CN1101055A - Silicon-nitrogen polymer and synthesizing method and usage thereof - Google Patents
Silicon-nitrogen polymer and synthesizing method and usage thereof Download PDFInfo
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- CN1101055A CN1101055A CN 93117929 CN93117929A CN1101055A CN 1101055 A CN1101055 A CN 1101055A CN 93117929 CN93117929 CN 93117929 CN 93117929 A CN93117929 A CN 93117929A CN 1101055 A CN1101055 A CN 1101055A
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Abstract
The invention relates to a silazine polymer synthesized by using chlorosilicane and organic chlorosilicane as raw material and synthesis thereof. Said silazine polymer can be used as cross linking agent for silicone rubber and silicon resin to make its thermal stability increase greatly eg. the thermal stability of silicon rubber is raised from the 200 degree C. of existing cross linking system asing ethyl silicate as raw material and organic tin us catalyst to 350 degree C. The mixed material of said resin and rubber can also be used as high-temp. embedding material with good performance as well as coatings and binding agent etc.
Description
The present invention relates to a kind of be used for the organosilicon macromolecule processing aid with and synthetic method and application.
Two component condensed room temperature vulcanized silicone rubbers are that linking agent, dibutyl tin laurate are that catalyzer carries out cross-linking vulcanized reaction and obtains cross-linked rubber usually with the ethyl orthosilicate:
Because this class glue has many excellent properties, processing and easy to use simultaneously is so obtained using widely.But also exist some serious problems, mainly be that remaining organotin catalysts is when temperature is high, can cause the main chain degraded of cross-linked rubber rapidly, and emit the low molecular weight polyorganosiloxane ring body and cross-linked rubber hardness is reduced rapidly, particularly this degraded is more outstanding under sealing and inert atmosphere conditions, so this class glue can only use about 200 ℃ usually, and remaining catalyzer also can influence the electrical property (Polym.Eng.Sci. of cross-linked rubber when high temperature, 1986,26(13), 940).In addition, so this class glue uses is that their mechanical property of polysiloxane of lower molecular weight is lower than the mechanical property of high-temperature silicon disulfide rubber.Their cohesive strength is also relatively poor simultaneously, so their use range is restricted.In order to use no or little catalyzer, United States Patent (USP) 3338868,3451964 was once reported and was made linking agent with the silazane of alkylamine, as CH
3Si(N-iPr
2)
3Deng, but can emit the organic amine of pungency and deep-etching, so be difficult to be applied.
Purpose of the present invention provides a kind of silazine link (polymkeric substance Si-NH-Si-) that contains, and synthetic method, it is applied in the organosilicon superpolymer, at room temperature they can be quickly and the silicon hydroxyl reaction, it is crosslinked to make this eka-silicon superpolymer carry out on-catalytic, stop or delay polymeric main chain thermal destruction, make its heat resistance bring up to anti-about 350 ℃, the chain propagation agent that next this class linking agent is again the silicon superpolymer, the mechanical property of crosslinked polymkeric substance is improved, simultaneously may improve its adhesive property again, the problems referred to above that this class organosilicon superpolymer is existed obtain improvement in various degree.
Content of the present invention provides a kind of by chlorosilane and organochlorosilane silicon-nitrogen polymer that contains silazine link (Si-NH-Si-) that to be raw material generate through ammonolysis reaction and the linking agent that is applicable to the organosilicon superpolymer:
Wherein R=Me, ph, Vi, OR, H, (Si-)
x
n＝1～3， m＝5～1000， X＝1～10
Its synthetic method and step are as follows:
(1) taking by weighing chlorosilane 0～20%(mol) and organochlorosilane 80～100%(mol) in proportion is dissolved in the organic solvent that particle potassium hydroxide or molecular sieve drying are crossed, consumption of organic solvent is 2-6 times of adding chlorosilane and the total consumption of organochlorosilane reactant (weight), feeds NH under stirring and water-bath cooling
3, carry out ammonia and separate, logical NH
3Speed be 40～250ml/ branch;
(2) as reaction mixture absorption of N H no longer
3After, turn down logical NH
3Speed to 10～100ml/ branch, logical again NH
31.5 after～2.5 hours, stopped reaction;
(3) remove by filter ammonium chloride, and with organic solvent washing ammonium chloride 2-5 time;
(4) with the organic solvent that boils off in the filtrate;
(5) with decompression under 40～80/mmHg and 80 ℃-120 ℃, further boil off remaining solvent and most oligomer, obtain lurid silicon-nitrogen polymer, viscosity is 200～3000CP, productive rate 60～85%.
The selected chlorosilane of the present invention comprises: SiCl
4, HSiCl
3, Cl
3Si-(SiCl
2)
xAmong the Cl etc. any; Organochlorosilane comprises: Me
3SiCl, Me
2SiCl
2, MeSiCl
3, PhSiCl
3, ph
2SiCl
2, MeHSiCl
2, Me
2Si(OEt) Cl, MeSi(OEt) Cl
2Deng in any one or two kinds of; Also can be three kinds.Used organic solvent is any one or two kinds of mixed solvents in fat or aromatic hydrocarbon and the halides thereof, and is better with toluene or sherwood oil (60～120 ℃).
Since silicon-nitrogen polymer of the present invention at room temperature can be quickly with the organosilicon superpolymer in hydroxyl reaction, make it carry out non-catalytic crosslinking reaction, can stop and delay the thermal destruction of main chain in the polymkeric substance, thereby improved the heat resistance of organosilicon polymer, simultaneously, the effect that also has chain propagation agent.Therefore be used for the linking agent of organosilicon superpolymer with silicon-nitrogen polymer of the present invention, this polymeric crosslinker is used as silicon rubber, and the batch mixing of silicone resin gained can be used as aspects such as high temperature resistant potting compound, coated material, tackiness agent.Not only can improve its thermostability greatly, and significantly improve its mechanical property.As be used for the linking agent of room temperature-vulcanized methyl silicone rubber with silicon-nitrogen polymer, than the catalytic crosslinker with ethyl orthosilicate, organotin system, its cross-linked rubber heat resistance is brought up to 350 ℃ (Fig. 1) from 200 ℃.Through under 350 ℃ of sealing nitrogen aging 24 hours, mechanical property almost constant (table 1) was better than ethyl orthosilicate greatly, organotin catalytic crosslinker, silicone rubber adhesive adhesiveproperties also be greatly improved (table 2)
* TS-tensile strength (kg/cm
2)
* E-elongation (%)
* * H-hardness (Shao Shi)
Example 1
In there-necked flask, add 8.5g(0.05ml) SiCl
4, MeSiCl 285g(1.9mol)
3, Me 96.8g(0.75mol)
2SiCl
2With the sherwood oil (60～90 ℃) of 1500ml, under stirring and water-bath cooling, feed NH
3, logical NH
3Speed control do not have NH at tail gas
3Emit (about 16 hours), this moment, reaction was complete substantially, and suitably turned down logical NH
3Speed, logical again NH
3About two hours, get final product stopped reaction, remove by filter ammonium chloride, and with petroleum ether ammonium chloride three times, with distillation and underpressure distillation except that desolvating and oligomer.Get the silicon-nitrogen polymer of 152g.Productive rate 83%.Use the coulometric titration method, measuring nitrogen content is 27.78%, and calculated value is 28.44%.
Example 2
In there-necked flask, add 149.5g(1mol) MeSiCl
3, Me 64.5g(0.5mol)
2SiCl
2With the toluene of 800ml, react and handle by the operation of example 1 and reaction conditions, the silicon-nitrogen polymer of 84.5g, productive rate is 82%, nitrogen content 26.67%, (calculated value is 27.18%)
Example 3
In there-necked flask, add 6.8g(0.04mol) SiCl
4, MeSiCl 149.5g(1mol)
3, Me 103.2g(0.8mol)
2SiCl
2With the toluene of 1000ml, with the operation and the reaction conditions of example 1.Get the silicon-nitrogen polymer of 96g, productive rate 76%, nitrogen content 25.75%(calculated value 26.40%).
Example 4
In there-necked flask, add 10.1g(0.05mol) phSiCl
3, MeSiCl 134.5g(0.9mol)
3, Me 64.5g(0.5mol)
2SiCl
2With the toluene of 800ml,, get the silicon nitrogen polymer of 69.3g, productive rate 68%, nitrogen content 25.63%(calculated value 26.47%) with the operation steps and the reaction conditions of example 1.
Example 5
In beaker, be weighed into the silicon-nitrogen polymer that 100g107 silicon rubber (Beijing chemical industry two factories) and 5g example 2 make, mixing well the back outgased 3-5 minute under vacuum, pour into then in the mould of tetrafluoroethylene, the mensuration of thermal weight loss is carried out to cross-linked rubber in sulfuration back, and with use Si(OEl)
4Crosslinked cross-linked rubber contrast, its result such as Fig. 1.
Example 6
In beaker, be weighed into the silicon-nitrogen polymer that 100gSDL-1-41 sizing material (Sichuan two subsidiary factories of morning twilight chemical industry institute) and 5g example 2 make, mixing well the back outgased 5-10 minute under vacuum, pour into then in the mould of tetrafluoroethylene, obtain the thick sulfide film of 2mm after the sulfuration, and be cut into the test piece of 5 inferior bell shapes, wore out 24 hours under 350 ℃ sealing nitrogen, the mechanical property before and after cross-linked rubber is aging is as follows:
After wearing out before mechanical property is aging
Tensile strength (kg/cm
2) 13 12
Elongation (%) 240 250
Hardness (Shao Shi) 32 31
Example 7
In beaker, be weighed into 1152 silicone resin (two subsidiary factories of morning twilight chemical industry institute product) of 100g, 1gFe
2O
3With the silicon-nitrogen polymer linking agent of 0.5g, mix well the back coated on three 1 centimetre of wide copper sheets, in self-vulcanizing after 48 hours, the thick silicone resin film of 0.01～0.05mm that forms at copper sheet.The stove of then these copper sheets being put into 300 ℃ wore out 1000 hours, observed not cracking of silicone resin film.
Description of drawings:
Fig. 1 cross-linked rubber thermogravimetric curve
△ 250℃ Si（OEt）
4
■ 200℃ Si（OEt）
4
● 350 ℃ of silicon nitrogen linking agents
▲ 380 ℃ of silicon nitrogen linking agents
Claims (8)
1, a kind of silicon-nitrogen polymer is characterized in that the general formula of described polymkeric substance is:
Wherein R=Me, ph, Vi, OR, H,
n=1～3，
m=5～1000，
X=1～10
2, a kind of synthetic method of silicon-nitrogen polymer as claimed in claim 1 is characterized in that described method steps is as follows:
(1) get chlorosilane 0～20%(mol) and organochlorosilane 80～100%(mol) and be dissolved in the dry organic solvent of crossing, consumption of organic solvent is 2-6 a times of reactant consumption (weight), under stirring and water-bath cooling, feeds NH
3, speed 40～250ml/ branch;
(2) as reaction mixture absorption of N H no longer
3After, turn down logical NH
3Speed to 10～100ml/ branch, logical again NH
31.5 after～2.5 hours, stopped reaction;
(3) filter to remove ammonium chloride, and with organic solvent washing ammonium chloride 2-5 time;
(4) boil off organic solvent in the filtrate;
(5) under 40～80/mmHg and 80 ℃-120 ℃, boil off remaining solvent and oligomer.
3, the synthetic method of silicon-nitrogen polymer as claimed in claim 2 is characterized in that (1) described chlorosilane is SiCl
4, HSiCl
3, Cl
3Si-(SiCl
2)
xAmong-the Cl any.
4, the synthetic method of silicon-nitrogen polymer as claimed in claim 2 is characterized in that (1) described organochlorosilane is Me
3SiCl, Me
2SiCl
2, MeSiCl
3, PhSiCl
3, MeSiCl
2, Me
2Si(OEt) Cl, MeSi(OEt) Cl
2In any one or two kinds of.
5, the synthetic method of silicon-nitrogen polymer as claimed in claim 2 is characterized in that (1) described organochlorosilane is Me
3SiCl, Me
2SiCl
2, MeSiCl
3, PhSiCl
3, Me
2SiCl
2, Me
2Si(OEt) Cl, MeSi(OEt) Cl
2In any three kinds.
6, the synthetic method of silicon-nitrogen polymer as claimed in claim 2 is characterized in that described organic solvent is any or the two kinds of mixed solvents in fat or aromatic hydrocarbon and the halides thereof.
7, as claim 2, the synthetic method of 6 described silicon-nitrogen polymers is characterized in that described organic solvent is better with toluene or sherwood oil.
8, silicon-nitrogen polymer as claimed in claim 1 can be used as the organosilicon polymer linking agent, and it is used for silicon rubber, and the batch mixing of silicone resin gained can be used as resistant to elevated temperatures potting compound, coated material and tackiness agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93117929A CN1038136C (en) | 1993-09-30 | 1993-09-30 | Silicon-nitrogen polymer and synthesizing method and usage thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93117929A CN1038136C (en) | 1993-09-30 | 1993-09-30 | Silicon-nitrogen polymer and synthesizing method and usage thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1101055A true CN1101055A (en) | 1995-04-05 |
| CN1038136C CN1038136C (en) | 1998-04-22 |
Family
ID=4992219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93117929A Expired - Lifetime CN1038136C (en) | 1993-09-30 | 1993-09-30 | Silicon-nitrogen polymer and synthesizing method and usage thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1038136C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376711B (en) * | 2007-08-28 | 2011-08-31 | 中国科学院化学研究所 | High temperature resistant organosilicon adhesive, special silicon nitrogen polymer therefore and preparation |
| CN102399447A (en) * | 2011-09-19 | 2012-04-04 | 中国科学院化学研究所 | Non-cohesive high temperature resistant organic silicon sealant and preparation method thereof |
| CN102516774A (en) * | 2011-12-07 | 2012-06-27 | 中国科学院过程工程研究所 | Preparation method of modified silicon resin matrix and application of the modified silicon resin matrix |
| CN103193814A (en) * | 2013-04-02 | 2013-07-10 | 中国科学院化学研究所 | Silicon-nitrogen compound as well as preparation method and application thereof |
| CN103872412A (en) * | 2014-03-13 | 2014-06-18 | 苏州科茂电子材料科技有限公司 | Jacket of radiofrequency coaxial cable |
| CN103951981A (en) * | 2014-05-05 | 2014-07-30 | 中国科学院化学研究所 | Phosphorus-silicon polymer-containing flame-retardant room-temperature vulcanized silicone rubber composition and preparation method thereof |
| CN107474733A (en) * | 2017-08-18 | 2017-12-15 | 泰山医学院 | The synthetic method of polysilazane Ceramic precursor resin and a kind of antiradar coatings |
| CN109553777A (en) * | 2018-11-09 | 2019-04-02 | 中国科学院化学研究所 | A kind of room temperature curing agent of organosilicon material resistant to high temperature, preparation method and application |
| CN109593464A (en) * | 2018-11-09 | 2019-04-09 | 中国科学院化学研究所 | A kind of organic silicon rubber coating of room curing and high temperature resistant, preparation method and application |
| CN111892712A (en) * | 2020-07-24 | 2020-11-06 | 天鼎联创密封技术（北京）有限公司 | Flexible graphite-silicon nitrogen polymer elastic material and preparation method thereof |
| WO2022111288A1 (en) * | 2020-11-30 | 2022-06-02 | 北京宇航系统工程研究所 | Weather-resistant silazane rubber with three-dimensional network structure and preparation method therefor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03170533A (en) * | 1989-11-30 | 1991-07-24 | Tonen Corp | Polysilazane and its preparation |
| JPH0798865B2 (en) * | 1991-10-25 | 1995-10-25 | 信越化学工業株式会社 | Ceramics manufacturing method |
-
1993
- 1993-09-30 CN CN93117929A patent/CN1038136C/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376711B (en) * | 2007-08-28 | 2011-08-31 | 中国科学院化学研究所 | High temperature resistant organosilicon adhesive, special silicon nitrogen polymer therefore and preparation |
| CN102399447A (en) * | 2011-09-19 | 2012-04-04 | 中国科学院化学研究所 | Non-cohesive high temperature resistant organic silicon sealant and preparation method thereof |
| CN102399447B (en) * | 2011-09-19 | 2013-05-22 | 中国科学院化学研究所 | Non-cohesive high temperature resistant organic silicon sealant and preparation method thereof |
| CN102516774A (en) * | 2011-12-07 | 2012-06-27 | 中国科学院过程工程研究所 | Preparation method of modified silicon resin matrix and application of the modified silicon resin matrix |
| CN103193814A (en) * | 2013-04-02 | 2013-07-10 | 中国科学院化学研究所 | Silicon-nitrogen compound as well as preparation method and application thereof |
| CN103872412A (en) * | 2014-03-13 | 2014-06-18 | 苏州科茂电子材料科技有限公司 | Jacket of radiofrequency coaxial cable |
| CN103951981A (en) * | 2014-05-05 | 2014-07-30 | 中国科学院化学研究所 | Phosphorus-silicon polymer-containing flame-retardant room-temperature vulcanized silicone rubber composition and preparation method thereof |
| CN107474733A (en) * | 2017-08-18 | 2017-12-15 | 泰山医学院 | The synthetic method of polysilazane Ceramic precursor resin and a kind of antiradar coatings |
| CN107474733B (en) * | 2017-08-18 | 2020-01-31 | 山东第一医科大学(山东省医学科学院) | Synthesis method of polysilazane ceramic precursor resin and wave-absorbing coatings |
| CN109553777A (en) * | 2018-11-09 | 2019-04-02 | 中国科学院化学研究所 | A kind of room temperature curing agent of organosilicon material resistant to high temperature, preparation method and application |
| CN109593464A (en) * | 2018-11-09 | 2019-04-09 | 中国科学院化学研究所 | A kind of organic silicon rubber coating of room curing and high temperature resistant, preparation method and application |
| CN109553777B (en) * | 2018-11-09 | 2020-07-14 | 中国科学院化学研究所 | Room-temperature curing agent of high-temperature-resistant organosilicon material, preparation method and application |
| CN111892712A (en) * | 2020-07-24 | 2020-11-06 | 天鼎联创密封技术（北京）有限公司 | Flexible graphite-silicon nitrogen polymer elastic material and preparation method thereof |
| WO2022111288A1 (en) * | 2020-11-30 | 2022-06-02 | 北京宇航系统工程研究所 | Weather-resistant silazane rubber with three-dimensional network structure and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1038136C (en) | 1998-04-22 |
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Expiration termination date: 20130930 Granted publication date: 19980422 |