
Form conjugated system with triple carbon-carbon bonds, its resistance to elevated temperatures and pottery rate all can be made to obtain one and significantly improve.Owing to existing
Si-N key, polymer at high temperature surface meeting ceramic, form SiC, Si3N4Complex phase ceramic, plays heat insulation oxygen barrier to inner layer material
Protective effect, at high temperature there is higher quality retention rate.It may be used for preparing high temperature resistant composite, the material of resistance to ablation
Material, ceramic forerunner and high-temperaure coating etc..
The structural formula of the polycarbosilazanes of the high performance resin synthesized by the present invention-acetylenylaniline end-blocking is formula I institute
Show:
Wherein, the structure of phenylenediamine is para-position, meta and ortho position；The structure of acetylenylaniline is para-position, meta；R1、R2Point
Wei methyl, aryl；N is 50 ~ 180.
The present invention is with phenylenediamine, alkyl dichlorosilane, acetylenylaniline as raw material, and triethylamine is acid binding agent, organic solvent
For one or more in alkane that carbon number is 6 ~ 12, oxolane, ether, synthesize the poly-carbon of acetylenylaniline end-blocking
Silazane.Specifically comprise the following steps that
(1) under inert atmosphere, phenylenediamine mixes with organic solvent 1:3 ~ 7 in molar ratio, adds triethylamine, and stirring mixing is all
Even；The solution mixed with organic solvent 1:2 ~ 8 in molar ratio by alkyl dichlorosilane (structural formula is as shown in formula II), dropwise drips
In above-mentioned mixed solution, after dropping, react 3 ~ 10 hours at-10 ~ 25 DEG C, obtain the poly-carbon silicon nitrogen of silicon chlorine key end-blocking
Alkane.
Wherein, the structure of phenylenediamine is para-position, meta and ortho position；The structure of acetylenylaniline is para-position, meta；R1、R2Point
Wei methyl, aryl；N is 50 ~ 180.
(2), under inert atmosphere, acetylenylaniline mixes with organic solvent 1:2 ~ 8 in molar ratio, is dropwise added drop-wise to the first step
In reaction mixture, react 5 ~ 15 hours at-10 ~ 25 DEG C, obtain the polycarbosilazanes of acetylenylaniline end-blocking.
(3) reaction terminates rear sucking filtration, takes off a layer clear filtrate, is placed in Rotary Evaporators removing solvent, obtains viscous solution
Body, is product.
The present invention is by phenylenediamine and alkyl dichlorosilane generation aminolysis reaction, is introduced with HC ≡ C-group by Si-N key
In the middle of polymer, it is that the polymer backbone conformation a large amount of phenyl ring of introducing increase its thermostability with phenylenediamine.The amine solution of chlorosilane
Reaction is easier to carry out, easily-controlled reaction conditions, and technological process is simple, and operation is simple.Gained high performance resin-acetylene
The polycarbosilazanes of base aniline end-blocking is thick liquid.Its hot setting thing has good resistance to elevated temperatures and has higher pottery
Porcelain rate.It may be used for preparing high temperature resistant composite, ablation resistant material, ceramic forerunner and high-temperaure coating etc..
Specific implementation method
Embodiment 1: between p-phenylenediamine preparation, (wherein phenylenediamine is para-position to the polycarbosilazanes of acetylenylaniline end-blocking；Second
Alkynyl aniline is meta；R1For methyl；R2For methyl)
Under inert atmosphere, in the four-hole boiling flask of 500ml, add p-phenylenediamine 0.06mol, oxolane 0.48mol with
And triethylamine 0.24mol.Ice bath controls temperature about-30 DEG C, adds dimethyldichlorosilane 0.12mol and four in constant pressure funnel
Hydrogen furan 0.60mol mixed solution, is dropwise added drop-wise in four-hole bottle, strengthens stirring dynamics simultaneously.It is observed that solution has
Substantial amounts of triethylamine hydrochloride white precipitate.After dropping, react 4 hours at 20 DEG C.After first step reaction terminates, on the rocks
Bath controls temperature at about-30 DEG C, dropwise drips 3-aminophenylacetylene 0.12mol and tetrahydrochysene to reaction system by constant pressure funnel
The mixed liquor of furan 0.60mol.After dropping, react 6 hours at 20 DEG C.After reaction terminates, by suspension sucking filtration for several times,
Take filtrate, be evaporated off oxolane collecting 22.17g viscous deep yellow liquid, obtain product.Productivity is 90.65%.
DSC result is as it is shown in figure 1, its solidification temperature peak is at 265.0 DEG C.
The DSC figure of the polycarbosilazanes of acetylenylaniline end-blocking between the preparation of Fig. 1 p-phenylenediamine
Being studied the thermostability of this polycarbosilazanes solidfied material, test result is as in figure 2 it is shown, at nitrogen atmosphere
In, temperature during mass loss 5% is 241.84 DEG C, and the quality retention rate at 1000 DEG C is 47.82%.
The TGA figure of the polycarbosilazanes of acetylenylaniline end-blocking between the preparation of Fig. 2 p-phenylenediamine
Embodiment 2: (wherein phenylenediamine is ortho position to the polycarbosilazanes of acetylenylaniline end-blocking in o-phenylenediamine preparation；Second
Alkynyl aniline is para-position；R1For methyl；R2For phenyl)
Operate with the device identical with example 1.Under inert atmosphere, in the four-hole boiling flask of 500ml, add adjacent benzene two
Amine 0.06mol, oxolane 0.48mol and triethylamine 0.18mol.Ice bath controls temperature about-30 DEG C, adds in constant pressure funnel
Enter dichloromethyl phenylsilane 0.09mol and oxolane 0.60mol mixed solution, and be dropwise added drop-wise in four-hole bottle, simultaneously
Strengthen stirring dynamics.It is observed that solution has substantial amounts of triethylamine hydrochloride white precipitate.After dropping, at 20 DEG C
React 4 hours.The first step reaction terminate after, add ice bath control temperature at about-30 DEG C, by constant pressure funnel to reaction system by
Dropping p-aminophenyl acetylene 0.06mol and the mixed liquor of oxolane 0.60mol.After dropping, at 20 DEG C, react 6 little
Time.After reaction terminates, by suspension sucking filtration for several times, take filtrate, oxolane is evaporated off collects 24.93g thickness light yellow
Liquid, obtains product.Productivity is 85.95%.
DSC result is as it is shown on figure 3, its solidification temperature peak is at 270.1 DEG C.
The thermostability of this polycarbosilazanes solidfied material is studied, test result as shown in Figure 4, at nitrogen atmosphere
In, temperature during mass loss 5% is 317.90 DEG C, and the quality retention rate at 1000 DEG C is 56.15%.
Fig. 3 o-phenylenediamine preparation DSC figure to the polycarbosilazanes of acetylenylaniline end-blocking
Fig. 4 o-phenylenediamine preparation TGA figure to the polycarbosilazanes of acetylenylaniline end-blocking
Embodiment 3: (wherein phenylenediamine is meta to the polycarbosilazanes of acetylenylaniline end-blocking in m-diaminobenzene. preparation；Second
Alkynyl aniline is para-position；R1For phenyl；R2For phenyl)
Operate with the identical device of example 1,2.Under inert atmosphere, in the four-hole boiling flask of 500ml, add isophthalic
Diamidogen 0.06mol, oxolane 0.48mol and triethylamine 0.22mol.Ice bath controls temperature about-30 DEG C, in constant pressure funnel
Add diphenyl dichlorosilane 0.11mol and oxolane 0.60mol mixed solution, and be dropwise added drop-wise in four-hole bottle, simultaneously
Strengthen stirring dynamics.It is observed that solution has substantial amounts of triethylamine hydrochloride white precipitate.After dropping at 20 DEG C
React 4 hours.The first step reaction terminate after, add ice bath control temperature at about-30 DEG C, by constant pressure funnel to reaction system by
Dropping p-aminophenyl acetylene 0.10mol and the mixed liquor of oxolane 0.60mol.After dropping, at 20 DEG C, react 6 little
Time.After reaction terminates, by suspension sucking filtration for several times, take filtrate, oxolane is evaporated off collects 19.31g thickness light yellow
Liquid, obtains product.Productivity is 91.32%.
DSC result is as it is shown in figure 5, its solidification temperature peak is at 256.8 DEG C.
Fig. 5 m-diaminobenzene. preparation DSC figure to the polycarbosilazanes of acetylenylaniline end-blocking
The thermostability of this polycarbosilazanes solidfied material is studied, test result as shown in Figure 6, at nitrogen atmosphere
In, temperature during mass loss 5% is 443.35 DEG C, and the quality retention rate at 1000 DEG C is 58.29%.
Fig. 6 m-diaminobenzene. preparation TGA figure to the polycarbosilazanes of acetylenylaniline end-blocking
Claims (3)
1. the polycarbosilazanes of a high performance resin-acetylenylaniline end-blocking, it is characterised in that it has a following molecular structure:
Wherein, the structure of phenylenediamine is para-position, meta and ortho position；The structure of acetylenylaniline is para-position, meta；R1、R2It is respectively
Methyl, phenyl；N is 50～180.
2. the preparation method of the polycarbosilazanes of the high performance resin described in claim 1-acetylenylaniline end-blocking, its feature exists
In carrying out in the steps below:
(1) under inert atmosphere, phenylenediamine mixes with organic solvent 1:3 in molar ratio～7, adds triethylamine, is uniformly mixed；
The solution mixed with organic solvent 1:2 in molar ratio～8 by alkyl dichlorosilane, is dropwise added drop-wise in above-mentioned mixed solution, drips
After adding, react 3～10 hours at-10～25 DEG C, obtain the polycarbosilazanes of silicon chlorine key end-blocking, its structure such as formula II institute
Show:
Wherein, the structure of phenylenediamine is para-position, meta and ortho position；The structure of acetylenylaniline is para-position, meta；R1、R2It is respectively
Methyl, phenyl；N is 50～180；
(2) acetylenylaniline mixes with organic solvent 1:2 in molar ratio～8, is dropwise added drop-wise in first step reaction mixture ,-
React 5～15 hours at 10～25 DEG C, obtain the polycarbosilazanes of acetylenylaniline end-blocking.
The preparation method of the polycarbosilazanes of high performance resin the most according to claim 2-acetylenylaniline end-blocking, described
Organic solvent be carbon number be 6～12 alkane, oxolane, one or more in ether.
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