CN1066164C - Polyfluoro-phosphazene and producing process thereof - Google Patents
Polyfluoro-phosphazene and producing process thereof Download PDFInfo
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- CN1066164C CN1066164C CN94107056A CN94107056A CN1066164C CN 1066164 C CN1066164 C CN 1066164C CN 94107056 A CN94107056 A CN 94107056A CN 94107056 A CN94107056 A CN 94107056A CN 1066164 C CN1066164 C CN 1066164C
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- polyfluoro
- phosphonitrile
- phosphazene
- phosphonitrilic chloride
- rubber
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Abstract
The present invention discloses polyfluoro-phosphonitrile as inorganic fluorine rubber and a manufacturing method thereof. The present invention uses phosphonitrilic chloride as a raw material, and a fluoric reaction is carried out between a fluorating agent and the phosphonitrilic chloride to obtain fluoro phosphonitrile which is linearly polymerized to obtain the linear polyfluoro-phosphonitrile; the value of the molecular formula of the polyfluoro-phosphonitrile is taken as 450 to 140*10<4>. The linear polyfluoro-phosphonitrile can be made into reticular polyfluoro-phosphonitrile under the action of a crosslinking agent.
Description
The present invention relates to the viton field, relate in particular to a kind of manufacture method of inorganic fluorine rubber-polyfluoro-phosphazene,
General rubber is generally natural rubber and synthetic rubber in the prior art, and this two classes rubber all belongs to organic rubber.They are aging at oxytolerant at least, anti-ozone ageing, and it is relatively poor that performances such as flame resistivity a kind of, and particularly thermotolerance is generally not enough, and it can't be applied in hot environment.
" preparation of Experiment of Polymer Chemistry chamber " the 127th page that Science Press publishes in November, 1981 discloses a kind of inorganic rubber that is polymerized by phosphonitrilic chloride, though it is the ideal elastomerics, and very stable below 300 ℃, but because facile hydrolysis is restricted its practical application.
Purpose of the present invention is exactly the manufacture method that a kind of inorganic rubber-polyfluoro-phosphazene is provided at above-mentioned the deficiencies in the prior art, the polyfluoro-phosphazene that obtains not only has the character of conventional rubber, remedy natural rubber and elastomeric deficiency and inferior position on the performances such as, anti-ozone ageing aging in thermotolerance, oxytolerant, and its water-tolerant, thereby overcome phosphonitrilic chloride polyrubber facile hydrolysis and the difficulty that is difficult to practical application.
Technical scheme of the present invention is: a kind of manufacture method of line style polyfluoro-phosphazene, comprise operations such as monomer preparation, polymerization, its key is: be raw material with the phosphonitrilic chloride, carry out fluoro-reaction with fluorizating agent and phosphonitrilic chloride and obtain the fluoro phosphonitrile, again the fluoro phosphonitrile is carried out linear polymerization and promptly get the line style polyfluoro-phosphazene, described fluorizating agent is antimony trifluoride or antimony trifluoride and antimony pentachloride, and polymeric reaction condition is that temperature is 300～350 ℃, and pressure is 15kg/cm
2, pH value is 1～4.
The present invention is improved water resistance owing to the chlorine that has replaced with fluorine in the inorganic rubber phosphonitrilic chloride at all.Products obtained therefrom of the present invention is facile hydrolysis not, thereby has solved a depolymerization difficult problem that causes because of hydrolysis, and it not only has the character of conventional rubber, and aspects such as, anti-ozone ageing aging in thermotolerance, oxytolerant, flame resistivity, photostabilization and anti-resistance to air loss also have superperformance.In addition, compare its manufacturing cost with organic rubber very low for products obtained therefrom of the present invention.
The invention will be further described below in conjunction with embodiment.
The present invention is raw material (preparation of phosphonitrilic chloride is referring to " preparation of Experiment of Polymer Chemistry chamber " the 129th page) with the phosphonitrilic chloride, or be raw material preparation phosphonitrilic chloride earlier with phosphorus pentachloride and ammonium chloride, replace preparation fluoro phosphonitrile with fluorine again, carry out linear polymerization at last and the line style polyfluoro-phosphazene.
1, the preparation of phosphonitrilic chloride:
450 gram phosphorus pentachlorides are dissolved in 1200 milliliters of exsiccant symmetric tetrachloroethanes, add the dry ammonium chloride of crossing of 140 grams, refluxed about 12 hours, on the condensation mouth of pipe, place monochlor(in)ate calcium pipe then.After the thing cooling to be mixed, leach unreacted ammonium chloride, residuum is distillated solvent under 50～60 ℃ of negative pressure, remove oily matter and residual solvent again and promptly obtain phosphonitrilic chloride.This moment, products therefrom was cyclic tripolymer and tetrameric mixture, by Crystallization Separation, used 50% washing with alcohol again, can obtain the cyclic trimer phosphonitrilic chloride.
Reaction formula is:
2, the preparation of fluoro phosphonitrile:
With the cyclic trimer phosphonitrilic chloride under normal temperature, normal pressure with fluorizating agent such as antimony trifluoride or antimony pentafluoride effect, preparation fluoro phosphonitrile.Also can add antimony pentachloride in the above-mentioned fluorizating agent is catalyzer.
If with hydrofluoric acid is that fluorizating agent should be at 3～5kg/cm
2Under the pressure hydrofluoric acid contacted also with phosphonitrilic chloride with steam condition and can obtain the fluoro phosphonitrile.
3, the preparation of line style polyfluoro-phosphazene:
With the fluoro phosphonitrile produced at 300～350 ℃, about 15kg/cm
2Pressure is reaction down,
The polymerization degree n of line style polyfluoro-phosphazene is 450～140 * 10
4For the requirement of different n value, can when reaction, satisfy by middle control.Concrete operations are: under above-mentioned reaction conditions, the reactant pH value is controlled in 1～4, determines the reaction times by measuring product degree of polymerization or molecular weight, when the polymerization degree reaches institute's required value, adjust PH＞4, i.e. stopped reaction.For example, obtain the polymerization degree (mean value) and be 100,000 or 500,000 line style polyfluoro-phosphazene, the fluoro phosphonitrile that makes by 1,2 methods can be carried out polymerization by above-mentioned polymeric reaction condition, the while tracking and measuring polymerisate polymerization degree (measuring method is measured with the macromolecular compound polymerization degree), when the polymerization degree is 100,000 or 500,000, adjust PH＞4 or be alkalescence that promptly to get the polymerization degree be 100,000 or 500,000 line style polyfluoro-phosphazene.
The line style polyfluoro-phosphazene has many-sided purposes.Wherein can be made into high temperature resistantly than the low polymerization degree product, wear-resistant paint, higher degrees of polymerization product can be made into particularly high-temperature resistant rubber material of various rubber items.
4, the line style polyfluoro-phosphazene that makes of the present invention can also be made netted polyfluoro-phosphazene as intermediate under the effect of linking agent:
Molecular weight can be in room temperature, meta-acid environment form sulfide below 60,000 in the presence of linking agent and catalyzer such as tetraethoxy and dibutyl two lauric acid and a small amount of superoxide, this base polymer can natural arbitrarily moulding, many elastomeric materials as fields such as electron tube, aviation, automobile, steamers can use in-50～250 ℃ of scopes and not lose its rubber property.
Molecular weight more than 60,000 must moulding in shaper, detailed process is: count by weight, get 100 parts of line style polyfluoro-phosphazenes, 10～20 parts of silane coupling agents (the Wuhan University chemical plant produces), 10 parts of fluorosilicones, 30～50 parts of white carbon blacks and 2～4 parts of sulphur, after mixing at 170 ℃, 8kg/cm
2Under reacted 30 minutes, be warmed up to again 175 ℃ the reaction moulding in 4 hours.
The Specifeca tion speeification of netted polyfluoro-phosphazene: brittle point-68 ℃, second-order transition temperature-66 ℃, hardness 35～90, compression set (149 ℃, 70 hours) 10～50%, elongation at break 75～250%.5, the salient features of polyfluoro-phosphazene that makes with the present invention and conventional rubber relatively
| Salient features | Polyfluoro-phosphazene | Natural rubber (polyisoprene) | Natural synthetic rubber (polyisoprene) |
| Tensile strength (kg/cm 2) extension (%) maximum operation (service) temperature (℃) temperature limit commonly used (℃) the anti-air-tightness of the anti-ozone aging flame resistance of resistance to water oxygen resistence light resistance | 250～300 600～850 400 350 is good good | 250～300 650～900 120 70～80 is good bad | 200～300 600～900 120 70～80 is good bad |
As can be seen from the table, the polyfluoro-phosphazene that the present invention makes not only has the characteristic of conventional rubber, and has superperformance at aspects such as ageing-resistant, high temperature resistant, water tolerance, flame resistivitys.Both can be used as the high temperature resistant elastomeric material that waits particular requirement, also can be used as the equivalent material of conventional rubber.
Claims (1)
1, a kind of manufacture method of line style polyfluoro-phosphazene, comprise operations such as monomer preparation, polymerization, it is characterized in that: be raw material with the phosphonitrilic chloride, carry out fluoro-reaction with fluorizating agent and phosphonitrilic chloride and obtain the fluoro phosphonitrile, again the fluoro phosphonitrile is carried out linear polymerization and promptly get the line style polyfluoro-phosphazene, fluorizating agent is antimony trifluoride or antimony trifluoride and antimony pentachloride, and polymeric reaction condition is 300～350 ℃ of temperature, pressure 15kg/cm
2, pH value 1～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94107056A CN1066164C (en) | 1994-06-10 | 1994-06-10 | Polyfluoro-phosphazene and producing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94107056A CN1066164C (en) | 1994-06-10 | 1994-06-10 | Polyfluoro-phosphazene and producing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1114325A CN1114325A (en) | 1996-01-03 |
| CN1066164C true CN1066164C (en) | 2001-05-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94107056A Expired - Fee Related CN1066164C (en) | 1994-06-10 | 1994-06-10 | Polyfluoro-phosphazene and producing process thereof |
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| CN (1) | CN1066164C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109613785B (en) * | 2018-09-29 | 2022-03-25 | 北京计算科学研究中心 | Application of poly (difluorophosphazene) |
| CN109852242A (en) * | 2018-12-12 | 2019-06-07 | 北京化工大学 | A kind of hydrophobic oil resistant flame-retardant anti-corrosion multifunctional coating and preparation method |
| CN112490583A (en) * | 2020-11-27 | 2021-03-12 | 河北金力新能源科技股份有限公司 | Polyethylene diaphragm with high diaphragm breaking temperature and preparation method and application thereof |
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1994
- 1994-06-10 CN CN94107056A patent/CN1066164C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1114325A (en) | 1996-01-03 |
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