CN1114325A - Polyfluoro-phosphazene and producing process thereof - Google Patents
Polyfluoro-phosphazene and producing process thereof Download PDFInfo
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- CN1114325A CN1114325A CN94107056A CN94107056A CN1114325A CN 1114325 A CN1114325 A CN 1114325A CN 94107056 A CN94107056 A CN 94107056A CN 94107056 A CN94107056 A CN 94107056A CN 1114325 A CN1114325 A CN 1114325A
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- phosphazene
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Abstract
The method for producing polyfluoro-phosphazene, an inorganic fluoro rubber, includes such steps as fluoric reaction of phosphazene chloride with fluorinating agent to obtain fluoro-phosphazene, and linear polymerization to obtain polyfluoro-phosphazene. Under the action of crosslinking agent, it may become netted polyfluoro-phosphazene.
Description
The invention relates to the field of fluororubber, in particular to inorganic fluororubber-polyfluoro phosphazene and a preparation method thereof.
The rubber commonly used in the prior art is generally natural rubber and synthetic rubber, and the two types of rubber belong to organic rubber. They are poor in at least one of oxidation aging resistance, ozone aging resistance, flame resistance and the like, and particularly, the heat resistance is generally insufficient, so that they cannot be applied in a high-temperature environment.
On page 127 of the laboratory preparation of Polymer chemistry published by scientific Press in 11.1, page 127, an inorganic rubber is disclosed which is polymerized from phosphonitrile chloride, and although it is an ideal elastomer and stable at temperatures below 300 ℃, it is subject to hydrolysis, which limits its practical application.
The invention aims to provide an inorganic rubber-polyfluoro phosphazene and a manufacturing method thereof aiming at the defects of the prior art, the obtained polyfluoro phosphazene not only has the properties of general rubber, but also makes up the defects and disadvantages of natural rubber and synthetic rubber in the performances of heat resistance, oxygen aging resistance, ozone aging resistance and the like, and has good water resistance, thereby overcoming the difficulty that the phosphonitrile chloride polymer rubber is easy to hydrolyze and difficult to be practically applied.
The technical scheme of the invention is as follows: a linear polyfluoro phosphazene having a molecular formula
The value of n is 450-140 multiplied by 104。
The reticular polyfluoro phosphazene is prepared by taking the linear polyfluoro phosphazene as an intermediate product through a crosslinking reaction.
The method for preparing the linear polyfluoro phosphazene comprises the procedures of monomer preparation, polymerization and the like, and is characterized in that: phosphonitrile chloride is used as a raw material, a fluorination agent and the phosphonitrile chloride are subjected to fluorination reaction to obtain fluoro phosphonitrile, and then the fluoro phosphonitrile is subjected to linear polymerization.
The fluorinating agent is antimony trifluoride or antimony trifluoride and antimony pentachloride.
The polymerization conditions are a temperature of 300 to 350 ℃ and a pressure of 15kg/cm2The pH value is 1-4.
The invention replaces chlorine in inorganic rubber phosphonitrile chloride with fluorine, thus fundamentally improving water resistance and being difficult to hydrolyze, thereby solving the problem of depolymerization caused by hydrolysis. It not only has the properties of general rubber, but also has good properties in the aspects of heat resistance, oxidation and ageing resistance, ozone and ageing resistance, flame resistance, light resistance, air tightness resistance and the like, and in addition, compared with organic rubber, the preparation cost of the rubber is very low.
The present invention will be described in more detail with reference to examples.
The linear polyfluoro phosphazene is prepared by taking phosphonitrile chloride as a raw material (see page 129 of high molecular chemistry laboratory preparation), or by taking phosphorus pentachloride and ammonium chloride as raw materials, preparing phosphonitrile chloride, then replacing with fluorine to prepare fluoro phosphazene, and finally performing linear polymerization.
1. Preparation of phosphonitrile chloride:
450 g of phosphorus pentachloride is dissolved in 1200 ml of dry, symmetrical tetrachloroethane, 140 g of dried ammonium chloride are added, reflux is carried out for about 12 hours, and then a calcium chloride tube is placed on the mouth of the condenser tube. And after the mixture is cooled, filtering out unreacted ammonium chloride, distilling the residue at the negative pressure of 50-60 ℃ to obtain the solvent, and removing the oily matter and the residual solvent to obtain the phosphonitrile chloride. The product obtained in the reaction is a mixture of cyclic trimer and tetramer, and the cyclic trimer phosphonitrile chloride can be obtained by crystallization separation and then washing with50% ethanol.
The reaction formula is as follows:
2. preparation of fluorinated phosphazene:
the cyclic trimer phosphonitrile chloride reacts with fluorinating agent such as antimony trifluoride or antimony pentafluoride at normal temperature and normal pressure to prepare the fluoro phosphonitrile. Antimony pentachloride can be added into the fluorinating agent as a catalyst.
If hydrofluoric acid is used as the fluorinating agent, it should be 3-5 kg/cm2The fluorinated phosphazenes can also be obtained by contacting hydrofluoric acid in the vapor state under pressure with phosphonitrile chloride.
3. Preparation of linear polyfluoro phosphazene:
the prepared fluophosphazene is at 300-350 ℃ and about 15kg/cm2Reacting under pressure to obtain the linear polyfluoro phosphazene.
The polymerization degree n of the linear polyfluoro phosphazene is 450-140 multiplied by 104. For different n value requirements, it can be satisfied by central control during the reaction. The specific operation is as follows: under the reaction conditions, the PH value of the reactant is controlled within 1-4, the reaction time is determined by measuring the polymerization degree or molecular weight of the product, and when the polymerization degree reaches the required value, the reaction is stopped by adjusting the PH to be more than 4. For example, to obtain a linear polyfluorophosphazene having a degree of polymerization (average value) of 10 ten thousand or 50 ten thousand, the fluorophosphazene prepared by the methods 1 and 2 may be polymerized under the above-mentioned polymerization conditions, and the polymerization degree of the polymerization product may be determined by tracking (the determination method is the same as that of the polymerization degree of the polymer compound), and when the polymerization degree is 10 ten thousand or 50 ten thousand, the pH is adjusted to be greater than 4 or basic, to obtain a linear polyfluorophosphazene having a polymerization degree of 10 ten thousand or 50 ten thousandPolyfluoro phosphazenes.
Linear polyfluoro phosphazenes have many applications. The product with lower polymerization degree can be made into high temperature resistant and wear resistant coating, and the product with higher polymerization degree can be made into various rubber products, in particular high temperature resistant rubber materials.
4. The reticular polyfluoro phosphazene can be prepared by taking linear polyfluoro phosphazene as an intermediate under the action of a cross-linking agent:
the polymer can be randomly and naturally molded, is used as a rubber material in the fields of electron tubes, aviation, automobiles, ships and the like, and can be used within the temperature range of-50-250 ℃ without losing the rubber characteristics.
The method comprises the following steps of (1) forming a whisker with a molecular weight of more than sixty thousand in a shaping mold: according to parts by weight, 100 parts of linear polyfluoro phosphazene, 10-20 parts of silane coupling agent (produced by Wuhan university chemical plant), 10 parts of fluorosilicone, 30-50 parts of white carbon black and 2-4 parts of sulfur are mixed and then are mixed at 170 ℃ and 8kg/cm2The reaction is carried out for 30 minutes, and the temperature is raised to 175 ℃ for 4 hours for forming.
The main performance parameters of the reticular polyfluoro phosphazene are as follows: the brittle point is-68 ℃, the glass transition temperature is-66 ℃, the hardness is 35-90, the compression deformation (149 ℃, 70 hours) is 10-50%, and the elongation at break is 75-250%.
5. Comparison of the principal Properties of polyfluoro phosphazenes with general purpose rubbers
| Main performance | Polyfluoro phosphazenes | Natural rubber (polyisoprene) | Synthetic natural rubber (polyisoprene) |
| Tensile Strength (kg/cm)2) Elongation (%) Maximum service temperature (. degree. C.) Temperature limit (. degree. C.) in general Water resistance Resistance to oxygen Light resistance Ozone aging resistance Flame resistance Air tightness resistance | 250～300 600～850 400 350 Good wine Good wine Good wine Good wine Good wine Good wine | 250～300 650～900 120 70～80 Superior food Good wine Bad quality Bad quality Bad quality Bad quality | 200～300 600～900 120 70～80 Good wine Good wine Bad quality Bad quality Bad quality Bad quality |
As can be seen from the table, the rubber composition of the present invention not only has the characteristics of general-purpose rubber, but also has good performance in aging resistance, high temperature resistance, water resistance, flameresistance, etc. The rubber can be used as a rubber material with special requirements such as high temperature resistance and the like, and can also be used as a substitute material of general rubber.
Claims (5)
1. A linear polyfluoro phosphazene having the formula:
the value of n is 450-140 multiplied by 104。
2. A reticulated polyfluoro phosphazene crosslinked from the linear polyfluoro phosphazene of claim 1.
3. A method of making a linear polyfluoro phosphazene of claim 1 comprising the steps of monomer preparation, polymerization, and the like, wherein: phosphonitrile chloride is used as a raw material, chlorination reaction is carried out on the phosphonitrile chloride by using a fluorinating agent to obtain fluoro phosphonitrile, and linear polymerization is carried out on the fluoro phosphonitrile.
4. The manufacturing method according to claim 3, characterized in that: the fluorinating agent is antimony trifluoride or antimony trifluoride and antimony pentachloride.
5. The manufacturing method according to claim 3 or 4, characterized in that: the polymerization reaction conditions are that the temperature is 300-350 ℃ and the pressure is 15kg/cm2And the pH value is 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 |
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| Publication Number | Publication Date |
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| CN1114325A true CN1114325A (en) | 1996-01-03 |
| CN1066164C CN1066164C (en) | 2001-05-23 |
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| 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109613785A (en) * | 2018-09-29 | 2019-04-12 | 北京计算科学研究中心 | A kind of application of double fluorine phosphonitriles |
| 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 |
-
1994
- 1994-06-10 CN CN94107056A patent/CN1066164C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109613785A (en) * | 2018-09-29 | 2019-04-12 | 北京计算科学研究中心 | A kind of application of double fluorine phosphonitriles |
| 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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| Publication number | Publication date |
|---|---|
| CN1066164C (en) | 2001-05-23 |
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