CN104072785B - A kind of dissaving polymer and preparation method thereof - Google Patents
A kind of dissaving polymer and preparation method thereof Download PDFInfo
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- CN104072785B CN104072785B CN201410246942.8A CN201410246942A CN104072785B CN 104072785 B CN104072785 B CN 104072785B CN 201410246942 A CN201410246942 A CN 201410246942A CN 104072785 B CN104072785 B CN 104072785B
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- 0 C*NS(C)(C(C)S(C)N(C)S(C)NS(C)(NC)NS(C)(C)C)NS(C)(C)C Chemical compound C*NS(C)(C(C)S(C)N(C)S(C)NS(C)(NC)NS(C)(C)C)NS(C)(C)C 0.000 description 1
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a kind of dissaving polymer and preparation method thereof, dichloromethyl vinyl silanes and borane dimethyl sulphide compound is reacted with certain proportion in certain solvent at a certain temperature and is obtained containing BC3The intermediate of structure, is subsequently adding a certain proportion of dichloromethyl vinyl silanes, and dichloro methyl silane and two sila azane of hexamethyl react to form polymer at a certain temperature, and finally decompression pumps small molecule at relatively high temperatures, obtains pure end-product.The characteristics of present invention has easy to operate, equipment requirement is low, is adapted to popularization and application.
Description
Technical field
The invention belongs to technical field of chemistry, is related to a kind of dissaving polymer and preparation method thereof, specifically, it is related to
Solvable Si-B-C-N dissaving polymer of a kind of normal temperature and preparation method thereof.
Background technology
Organic precursor method method is good because of its molecule designability, and crosslinking temperature is low, it is easy to machine-shaping, ceramic conversion cracking temperature
The features such as spending low and functional ceramic product, is the popular method for preparing now Si-B-C-N ceramic materials.Using containing double
The chlorosilane of key and borane complex occur after hydroboration obtains the intermediate product containing B structure, then with aminated compounds and
Intermediate reaction, ammonolysis obtain the ceramics that the polymer containing Si, B, C and N element sinters into and have high temperature resistant, anti-oxidant, corrosion resistant
The advantages of erosion, low-density, in the numerous areas extensive application prospect such as Aeronautics and Astronautics, the energy, machinery, traffic and metallurgy.So
And in existing document report, above-mentioned preparation method usually because the aminated compounds activity for selecting is too strong, the polymer for obtaining
It is insoluble not melt, both it is difficult to change its form and cause the limitation in processing method, it is also difficult to and other compounds uniformly mix
Disperse and limit range of application.
The content of the invention
It is an object of the invention to overcome the insoluble insoluble defect of Si-B-C-N precursors present in prior art, there is provided
A kind of dissaving polymer and preparation method thereof, by dichloromethyl vinyl silanes and borane dimethyl sulphide compound certain
At a temperature of reacted in certain solvent with certain proportion and obtain containing BC3The intermediate of structure, is subsequently adding a certain proportion of dichloro
Ethylene methacrylic base silane, dichloro methyl silane and two sila azane of hexamethyl react to form polymer at a certain temperature, finally
Decompression at relatively high temperatures pumps small molecule, obtains pure end-product.
Its concrete technical scheme is：
A kind of dissaving polymer, its structural formula is：
A kind of dissaving polymer and preparation method thereof, comprises the following steps：
Step a, the synthesis of intermediate product TDSB：In the case where argon gas and condition of ice bath is passed through in advance, burn to the single port of 250ml
Bottle, respectively with syringe by 3: 1 injection in molar ratio of dichloromethyl vinyl silanes and borane dimethylsulf iotade；Feed intake after finishing,
Allow ice cube to melt naturally, be slowly increased to room temperature；It is fierce to stir, react 24h；
Step b, the synthesis of dissaving polymer：In the case where argon gas and room temperature condition is led to, to the single-necked flask in step a,
A certain amount of dichloromethyl vinyl silanes, two sila azane of dichloro methyl silane and hexamethyl are injected separately into syringe；Note
Shoot away after finishing, be warming up to 60 DEG C, react 2h, then heat to 110 DEG C, react 12h, and collect the small molecule chemical combination being steamed out
Thing；It is last that 2h is reacted at 180 DEG C, and decompression pumps micromolecular compound, obtains dissaving polymer.
Further preferably,
In step a, the structural formula of intermediate product TDSB is
Further preferably, in step b synthesis of super branched polymer be PSBCN-1, TDSB used, dichloro methyl silane and six
The amount ratio of the material of two sila azane of methyl is 1: 5: 11；Synthesis of super branched polymer TDSB, dichloromethyl as used by PSBCN-2
Vinyl silanes, the amount ratio of the material of two sila azane of dichloro methyl silane and hexamethyl are 1: 1: 2: 9.
Further preferably, the dissaving polymer is PSBCN-1, dissolves in tetrahydrofuran, chloroform and toluene etc. organic
Solvent, structural formula is
Further preferably, the dissaving polymer is PSBCN-2, dissolves in tetrahydrofuran, chloroform and toluene etc. organic
Solvent, structural formula is
Compared with prior art, beneficial effects of the present invention are：
1) prepared by one kettle way, and easy to operate, equipment requirement is low；2) difficult detached ammonium salt, the by-product of generation will not be produced
Thing trim,ethylchlorosilane low boiling point, easily takes away, and the product purity for obtaining is very high；3) polymer for synthesizing is dissolved in four
The common solvents such as hydrogen furans, are not only advantageous to follow-up characterization test, are conducive to various processing methods such as solution-polymerized SBR, Er Qieke
Multifunctional material is prepared by solwution method blending with other compounds.
Specific embodiment
Technical scheme is described in more detail with reference to specific embodiment.
Embodiment 1, the synthesis of polymer P SBCN-1.
In the case where high-purity argon gas (purity 99.999%, similarly hereinafter) and condition of ice bath is passed through in advance, to the single-necked flask of 250ml
In, inject the dichloromethyl vinyl silanes and borane dimethylsulfide that 10.68g concentration is 2mol/L of 10.50g respectively with syringe
The tetrahydrofuran solution of ether.Feed intake after finishing, close gas valve, allow ice cube to melt naturally, be slowly increased to room temperature.Fiercely stir
Mix, after reaction 24h, reaction bulb is transferred to remain has in the oil bath pan of dimethicone.Open gas valve and be passed through argon gas, with note
After emitter is injected separately into the two sila azane of hexamethyl of the dichloro methyl silane and 44.18g of 14.47g, distilling apparatus is connected, after
Gas valve is closed after continuous ventilation 5min.Oil bath pot temperature is risen to into 60 DEG C, after reaction 2h, oil bath pot temperature 110 DEG C is risen to into,
Oil bath pot temperature, after steaming most of tetrahydrofuran and trim,ethylchlorosilane, is risen to 180 DEG C by reaction 12h, reacts 2h.Open
Gas valve is passed through high-purity argon gas, sheds distilling apparatus, beyond the Great Wall bottle stopper, closes gas valve.Ventilation nozzle in single-necked flask
Connect the vacuum plant with cold-trap.Vavuum pump is opened, and is pumped in pipeline after air, liquid nitrogen is poured into toward cold-trap, it is slow to open single
Gas valve on mouth flask, is kept for 180 DEG C, and decompression pumps small molecule, after about 2h, foam generation is there is no longer in reaction bulb,
Oil bath pan temperature control switch is closed, is allowed oil bath temperature to be down to less than 50 DEG C, is obtained faint yellow sticky oil product.Finally, close anti-
Breather valve on bottle is answered, vacuum plant is shed, and high-purity argon gas is passed through toward reaction bulb.
Jing is weighed and is obtained product 17.23g.Jing is measured, and number-average molecular weight Mn of product is 2900g/mol, weight average molecular weight
Mw is 4700g/mol, and polydispersity coefficient Mw/Mn is 1.614.
Embodiment 2, the synthesis of polymer P SBCN-2.
In the case where high-purity argon gas and condition of ice bath is passed through in advance, in the single-necked flask of 250ml, injected with syringe respectively
Tetrahydrofuran solution of the dichloromethyl vinyl silanes and 10.71g concentration of 10.63g for the borane dimethylsulf iotade of 2mol/L.Throw
After material is finished, gas valve is closed, is allowed ice cube to melt naturally, is slowly increased to room temperature.It is fierce to stir, after reaction 24h, by reaction bulb
Being transferred to surplus has the oil bath pan of dimethicone.Open gas valve and be passed through high-purity argon gas, 5.96g is injected separately into syringe
Dichloro methyl silane, the dichloromethyl vinyl silanes of 3.70g and 32.38g two sila azane of hexamethyl after, connect distillation
Device, closes gas valve after continuing ventilation 5min.Oil bath pot temperature is risen to into 60 DEG C, after reaction 2h, by oil bath pot temperature liter
To 110 DEG C, 12h is reacted, after steaming most of tetrahydrofuran and trim,ethylchlorosilane, oil bath pot temperature 180 DEG C is risen to into, reacted
2h.Open gas valve and be passed through high-purity argon gas, shed distilling apparatus, beyond the Great Wall bottle stopper, close gas valve.In single-necked flask
Ventilation nozzle connects the vacuum plant with cold-trap.Vavuum pump is opened, is pumped in pipeline after air, is poured liquid nitrogen toward cold-trap into, slowly
The gas valve in single-necked flask is opened, is kept for 180 DEG C, decompression pumps small molecule, after about 2h, foam is there is no longer in reaction bulb
Produce, close oil bath pan temperature control switch, allow oil bath temperature to be down to less than 50 DEG C, obtain faint yellow sticky oil product.Finally, close
Breather valve on reaction bulb is closed, vacuum plant is shed, and high-purity argon gas is passed through toward reaction bulb.
Jing is weighed and is obtained product 13.53g.Jing is measured, and number-average molecular weight Mn of product is 2700g/mol, weight average molecular weight
Mw is 4600g/mol, and polydispersity coefficient Mw/Mn is 1.702.
Presently preferred embodiments of the present invention is the foregoing is only, is merely illustrative for invention, and it is nonrestrictive.
Those skilled in the art understanding, can carry out many changes in the spirit and scope limited by invention claim to which, change,
It is even equivalent, but fall within protection scope of the present invention.
Claims (6)
1. a kind of dissaving polymer, it is characterised in that its structural formula is：
2. a kind of preparation method of dissaving polymer, it is characterised in that comprise the following steps：
Step a, the synthesis of intermediate product TDSB：In the case where argon gas and condition of ice bath is passed through in advance, to the single-necked flask of 250ml, point
Not with syringe by 3: 1 injection in molar ratio of dichloromethyl vinyl silanes and borane dimethylsulf iotade；Feed intake after finishing, allow ice cube
Naturally melt, be slowly increased to room temperature；It is fierce to stir, react 24h；
Step b, the synthesis of dissaving polymer：In the case where argon gas and room temperature condition is led to, to the single-necked flask in step a, with note
Emitter is injected separately into a certain amount of dichloromethyl vinyl silanes, two sila azane of dichloro methyl silane and hexamethyl；Inject
Bi Hou, is warming up to 60 DEG C, reacts 2h, then heats to 110 DEG C, reacts 12h, and collects the micromolecular compound being steamed out；Most
React 2h afterwards at 180 DEG C, and decompression pumps micromolecular compound, obtains dissaving polymer.
3. the preparation method according to claim 2 dissaving polymer, it is characterised in that
In step a, the structural formula of intermediate product TDSB is
4. the preparation method according to claim 2 dissaving polymer, it is characterised in that synthesis of super branched polymer in step b
For PSBCN-1, TDSB used, the amount ratio of the material of two sila azane of dichloro methyl silane and hexamethyl are 1: 5: 11；Synthesis is super
Branched polymer TDSB, dichloromethyl vinyl silanes, two sila nitrogen of dichloro methyl silane and hexamethyl as used by PSBCN-2
The amount ratio of the material of alkane is 1: 1: 2: 9.
5. the preparation method according to claim 4 dissaving polymer, it is characterised in that the dissaving polymer is PSBCN-
1, the organic solvents such as tetrahydrofuran, chloroform and toluene are dissolved in, structural formula is
6. the preparation method according to claim 4 dissaving polymer, it is characterised in that the dissaving polymer is PSBCN-
2, the organic solvent of tetrahydrofuran, chloroform and toluene is dissolved in, structural formula is
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| CN106752937B (en) * | 2016-12-06 | 2019-05-14 | 广州弘海化工科技有限公司 | A kind of low-temperature setting superhigh temperature resistant coating, preparation method and applications |
| CN114276149A (en) * | 2022-01-17 | 2022-04-05 | 西北工业大学 | Hafnium-containing silicon-boron-carbon-nitrogen high-temperature wave-absorbing ceramic and preparation method and application thereof |
| CN114560708B (en) * | 2022-03-15 | 2023-04-18 | 深圳市基克纳科技有限公司 | Method for converting porous ceramic by utilizing self-reaction pore-forming polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504269A (en) * | 2011-10-12 | 2012-06-20 | 中国人民解放军国防科学技术大学 | Preparation method of polyborosilazane precursor |
| CN102701771A (en) * | 2012-05-28 | 2012-10-03 | 东华大学 | Preparation method for SiBNC fiber/SiBNC composite material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504269A (en) * | 2011-10-12 | 2012-06-20 | 中国人民解放军国防科学技术大学 | Preparation method of polyborosilazane precursor |
| CN102701771A (en) * | 2012-05-28 | 2012-10-03 | 东华大学 | Preparation method for SiBNC fiber/SiBNC composite material |
Non-Patent Citations (2)
| Title |
|---|
| SiBNC体系陶瓷先驱体的研究进展;唐云等;《高分子材料科学与工程》;20080430;第24卷(第4期);23-27 * |
| 聚硼硅氮烷陶瓷前驱体分子结构设计和合成;孔杰等;《化学进展》;20071130;第19卷(第11期);1971-1799 * |
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