CN113045758B - Preparation method of high-tensile halogen-free flame-retardant polyphosphazene elastomer - Google Patents
Preparation method of high-tensile halogen-free flame-retardant polyphosphazene elastomer Download PDFInfo
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- CN113045758B CN113045758B CN202110451634.9A CN202110451634A CN113045758B CN 113045758 B CN113045758 B CN 113045758B CN 202110451634 A CN202110451634 A CN 202110451634A CN 113045758 B CN113045758 B CN 113045758B
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- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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Abstract
The invention discloses a preparation method of a high-tensile halogen-free flame-retardant polyphosphazene elastomer, which adopts the technical scheme that dimethyl-silicone glycol reacts with sodium hydride at the temperature of 0-60 ℃ to prepare dimethyl-silicone glycol monosodium, and then dimethyl-silicone glycol monosodium and sodium phenolate are mixed to react with linear polydichlorophosphazene to prepare the novel dimethyl-hydroxy-siloxy-phenoxy polyphosphazene elastomer through substitution reaction. The synthesis process of the dimethyl hydroxyl siloxy-phenoxy polyphosphazene elastomer is simple and convenient, and is convenient for industrial production; the dimethyl hydroxyl siloxy-phenoxy polyphosphazene elastomer is green and environment-friendly, has good flame retardant property and tensile property, and has good application prospect in the aspect of being used as a high-tensile halogen-free intrinsic flame retardant elastic material.
Description
The technical field is as follows:
the high-tensile halogen-free flame-retardant polyphosphazene elastomer prepared by the invention has good tensile property and flame retardant property, does not contain halogen elements, meets the requirement of environmental protection, has simple and convenient production process, and has industrial production and application prospects.
Background art:
polyphosphazene is an inorganic macromolecule with phosphorus and nitrogen alternately arranged on a main chain, and the polymer has an intrinsic flame retardant property due to the synergistic flame retardant property of phosphorus and nitrogen elements on the main chain. Two chlorine atoms connected with phosphorus atoms on the main chain of the polydichlorophosphazene have high reactivity and are easy to be substituted by nucleophilic reagents, and the polyphosphazene derivatives with different functions can be obtained by changing the type, the proportion and the like of the polyphosphazene side groups.
Current research reports on polyphosphazene elastomers focus primarily on haloalkoxy polyphosphazenes, phenoxy-substituted polyphosphazenes, and alkoxy-substituted polyphosphazenes, such as: the trifluoroethoxy and octafluoropentyloxy mixed substituted polyphosphazene elastomer prepared from the kudzu, slow waves and the like has excellent flame retardance and thermal stability, and the material has an application prospect in the field of aerospace, but does not meet the requirement of environmental protection because the material contains halogen elements; zhang wenhao, etc. prepares phenoxy substituted polyphosphazene and phenoxy alkoxy mixed substituted polyphosphazene, the phenoxy substituted polyphosphazene is affected by the steric hindrance of benzene ring and has poor tensile property, and the phenoxy alkoxy mixed substituted polyphosphazene has poor flame retardant property.
The polyphosphazene elastomer with good flame retardant property and tensile property is prepared, does not contain halogen elements, meets the environmental protection requirement, and has industrial production and application prospects.
The invention content is as follows:
in order to overcome the defects of the prior art, the invention provides a novel method for preparing a high-tensile halogen-free flame-retardant polyphosphazene elastomer, and successfully synthesizes the high-tensile halogen-free flame-retardant polyphosphazene elastomer.
The technical scheme adopted by the invention is as follows: firstly, dimethyl-silicone glycol reacts with sodium hydride to prepare dimethyl-silicone glycol monosodium, and then the dimethyl-silicone glycol monosodium and sodium phenolate are mixed and subjected to substitution reaction with linear polydichlorophosphazene to prepare the novel dimethyl-hydroxy-siloxy-phenoxy polyphosphazene elastomer. The process for synthesizing the dimethyl hydroxyl siloxy-phenoxy polyphosphazene elastomer is simple and convenient, and is convenient for industrial production. The synthesized dimethyl hydroxyl siloxy-phenoxy polyphosphazene elastomer does not contain halogen elements, and the lateral group phenoxy and the dimethyl hydroxyl siloxy can synergistically improve the flame retardant property of polyphosphazene products; the flexibility of the side group dimethyl hydroxyl siloxy is better, and the side group dimethyl hydroxyl siloxy can be used for improving the tensile property of the polyphosphazene elastomer by cooperating with the main chain.
A preparation method of a high-tensile halogen-free flame-retardant polyphosphazene elastomer is characterized by comprising the following steps:
a. preparation of a dimethyl-silanediol monosodium nucleophile: taking sodium hydride and dimethyl silicon glycol with the molar ratio of 1;
b. preparation of dimethylhydroxystiloxy-phenoxy polyphosphazene: taking linear polydichlorophosphazene and nucleophilic reagent with the molar ratio of 1;
c. product post-treatment: and pouring the reaction solution into deionized water to separate out a product and remove sodium chloride, washing the product with n-heptane to remove organic matters such as dimethyl-silicone glycol and the like, and drying the washed product in a vacuum drying oven at 40-60 ℃ for 24-48h to obtain the novel gray-white dimethyl-hydroxy-siloxy-phenoxy polyphosphazene elastomer.
Compared with the prior art, the invention has the following advantages: the synthesis process of the product of the dimethyl hydroxyl siloxy-phenoxy polyphosphazene elastomer is simple, and the final product can be obtained through mixed substitution reaction, washing and drying. The phosphorus and nitrogen contained in the main chain of the dimethyl hydroxyl siloxy-phenoxy polyphosphazene elastomer can play a role in cooperative flame retardance, the phenoxy and the dimethyl hydroxyl siloxy on the side chain can also improve the flame retardance of the polyphosphazene in a cooperative manner, the dimethyl hydroxyl siloxy-phenoxy polyphosphazene elastomer without halogen elements meets the environmental protection requirement, the LOI value is 27.8-30.5%, and the UL-94 vertical combustion reaches the V-0 level; the product has good flexibility of the side group dimethyl hydroxyl siloxy, can improve the tensile property of the polyphosphazene elastomer by cooperating with the main chain, and has the elongation at break of 348 to 1914 percent. The dimethyl hydroxyl siloxy-phenoxy polyphosphazene elastomer synthesized by the invention is environment-friendly, has good flame retardant property and tensile property, and has good application prospect when being used as a high-tensile halogen-free intrinsic flame retardant elastic material.
The specific implementation mode is as follows:
in order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples, and the examples should not be construed as limiting the scope of the present invention.
Example 1
Taking 0.0431mol of sodium hydride and 0.0431mol of dimethyl-silicon glycol (the mol ratio is 1; taking 0.431mol of linear polydichlorophosphazene and 0.862mol of nucleophile (mol ratio is 1; pouring the reaction solution into deionized water to separate out a product and remove sodium chloride, washing the product with n-heptane to remove dimethyl silicon glycol, and drying the washed product in a vacuum drying oven at 40 ℃ for 48 hours to obtain an off-white dimethyl hydroxyl siloxane-phenoxy polyphosphazene elastomer; the product has the characteristics that the UL-94 vertical burning grade reaches the V-0 grade, the limiting oxygen index LOI is 30.2 percent, and the elongation at break reaches 348 percent.
Example 2
Taking 0.1724mol of sodium hydride and 0.1724mol of dimethyl silicon glycol (the mol ratio is 1; taking 0.431mol of linear polydichlorophosphazene and 0.862mol of nucleophile (mol ratio is 1; pouring the reaction solution into deionized water to separate out a product and remove sodium chloride, washing the product with n-heptane to remove dimethyl silicon glycol, and drying the washed product in a vacuum drying oven at 60 ℃ for 24 hours to obtain an off-white dimethyl hydroxyl siloxane-phenoxy polyphosphazene elastomer; the product has the characteristics that the UL-94 vertical burning grade reaches the V-0 grade, the limiting oxygen index LOI is 29.4 percent, and the elongation at break reaches 941 percent.
Embodiment 3
Taking 0.3448mol of sodium hydride and 0.3448mol of dimethyl silicon glycol (the mol ratio is 1; taking 0.431mol of linear polydichlorophosphazene and 0.862mol of nucleophile (mol ratio is 1; pouring the reaction solution into deionized water to separate out a product and remove sodium chloride, washing the product with n-heptane to remove dimethyl silicon glycol, and drying the washed product in a vacuum drying oven at 60 ℃ for 24 hours to obtain an off-white dimethyl hydroxyl siloxane-phenoxy polyphosphazene elastomer; the product has the characteristics that the UL-94 vertical burning grade reaches the V-0 grade, the limiting oxygen index LOI is 27.8 percent, and the breaking elongation reaches 1914 percent.
Claims (3)
1. A preparation method of a high-tensile halogen-free flame-retardant polyphosphazene elastomer is characterized by comprising the following steps:
preparation of a dimethyl-silanediol monosodium nucleophile: taking sodium hydride and dimethyl silicon glycol according to a molar ratio of 1;
preparation of dimethylhydroxystiloxy-phenoxy polyphosphazene: taking linear polydichlorophosphazene and nucleophilic reagent with the molar ratio of 1;
product post-treatment: and pouring the reaction liquid into deionized water to separate out a product, removing sodium chloride, washing the product with n-heptane to remove dimethyl silicon glycol, and drying the washed product in a vacuum drying oven at 40-60 ℃ for 24-48h to obtain the offwhite dimethylhydroxysiloxy-phenoxy polyphosphazene elastomer.
2. The method for preparing high-tensile halogen-free flame-retardant polyphosphazene elastomer according to claim 1, wherein the structural formula of the prepared dimethyl hydroxy siloxy-phenoxy polyphosphazene elastomer is as follows:
3. the method for preparing high-tensile halogen-free flame-retardant polyphosphazene elastomer according to claim 1, wherein the prepared dimethyloxysiloxy-phenoxy polyphosphazene elastomer has a limiting oxygen index LOI of 27.8-30.2%, a UL-94 vertical burning level of V-0 and an elongation at break of 348-1914%.
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