CN105622946A - Preparation method of ceramic precursor polyborosilazane PBSZ resin - Google Patents
Preparation method of ceramic precursor polyborosilazane PBSZ resin Download PDFInfo
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- CN105622946A CN105622946A CN201610157562.6A CN201610157562A CN105622946A CN 105622946 A CN105622946 A CN 105622946A CN 201610157562 A CN201610157562 A CN 201610157562A CN 105622946 A CN105622946 A CN 105622946A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/486—Boron containing organic compounds, e.g. borazine, borane or boranyl
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Abstract
The invention discloses a preparation method of ceramic precursor polyborosilazane PBSZ resin, and relates to a preparation method of resin. The method comprises the steps of firstly performing hydrobration reaction of dichloromethylvinylsilane, preparing diborane through sodium borohydride and boron trifluoride diethyl etherate solution, and leading the diborane into a hydroboration reactor through nitrogen loading to be reacted with the dichloromethylvinylsilane; then performing ammonolysis reaction, preventing hydrolysis of the hydroborated dichloromethylvinylsilane sensitive to water and air through a systematic desensitization, to guarantee the smooth proceed of the reaction and achieve the purpose of improving the quality and yield of low polymer products, and enabling ammonolysis reaction to be more completely and thoroughly through a repeated ammonolysis reaction method, so as to achieve the purpose of uniformity of low polymer molecular weight; enabling low polymer molecules to be connected with one another to form high polymer through a catalytic thermal polymerization method during thermochemical polymerization, so as to achieve the purpose of obtaining high molecular weight PBSZ resin (0.2 million).
Description
Technical field
The present invention relates to the preparation method of a kind of resin, particularly relate to the preparation method of a kind of ceramic forerunner PVDF hollow fiber membrane PBSZ resin.
Background technology
A kind of novel high-performance stupalith of SiBCN pottery conduct is than SiC, Si3N4, the ternary system pottery such as the binary system such as BN pottery and SiCN, SiCO there is more excellent high-temperature stability, the research such as Riedel finds that the high-temperature stability of SiBCN pottery can reach 2000 DEG C. Therefore SiBCN pottery can be applicable to the fields such as advanced aerospacecraft structure unit, high-temperature engine, turbine, atomic reactor wall, pyrostat.
The high-performance of SiBCN pottery comes from being uniformly distributed of composition ceramic element. Presoma conversion method is the effective ways of preparation SiBCN pottery. Presoma conversion method is obtained by chemical synthesis process to can be passed through the precursor polymer that thermal treatment is converted into stupalith, utilizes good rheological, the workability of polymkeric substance, carries out forming process, and thermo-cracking obtains advanced ceramics material afterwards. The presoma PVDF hollow fiber membrane of root SiBCN pottery according to the literature mainly contains following several types: silicon base borazine derivative, silicon base dichloride boron ammonia/amine hydrolysis products and by the crosslinked poly-silazane of C-B-C. But can reaching the Si of molecular level, B, C, being uniformly distributed of N element, the preparation method of the PVDF hollow fiber membrane that can reach again higher molecular weight has no report.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of ceramic forerunner PVDF hollow fiber membrane PBSZ resin, the present invention adopts homemade diborane gas as hydroborating agents, this reagent has the reactive behavior higher than borane complex, avoids being separated of product and organic ligand simultaneously. The molecular weight (Mw) of product reaches 200,000, presents white solid form, can be dissolved in the organic solvents such as dehydrated alcohol, tetrahydrofuran (THF), chloroform.
It is an object of the invention to be achieved through the following technical solutions:
A preparation method for ceramic forerunner PVDF hollow fiber membrane PBSZ resin, described method comprises following process:
First hydroborating agents is homemade diborane, there is very high reactive behavior, method is entered by slow for boron trifluoride ether solution pump in the diethylene glycol dimethyl ether solution of sodium borohydride, reacting under normal temperature and namely obtain diborane, the diborane of generation imports to through nitrogen load and makes methyl ethylene dichlorosilane generation hydroboration in hydroboration device; Secondly the ammonolysis reaction of hydroboration product carries out desensitization process before starting in advance, i.e. first the air in removal system and water vapor, and method is that through drying installation, high pure nitrogen is entered reactor, then discharges through other device, keeps 0.5��1 hour; Secondly fill process not with air contact, method enters reactor under suction function successively by through the normal hexane of rectifying and the hydroboration product of methyl ethylene dichlorosilane; Keeping reaction system and the isolation of air and water vapor in last whole reaction process, method is that reaction carries out until system is aobvious alkaline at 0 DEG C, and remains the circulation of ammonia; The preparation method of diborane and introduction method, slow for boron trifluoride ether solution pump is entered in the diethylene glycol dimethyl ether solution of sodium borohydride by preparation method, is obtained by reacting diborane under normal temperature; Introduction method is, with nitrogen load, diborane imports hydroboration device; Borine generating unit, hydroboration device and linking conduit height are airtight, cause significant loss in order to avoid diborane leaks and blast; The solvent used in reaction process must carry out rectifying and processed, to remove the minor amount of water wherein contained; The product of preliminary ammonolysis reaction is carried out two ammonolysis reactions, and reaction repeated ensure that the abundant ammonia solution of Si-Cl key, obtains the oligopolymer of molecular weight equilibrium; The catalytic thermal polyreaction of oligopolymer makes oligopolymer become superpolymer, and molecular weight reaches 200,000.
The preparation method of described a kind of ceramic forerunner PVDF hollow fiber membrane PBSZ resin, the solvent of described hydroboration is tetrahydrofuran (THF).
Advantage and the effect of the present invention be:
1, the present invention adopts homemade diborane gas as hydroborating agents, and this reagent has the reactive behavior higher than borane complex, avoids being separated of product and organic ligand simultaneously.
Reaction raw materials had both been carried out effective protection by the nitrogen load diborane hydroboration method that 2, the present invention selects, and homemade diborane is imported hydroboration device hydroboration carries out smoothly to ensure simultaneously.
3, the present invention adopts two ammonolysis reaction processes, and what make that the ammonolysis reaction of hydroborated methyl ethylene dichlorosilane carries out is more abundant.
4, the present invention adopt catalytic thermal polymerization process to make oligopolymer and ring-type small molecules are crosslinked becomes macromole.
5, reaction solvent for use normal hexane and tetrahydrofuran (THF) are after rectifying, it is possible to recycling, the rate of recovery reaches more than 85%. 6, the technical solution used in the present invention so that the molecular weight (Mw) of product reaches 200,000, presents white solid form, can be dissolved in the organic solvents such as dehydrated alcohol, tetrahydrofuran (THF), chloroform.
Accompanying drawing explanation
Fig. 1 is methyl ethylene dichlorosilane hydroboration setting drawing of the present invention;
Fig. 2 is systematic desensitization ammonolysis process schematic diagram of the present invention;
Fig. 3 is catalytic thermal polymerization schematic diagram of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Nitrogen load diborane hydroboration method: lead in advance in reaction unit into pure nitrogen, removal system air and water vapor, utilize low speed nitrogen gas stream that obtained diborane is imported hydroboration device afterwards, with methyl ethylene dichlorosilane generation hydroboration wherein.
Repeat ammonolysis process: filtered by the mixed solution of ammonolysis reaction, remove solid by-product ammonium chloride, and make liquid reenter reaction unit, repeat ammonolysis reaction, until reaction solution is weakly alkaline.
Catalytic thermal polymerization: ammonolysis reaction liquid is carried out catalytic thermal polymerization, makes it high molecular, ring-type small molecules and chain shape oligopolymer are cross-linked becomes macromole.
The hydroboration process of methyl ethylene dichlorosilane:
Borine producer and hydroboration device are passed through tubes connection, opens nitrogen, in borine producer, add the diethylene glycol dimethyl ether solution of sodium borohydride, hydroboration device adds the tetrahydrofuran solution of methyl ethylene dichlorosilane.
Entering in borine producer by boron trifluoride ether solution by the slow pump of volume pump, under normal temperature, reaction produces diborane, imports in hydroboration device through nitrogen load, makes methyl ethylene dichlorosilane generation hydroboration.
After reaction terminates, de-remove and reclaim tetrahydrofuran (THF), the hydroboration product pump of methyl ethylene dichlorosilane is entered storage tank 2.
Carry out ammonolysis reaction process:
1, ammonolysis reaction process
As shown in Figure 1, reactor 1 being provided with electric power and stirs 4, and be connected with moisture eliminator 3 with storage tank 2, while, is connected with vacuum pump 7 through resorber 6 with reflux tower 5, filtration unit 8 with 11 bottom valve j be connected with the opening for feed of storage tank 2.
First, high pure nitrogen enters reactor 1 through moisture eliminator 3, discharges through device 5,6,7, takes away the air in 1 and water vapour simultaneously, keep 0.5��1 hour.
2nd, stop logical nitrogen, start vacuum pump 7, open the connection valve h with 2, make the hydroboration methyl ethylene dichlorosilane in 2 and normal hexane enter reactor 1 under suction function successively.
3rd, close 7, lead to into ammonia, start motor 4, keep reaction system 0 DEG C simultaneously, until material is weakly alkaline in still, a large amount of white solid ammonium chloride occurs in 1.
2, ammonolysis reaction process is repeated
Bottom valve j by 1 opens, filtration unit 8 put into by reaction mass, after filtering solid by-product ammonium chloride, filtrate through storage tank 2 again pump enter reactor 1, repeat above-mentioned reaction process, final oligopolymer is released via bottom valve i, enter distillation tower 9, after desolvation for subsequent use by being pumped into storage tank 10, after one batch of production terminates, the normal hexane pump of recovery is entered reactor, normal hexane boiling it is heated in still, steam condensation in reflux tower 5, pass back in still, realize the flushing to reactor 1, clean waste liquid to discharge through valve J via after bottom valve j after filtration device 8 filtration, then the production of next batch is started.
4.3 catalytic thermal polymerization processes
As shown in Figure 2, polymerization reaction kettle 11 being provided with electric power and stirs 14, and be connected with drying tower 13 with storage tank 10, storage tank 12 is connected simultaneously.
In storage tank 12, pump enters the suspension liquid of normal hexane and catalyzer, and high pure nitrogen enters reactor 11 through drying tower 13, discharges through valve m. By the suspension liquid in the oligopolymer in storage tank 10 and storage tank 12 respectively pump enter polymeric kettle 11, heat the temperature 90 DEG C making reactor 11 reach required, heat polymerization is started after solvent evaporated, to still, viscosity reaches certain value, material is released to, container, material turns into white solid after being cooled to normal temperature from bottom through valve p. Measure molecular weight with light scattering method and reach 200,000.
Claims (2)
1. the preparation method of a ceramic forerunner PVDF hollow fiber membrane PBSZ resin, it is characterised in that, described method comprises following process:
First hydroborating agents is homemade diborane, there is very high reactive behavior, method is entered by slow for boron trifluoride ether solution pump in the diethylene glycol dimethyl ether solution of sodium borohydride, reacting under normal temperature and namely obtain diborane, the diborane of generation imports to through nitrogen load and makes methyl ethylene dichlorosilane generation hydroboration in hydroboration device; Secondly the ammonolysis reaction of hydroboration product carries out desensitization process before starting in advance, i.e. first the air in removal system and water vapor, and method is that through drying installation, high pure nitrogen is entered reactor, then discharges through other device, keeps 0.5��1 hour; Secondly fill process not with air contact, method enters reactor under suction function successively by through the normal hexane of rectifying and the hydroboration product of methyl ethylene dichlorosilane; Keeping reaction system and the isolation of air and water vapor in last whole reaction process, method is that reaction carries out until system is aobvious alkaline at 0 DEG C, and remains the circulation of ammonia; The preparation method of diborane and introduction method, slow for boron trifluoride ether solution pump is entered in the diethylene glycol dimethyl ether solution of sodium borohydride by preparation method, is obtained by reacting diborane under normal temperature; Introduction method is, with nitrogen load, diborane imports hydroboration device; Borine generating unit, hydroboration device and linking conduit height are airtight, cause significant loss in order to avoid diborane leaks and blast; The solvent used in reaction process must carry out rectifying and processed, to remove the minor amount of water wherein contained; The product of preliminary ammonolysis reaction is carried out two ammonolysis reactions, and reaction repeated ensure that the abundant ammonia solution of Si-Cl key, obtains the oligopolymer of molecular weight equilibrium; The catalytic thermal polyreaction of oligopolymer makes oligopolymer become superpolymer, and molecular weight reaches 200,000.
2. the preparation method of a kind of ceramic forerunner PVDF hollow fiber membrane PBSZ resin according to claim 1, it is characterised in that, the solvent of described hydroboration is tetrahydrofuran (THF).
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| CN201610157562.6A CN105622946A (en) | 2016-03-21 | 2016-03-21 | Preparation method of ceramic precursor polyborosilazane PBSZ resin |
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| CN201610157562.6A CN105622946A (en) | 2016-03-21 | 2016-03-21 | Preparation method of ceramic precursor polyborosilazane PBSZ resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000262A (en) * | 2016-07-01 | 2016-10-12 | 明辉大秦（上海）环保科技有限公司 | Industrial starch reaction device |
| CN110066397A (en) * | 2019-04-25 | 2019-07-30 | 中国人民解放军国防科技大学 | Series-parallel synthesis method of polyborosilazane |
Citations (3)
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| CN1800098A (en) * | 2005-01-05 | 2006-07-12 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of Si-B-C-N amorphous ceramic material for high temperature sensing device |
| CN101492295A (en) * | 2009-03-03 | 2009-07-29 | 北京航空航天大学 | Process for producing amorphous Si-B-C-N quaternionic ceramic forerunner matter and apparatus for producing the forerunner |
| CN104817701A (en) * | 2015-04-14 | 2015-08-05 | 沈阳化工大学 | Preparation method of polysilazane for preparation of SiCN nonoxide ceramic fibre |
-
2016
- 2016-03-21 CN CN201610157562.6A patent/CN105622946A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800098A (en) * | 2005-01-05 | 2006-07-12 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of Si-B-C-N amorphous ceramic material for high temperature sensing device |
| CN101492295A (en) * | 2009-03-03 | 2009-07-29 | 北京航空航天大学 | Process for producing amorphous Si-B-C-N quaternionic ceramic forerunner matter and apparatus for producing the forerunner |
| CN104817701A (en) * | 2015-04-14 | 2015-08-05 | 沈阳化工大学 | Preparation method of polysilazane for preparation of SiCN nonoxide ceramic fibre |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000262A (en) * | 2016-07-01 | 2016-10-12 | 明辉大秦（上海）环保科技有限公司 | Industrial starch reaction device |
| CN106000262B (en) * | 2016-07-01 | 2018-07-31 | 明辉大秦（上海）环保科技有限公司 | A kind of industrial starch reaction unit |
| CN110066397A (en) * | 2019-04-25 | 2019-07-30 | 中国人民解放军国防科技大学 | Series-parallel synthesis method of polyborosilazane |
| CN110066397B (en) * | 2019-04-25 | 2021-03-26 | 中国人民解放军国防科技大学 | Series-parallel synthesis method of polyborosilazane |
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Effective date of registration: 20170119 Address after: 201101 Shanghai City, Minhang District Xinlong Road No. 1111 Applicant after: Shanghai hope security equipment Co., Ltd. Address before: 110142 Shenyang economic and Technological Development Zone, Liaoning, No. 11 Applicant before: Shenyang University of Chemical Technology |
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Application publication date: 20160601 |
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