CN105694455B - A kind of material modified preparation method of polyphenylene sulfide - Google Patents

Abstract

The invention relates to a preparation method of a polymer material, in particular to a preparation method of a polyphenylene sulfide modified material, and belongs to the technical field of polymer materials. In the present invention, polyphenylene sulfide is subjected to sulfonation treatment, sulfonic acid group (‑SO ₃ H) is grafted, and then the sulfonic acid group of polyphenylene sulfide and the amine group (‑NH ₂ ) to carry out an acid-base reaction to modify polyphenylene sulfide to obtain a polyphenylene sulfide modified material. Compared with ordinary polyphenylene sulfide, the polyphenylene sulfide modified material prepared by the method of the present invention has flow behavior at a temperature above 45°C, and has the advantages of high fluidity at low temperature, good chemical and dimensional stability, etc., And it can reduce the melt spinning viscosity of polyphenylene sulfide fiber. The preparation process of the invention is simple and environment-friendly, and opens up a new approach in the preparation of polyphenylene sulfide with low viscosity and high fluidity.

Description

A kind of preparation method of polyphenylene sulfide modified material

technical field

The invention relates to a preparation method of a polymer material, in particular to a preparation method of a polyphenylene sulfide modified material, and belongs to the technical field of polymer materials.

Background technique

Polyphenylene sulfide has been favored in industrial applications because of its excellent heat resistance, corrosion resistance, flame retardancy, and dimensional stability. However, the strong rigidity of the polyphenylene sulfide molecular chain makes its brittleness and impact toughness inferior. High, the impact resistance is not strong, and there are also disadvantages such as unstable viscosity during high-temperature melting, easy oxidative cross-linking and not easy to process and form, which limits the processing of polyphenylene sulfide to a certain extent. At present, the research on polyphenylene sulfide focuses on fiber reinforced polyphenylene sulfide, inorganic filler modified polyphenylene sulfide, and blended modified polyphenylene sulfide, but inorganic filler modified polyphenylene sulfide will make it The mechanical strength is reduced, and the cost of fiber reinforced polyphenylene sulfide is high, and the strength of composite fiber is also reduced. Blending modified polyphenylene sulfide will improve its mechanical properties, but the molding effect is not good, and the size is not good. Stablize.

At present, there have been many literature reports on reinforced modified polyphenylene sulfide. It has always been a difficulty and a hot spot in the research of polyphenylene sulfide to obtain functional polyphenylene sulfide materials while keeping its mechanical properties unchanged. The modified polyphenylene sulfide prepared by the present invention has good fluidity at low temperature, which provides a new possibility for the processing and assembly of polyphenylene sulfide. There is great utility in illiquidity. In previous studies, processing defects such as high melt viscosity and poor fluidity of polyphenylene sulfide at high temperatures made it difficult to process polyphenylene sulfide. The innovation of this invention lies in the development of polyphenylene sulfide with good fluidity at low temperature. Preparation and modification technology of ether modified materials.

Chinese patent CN201110347014.7, the disclosure date is June 20, 2012, the title of the invention is "a silicone graft modified polyphenylene sulfide material and its preparation method", which is the polyphenylene sulfide powder, acetyl chloride , anhydrous AlCl ₃ powder in dichloromethane or dichloroethane to obtain acetylated polyphenylene sulfide modified powder, and then under the protection of nitrogen, acetylated modified polyphenylene sulfide, amino-containing organosilicon Reaction of solid, acetic acid and molecular sieve in anhydrous toluene or ethanol at 70-110°C for 0.5-36 hours to obtain organosilicon-modified polyphenylene sulfide. The reaction process of the invention is cumbersome, the reaction cycle is long, and the prepared polyphenylene sulfide has poor overall performance.

Chinese patent CN201310560625.9, the disclosure date is May 20, 2015, the title of the invention is "a silicone toughened and modified polyphenylene sulfide material and its preparation method", which is the coupling agent KH-560 Branches on the surface of SiO ₂ particles to prepare nano-SiO ₂ with hydrophobic surface, and then use suspension grafting and silane crosslinking technology to graft organosilicon monomers on polyphenylene sulfide, and then form a formula system with other additives through twin-screw The extruder blends and extrudes, and obtains a reinforced and toughened modified polyphenylene sulfide material after stretching, cooling, and pelletizing. Chinese patent CN201410723796.3, the disclosure date is March 4, 2015, and the title of the invention is "a preparation method of modified polyphenylene sulfide composite masterbatch", which uses titanium-silicon dioxide added to polyphenylene sulfide fibers Nano material, sodium dodecylbenzene sulfonate, heated, melted, mixed, dispersed, homogenized and extruded by a twin-screw extruder to produce a modified polyphenylene sulfide composite masterbatch, which strengthens the polyphenylene sulfide material strength, toughness. The strength and toughness of the polyphenylene sulfide modified by the above patents have been improved, but the final prepared polyphenylene sulfide can only flow under high temperature conditions above 280°C, and cannot flow under low temperature conditions.

Chinese patent CN201510101069.8, the publication date is May 27, 2015, the title of the invention is "a modified polyphenylene sulfide material suitable for 3D printing and its preparation method and application", which discloses a The modified polyphenylene sulfide material, the invention uses simple mixing and extrusion technology to modify polyphenylene sulfide, the processing temperature of the modified polyphenylene sulfide is greatly reduced, but the molding device The melting temperature has not been significantly lowered, and the toughness has been enhanced. The melting temperature of the polyphenylene sulfide prepared by the invention is about 220°C, which is much lower than that of general polyphenylene sulfide materials, but it is still not up to to below 100°C.

Chinese patent CN201510372128.5, the disclosure date is October 14, 2015, the title of the invention is "a modified polyphenylene sulfide and its preparation method", which is to weigh polyphenylene sulfide and nano-attapulgite by weight , glycerol, plastic powder, glass fiber, preservative, paraffin, hydrogen peroxide, ceramic powder and mica are stirred in a mixing equipment and heated to 80-120 ℃ semi-finished products; put the obtained semi-finished products into a twin-screw extruder to extrude out to obtain modified polyphenylene sulfide. The polyphenylene sulfide prepared by the invention has more excellent mechanical properties and greater elasticity, but the melting temperature of the polyphenylene sulfide is still relatively high.

Chinese patent CN200910108894.5, the disclosure date is January 6, 2010, the title of the invention is "a modified polyphenylene sulfide and its preparation method", which is polyphenylene sulfide, antioxidant, compatibilizer, Coupling agent, lubricant, glass fiber, etc. are mixed and extruded through a twin-screw extruder to obtain modified polyphenylene sulfide. Although the performance of the polyphenylene sulfide prepared by this invention has been improved, the processing temperature is still above 220° C., and the fluidity at high temperature has not been greatly improved.

At present, there are many methods for preparing high-performance polyphenylene sulfide, but the common method is to prepare functional polyphenylene sulfide through inorganic filling polyphenylene sulfide, organic compound blending modification, grafting and substitution reaction, which is characterized by processing consumption The time is long, the processing temperature is high, the fluidity is poor, and organic solvents are often used in the preparation reaction process, which is not conducive to environmental protection. At the same time, the processing and application of polyphenylene sulfide must be completed at high temperature. There is no literature report on the modification of polyphenylene sulfide. It is prepared as a polyphenylene sulfide material with flow characteristics under low temperature conditions.

Contents of the invention

Aiming at the problems existing in the above-mentioned technologies, the object of the present invention is to provide a preparation method of a polyphenylene sulfide modified material. To achieve the above object, the present invention is achieved through the following technical solutions:

A kind of preparation method of polyphenylene sulfide modified material, described preparation method is as follows:

a. Mix polyphenylene sulfide and chlorosulfonic acid with a particle size of 0.2-0.3 μm at a mass ratio of 1 to 50:100, and mechanically stir at 50°C for 24 hours to obtain a polyphenylene sulfide/chlorosulfonic acid mixture, then Wash the polyphenylene sulfide/chlorosulfonic acid mixed solution with deionized water until the filtrate pH=7 of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution to obtain preliminary sulfonated polyphenylene sulfide, and the obtained preliminary sulfonated polyphenylene sulfide After the phenylene sulfide was vacuum-dried at 70° C. for 12 hours, sulfonated polyphenylene sulfide with a particle size ranging from 10 to 50 μm was obtained.

b. Dissolve polyoxyethylene ether functionalized octadecadecyl tertiary amine in deionized water to prepare a water dispersion of polyoxyethylene ether functionalized octadecadecyl tertiary amine with a mass concentration of 10wt% to 50wt%, and sulfonated polyphenylene Add sulfide into deionized water, heat up to 70°C, and stir mechanically for 30 minutes to obtain an aqueous dispersion of sulfonated polyphenylene sulfide with a mass fraction of 5 wt%, and then disperse the water dispersion of polyoxyethylene ether functionalized octadecadec tertiary amine liquid and the aqueous dispersion of sulfonated polyphenylene sulfide are mixed according to the mass ratio, and the mass ratio of polyoxyethylene ether functionalized octadecyl tertiary amine to sulfonated polyphenylene sulfide is 0.5 to 1:1 to obtain sulfonated polyphenylene sulfide The mixed solution of phenylene sulfide/polyoxyethylene ether functionalized octadecadecium tertiary amine was mechanically stirred at a constant temperature at 70°C for 2 hours, then the mixed solution was dialyzed for 3 to 5 days, and the dialyzed liquid was taken out and dried under vacuum at 70°C. After drying for 24 hours, a polyphenylene sulfide modified material with fluidity at a temperature above 45° C. is obtained.

Due to the adoption of the above technical scheme, the preparation method of the polyphenylene sulfide modified material of the present invention has the following advantages:

In the present invention, polyphenylene sulfide is subjected to sulfonation treatment, and sulfonic _acid groups (-SO ₃ H) are grafted. ) to carry out an acid-base reaction to modify polyphenylene sulfide to obtain a polyphenylene sulfide modified material. Compared with ordinary polyphenylene sulfide, the polyphenylene sulfide modified material prepared by the method of the present invention has flow behavior at a temperature above 45°C, and has the advantages of high fluidity at low temperature, good chemical and dimensional stability, etc., And it can reduce the melt spinning viscosity of polyphenylene sulfide fiber. The polyphenylene sulfide modified material prepared by the invention has a simple preparation process and is environmentally friendly, and opens up a new approach in the method of preparing polyphenylene sulfide with low viscosity and high fluidity.

detailed description

The present invention will be described in further detail below in conjunction with specific examples.

A kind of preparation method of polyphenylene sulfide modified material, described preparation method is as follows:

a. Mix polyphenylene sulfide and chlorosulfonic acid with a particle size of 0.2-0.3 μm at a mass ratio of 1 to 50:100, and mechanically stir at 50°C for 24 hours to obtain a polyphenylene sulfide/chlorosulfonic acid mixture, then Wash the polyphenylene sulfide/chlorosulfonic acid mixed solution with deionized water until the filtrate pH=7 of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution to obtain preliminary sulfonated polyphenylene sulfide, and the obtained preliminary sulfonated polyphenylene sulfide After the phenylene sulfide was vacuum-dried at 70° C. for 12 hours, sulfonated polyphenylene sulfide with a particle size ranging from 10 to 50 μm was obtained.

b. Dissolve polyoxyethylene ether functionalized octadecadecyl tertiary amine in deionized water to prepare a water dispersion of polyoxyethylene ether functionalized octadecadecyl tertiary amine with a mass concentration of 10wt% to 50wt%, and sulfonated polyphenylene Add sulfide into deionized water, heat up to 70°C, and stir mechanically for 30 minutes to obtain an aqueous dispersion of sulfonated polyphenylene sulfide with a mass fraction of 5 wt%, and then disperse the water dispersion of polyoxyethylene ether functionalized octadecadec tertiary amine liquid and the aqueous dispersion of sulfonated polyphenylene sulfide, and the mass ratio of polyoxyethylene ether functionalized octadecyl tertiary amine to sulfonated polyphenylene sulfide is 0.5-1:1 to obtain sulfonated polyphenylene sulfide/ The mixed solution of polyoxyethylene ether functionalized octadecadecyl tertiary amine was mechanically stirred at a constant temperature at 70°C for 2 hours, and then dialyzed for 3 to 5 days. The polyphenylene sulfide modified material having fluidity under the condition of temperature above 45° C. is obtained.

specific embodiment

Example 1

a. Surface sulfonation of polyphenylene sulfide: Take 10g of polyphenylene sulfide powder, add it to 100g of chlorosulfonic acid, and mechanically blend and stir at 50°C for 24h; then wash the polyphenylene sulfide/chlorosulfonic acid with deionized water Mixed solution until the filtrate of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution pH = 7 to obtain preliminary sulfonated polyphenylene sulfide, and vacuum-dry the obtained preliminary sulfonated polyphenylene sulfide at 70°C for 12 hours to obtain sulfonated polyphenylene sulfide Polyphenylene sulfide.

b. Preparation of polyphenylene sulfide modified material: 0.75g of polyoxyethylene ether functionalized octadecyl tertiary amine was dissolved in deionized water to prepare polyoxyethylene ether functionalized octadecyl tertiary amine with a mass concentration of 10wt%. Water dispersion: take 1.5g of the sulfonated polyphenylene sulfide powder prepared in step 1 and disperse it into 30ml of deionized water, stir continuously and heat up to 70°C, then add the polyoxyethylene ether functionalized 18-tert-polyoxyethylene ether prepared above Aqueous dispersion of amines, to obtain a mixed dispersion of sulfonated polyphenylene sulfide/polyoxyethylene ether functionalized octadecadecyl tertiary amine, after stirring mechanically at a constant temperature at 70°C for 2 hours, the sulfonated polyphenylene sulfide/polyoxyethylene Put the mixed solution of ether-functionalized octadecadecyl tertiary amine into a dialysis bag for dialysis for 3 to 5 days, take out the dialysis liquid and dry it, and dry it in vacuum at 70°C for 24 hours to obtain Fluid polyphenylene sulfide modified material.

Example 2

a. Surface sulfonation of polyphenylene sulfide: Take 10g of polyphenylene sulfide powder, add it to 100g of chlorosulfonic acid, and mechanically blend and stir at 50°C for 24h; then wash the polyphenylene sulfide/chlorosulfonic acid with deionized water Mixed solution until the filtrate of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution pH = 7 to obtain preliminary sulfonated polyphenylene sulfide, and vacuum-dry the obtained preliminary sulfonated polyphenylene sulfide at 70°C for 12 hours to obtain sulfonated polyphenylene sulfide Polyphenylene sulfide.

b. Preparation of polyphenylene sulfide modified material: 0.75g of polyoxyethylene ether functionalized octadecyl tertiary amine was dissolved in deionized water to prepare polyoxyethylene ether functionalized octadecyl tertiary amine with a mass concentration of 20wt%. Water dispersion: take 1.5g of the sulfonated polyphenylene sulfide powder prepared in step 1 and disperse it into 30ml of deionized water, stir continuously and heat up to 70°C, then add the polyoxyethylene ether functionalized 18-tert-polyoxyethylene ether prepared above Aqueous dispersion of amines, to obtain a mixed dispersion of sulfonated polyphenylene sulfide/polyoxyethylene ether functionalized octadecadecyl tertiary amine, after stirring mechanically at a constant temperature at 70°C for 2 hours, the sulfonated polyphenylene sulfide/polyoxyethylene Put the mixed dispersion of ether-functionalized octadecadecyl tertiary amine into a dialysis bag for dialysis for 3 to 5 days, take it out and dry it, and vacuum dry it at 70°C for 24 hours to obtain fluidity at a temperature above 45°C. Polyphenylene sulfide modified material.

Example 3

a. Surface sulfonation of polyphenylene sulfide: Take 10g of polyphenylene sulfide powder, add it to 100g of chlorosulfonic acid, and mechanically blend and stir at 50°C for 24h; then wash the polyphenylene sulfide/chlorosulfonic acid with deionized water Mixed solution until the filtrate of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution pH = 7 to obtain preliminary sulfonated polyphenylene sulfide, and vacuum-dry the obtained preliminary sulfonated polyphenylene sulfide at 70°C for 12 hours to obtain sulfonated polyphenylene sulfide Polyphenylene sulfide.

b. Preparation of polyphenylene sulfide modified material: 0.75g of polyoxyethylene ether functionalized octadecyl tertiary amine was dissolved in deionized water to prepare polyoxyethylene ether functionalized octadecyl tertiary amine with a mass concentration of 30wt%. Water dispersion: take 1.5g of the sulfonated polyphenylene sulfide powder prepared in step 1 and disperse it into 30ml of deionized water, stir continuously and heat up to 70°C, then add the polyoxyethylene ether functionalized 18-tert-polyoxyethylene ether prepared above Aqueous dispersion of amines, to obtain a mixed dispersion of sulfonated polyphenylene sulfide/polyoxyethylene ether functionalized octadecadecyl tertiary amine, after stirring mechanically at a constant temperature at 70°C for 2 hours, the sulfonated polyphenylene sulfide/polyoxyethylene Put the mixed dispersion of ether-functionalized octadecadecyl tertiary amine into a dialysis bag for dialysis for 3 to 5 days, take it out and dry it, and vacuum dry it at 70°C for 24 hours to obtain fluidity at a temperature above 45°C. Polyphenylene sulfide modified material.

Example 4

a. Surface sulfonation of polyphenylene sulfide: Take 10g of polyphenylene sulfide powder, add it to 100g of chlorosulfonic acid, and mechanically blend and stir at 50°C for 24h; then wash the polyphenylene sulfide/chlorosulfonic acid with deionized water Mixed solution until the filtrate of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution pH = 7 to obtain preliminary sulfonated polyphenylene sulfide, and vacuum-dry the obtained preliminary sulfonated polyphenylene sulfide at 70°C for 12 hours to obtain sulfonated polyphenylene sulfide Polyphenylene sulfide.

b. Preparation of polyphenylene sulfide modified material: 0.75g of polyoxyethylene ether functionalized octadecyl tertiary amine was dissolved in deionized water to prepare polyoxyethylene ether functionalized octadecyl tertiary amine with a mass concentration of 40wt%. Water dispersion: take 1.5g of the sulfonated polyphenylene sulfide powder prepared in step 1 and disperse it into 30ml of deionized water, stir continuously and heat up to 70°C, then add the polyoxyethylene ether functionalized 18-tert-polyoxyethylene ether prepared above Aqueous dispersion of amines, to obtain a mixed dispersion of sulfonated polyphenylene sulfide/polyoxyethylene ether functionalized octadecadecyl tertiary amine, after stirring mechanically at a constant temperature at 70°C for 2 hours, the sulfonated polyphenylene sulfide/polyoxyethylene Put the mixed dispersion of ether-functionalized octadecadecyl tertiary amine into a dialysis bag for dialysis for 3 to 5 days, take it out and dry it, and vacuum dry it at 70°C for 24 hours to obtain fluidity at a temperature above 45°C. Polyphenylene sulfide modified material.

Example 5

a. Surface sulfonation of polyphenylene sulfide: Take 10g of polyphenylene sulfide powder, add it to 100g of chlorosulfonic acid, and mechanically blend and stir at 50°C for 24h; then wash the polyphenylene sulfide/chlorosulfonic acid with deionized water Mixed solution until the filtrate of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution pH = 7 to obtain preliminary sulfonated polyphenylene sulfide, and vacuum-dry the obtained preliminary sulfonated polyphenylene sulfide at 70°C for 12 hours to obtain sulfonated polyphenylene sulfide Polyphenylene sulfide.

b. Preparation of polyphenylene sulfide modified material: 0.75g of polyoxyethylene ether functionalized octadecyl tertiary amine was dissolved in deionized water to prepare polyoxyethylene ether functionalized octadecyl tertiary amine with a mass concentration of 50wt%. Water dispersion: take 1.5g of the sulfonated polyphenylene sulfide powder prepared in step 1 and disperse it into 30ml of deionized water, stir continuously and heat up to 70°C, then add the polyoxyethylene ether functionalized 18-tert-polyoxyethylene ether prepared above Aqueous dispersion of amines, to obtain a mixed dispersion of sulfonated polyphenylene sulfide/polyoxyethylene ether functionalized octadecadecyl tertiary amine, after stirring mechanically at a constant temperature at 70°C for 2 hours, the sulfonated polyphenylene sulfide/polyoxyethylene Put the mixed dispersion of ether-functionalized octadecadecyl tertiary amine into a dialysis bag for dialysis for 3 to 5 days, take it out and dry it, and vacuum dry it at 70°C for 24 hours to obtain fluidity at a temperature above 45°C. Polyphenylene sulfide modified material.

Example 6

a. Surface sulfonation of polyphenylene sulfide: Take 10g of polyphenylene sulfide powder, add it to 100g of chlorosulfonic acid, and mechanically blend and stir at 50°C for 24h; then wash the polyphenylene sulfide/chlorosulfonic acid with deionized water Mixed solution until the filtrate of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution pH = 7 to obtain preliminary sulfonated polyphenylene sulfide, and vacuum-dry the obtained preliminary sulfonated polyphenylene sulfide at 70°C for 12 hours to obtain sulfonated polyphenylene sulfide Polyphenylene sulfide.

b. Preparation of polyphenylene sulfide modified material: Dissolve 1g of polyoxyethylene ether functionalized octadecadec tertiary amine in deionized water to prepare polyoxyethylene ether functionalized octadecadec tertiary amine water with a mass concentration of 10wt% Dispersion liquid: take 1.5g of the sulfonated polyphenylene sulfide powder prepared in step 1 and disperse it into 30ml of deionized water, stir continuously and heat up to 70°C, then add the polyoxyethylene ether functionalized octadecadecyl tertiary amine prepared above The aqueous dispersion of the sulfonated polyphenylene sulfide/polyoxyethylene ether functionalized octadecadecyl tertiary amine mixed dispersion was obtained. After stirring mechanically at a constant temperature at 70°C for 3 hours, the sulfonated polyphenylene sulfide/polyoxyethylene ether Put the mixed dispersion of functionalized octadecadecyl tertiary amine into a dialysis bag for dialysis for 3 to 5 days, take it out and dry it, and dry it in vacuum at 70°C for 24 hours to obtain a polymer with fluidity at a temperature above 45°C. Phenyl sulfide modified material.

Example 7

a. Surface sulfonation of polyphenylene sulfide: Take 10g of polyphenylene sulfide powder, add it to 100g of chlorosulfonic acid, and mechanically blend and stir at 50°C for 24h; then wash the polyphenylene sulfide/chlorosulfonic acid with deionized water Mixed solution until the filtrate of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution pH = 7 to obtain preliminary sulfonated polyphenylene sulfide, and vacuum-dry the obtained preliminary sulfonated polyphenylene sulfide at 70°C for 12 hours to obtain sulfonated polyphenylene sulfide Polyphenylene sulfide.

b. Preparation of polyphenylene sulfide modified material: 1g of polyoxyethylene ether functionalized tertiary 18 amine was dissolved in deionized water to prepare water with a mass concentration of 20 wt% polyoxyethylene ether functionalized tertiary 18 amine Dispersion liquid: take 1.5g of the sulfonated polyphenylene sulfide powder prepared in step 1 and disperse it into 30ml of deionized water, stir continuously and heat up to 70°C, then add the polyoxyethylene ether functionalized octadecadecyl tertiary amine prepared above The aqueous dispersion of the sulfonated polyphenylene sulfide/polyoxyethylene ether functionalized octadecadecyl tertiary amine mixed dispersion was obtained. After stirring mechanically at a constant temperature at 70°C for 3 hours, the sulfonated polyphenylene sulfide/polyoxyethylene ether Put the mixed dispersion of functionalized octadecadecyl tertiary amine into a dialysis bag for dialysis for 3 to 5 days, take it out and dry it, and dry it in vacuum at 70°C for 24 hours to obtain a polymer with fluidity at a temperature above 45°C. Phenyl sulfide modified material.

Example 8

a. Surface sulfonation of polyphenylene sulfide: Take 10g of polyphenylene sulfide powder, add it to 100g of chlorosulfonic acid, and mechanically blend and stir at 50°C for 24h; then wash the polyphenylene sulfide/chlorosulfonic acid with deionized water Mixed solution until the filtrate of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution pH = 7 to obtain preliminary sulfonated polyphenylene sulfide, and vacuum-dry the obtained preliminary sulfonated polyphenylene sulfide at 70°C for 12 hours to obtain sulfonated polyphenylene sulfide Polyphenylene sulfide.

b. Preparation of polyphenylene sulfide modified material: Dissolve 1g of polyoxyethylene ether functionalized octadecyl tertiary amine in deionized water to prepare water with a mass concentration of 30wt% polyoxyethylene ether functionalized octadecyl tertiary amine Dispersion liquid: take 1.5g of the sulfonated polyphenylene sulfide powder prepared in step 1 and disperse it into 30ml of deionized water, stir continuously and heat up to 70°C, then add the polyoxyethylene ether functionalized octadecadecyl tertiary amine prepared above The aqueous dispersion of the sulfonated polyphenylene sulfide/polyoxyethylene ether functionalized octadecadecyl tertiary amine mixed dispersion was obtained. After stirring mechanically at a constant temperature at 70°C for 3 hours, the sulfonated polyphenylene sulfide/polyoxyethylene ether Put the mixed dispersion of functionalized octadecadecyl tertiary amine into a dialysis bag for dialysis for 3 to 5 days, take it out and dry it, and dry it in vacuum at 70°C for 24 hours to obtain a polymer with fluidity at a temperature above 45°C. Phenyl sulfide modified material.

Example 9

a. Surface sulfonation of polyphenylene sulfide: Take 10g of polyphenylene sulfide powder, add it to 100g of chlorosulfonic acid, and mechanically blend and stir at 50°C for 24h; then wash the polyphenylene sulfide/chlorosulfonic acid with deionized water Mixed solution until the filtrate of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution pH = 7 to obtain preliminary sulfonated polyphenylene sulfide, and vacuum-dry the obtained preliminary sulfonated polyphenylene sulfide at 70°C for 12 hours to obtain sulfonated polyphenylene sulfide Polyphenylene sulfide.

b. Preparation of polyphenylene sulfide modified material: Dissolve 1g of polyoxyethylene ether functionalized octadecyl tertiary amine in deionized water to prepare water with a mass concentration of 40wt% polyoxyethylene ether functionalized octadecyl tertiary amine Dispersion liquid: take 1.5g of the sulfonated polyphenylene sulfide powder prepared in step 1 and disperse it into 30ml of deionized water, stir continuously and heat up to 70°C, then add the polyoxyethylene ether functionalized octadecadecyl tertiary amine prepared above The aqueous dispersion of the sulfonated polyphenylene sulfide/polyoxyethylene ether functionalized octadecadecyl tertiary amine mixed dispersion was obtained. After stirring mechanically at a constant temperature at 70°C for 3 hours, the sulfonated polyphenylene sulfide/polyoxyethylene ether Put the mixed dispersion of functionalized octadecadecyl tertiary amine into a dialysis bag for dialysis for 3 to 5 days, take it out and dry it, and dry it in vacuum at 70°C for 24 hours to obtain a polymer with fluidity at a temperature above 45°C. Phenyl sulfide modified material.

Example 10

a. Surface sulfonation of polyphenylene sulfide: Take 10g of polyphenylene sulfide powder, add it to 100g of chlorosulfonic acid, and mechanically blend and stir at 50°C for 24h; then wash the polyphenylene sulfide/chlorosulfonic acid with deionized water Mixed solution until the filtrate of the washed polyphenylene sulfide/chlorosulfonic acid mixed solution pH = 7 to obtain preliminary sulfonated polyphenylene sulfide, and vacuum-dry the obtained preliminary sulfonated polyphenylene sulfide at 70°C for 12 hours to obtain sulfonated polyphenylene sulfide Polyphenylene sulfide.

b. Preparation of polyphenylene sulfide modified material: Dissolve 1g of polyoxyethylene ether functionalized octadecyl tertiary amine in deionized water to prepare water with a mass concentration of 50wt% polyoxyethylene ether functionalized octadecyl tertiary amine Dispersion liquid: take 1.5g of the sulfonated polyphenylene sulfide powder prepared in step 1 and disperse it into 30ml of deionized water, stir continuously and heat up to 70°C, then add the polyoxyethylene ether functionalized octadecadecyl tertiary amine prepared above The aqueous dispersion of the sulfonated polyphenylene sulfide/polyoxyethylene ether functionalized octadecadecyl tertiary amine mixed dispersion was obtained. After stirring mechanically at a constant temperature at 70°C for 3 hours, the sulfonated polyphenylene sulfide/polyoxyethylene ether Put the mixed dispersion of functionalized octadecadecyl tertiary amine into a dialysis bag for dialysis for 3 to 5 days, take it out and dry it, and dry it in vacuum at 70°C for 24 hours to obtain a polymer with fluidity at a temperature above 45°C. Phenyl sulfide modified material.

Claims (1)

1. a preparation method of polyphenylene sulfide modified material, described preparation method according to the following steps: a. Mix polyphenylene sulfide and chlorosulfonic acid with a particle size of 0.2-0.3 μm at a mass ratio of 1 to 50:100, and mechanically stir at 50°C for 24 hours to obtain a polyphenylene sulfide/chlorosulfonic acid mixture, then Wash the polyphenylene sulfide/chlorosulfonic acid mixed solution with deionized water until the pH of the washed filtrate is 7 to obtain preliminary sulfonated polyphenylene sulfide, and dry the obtained preliminary sulfonated polyphenylene sulfide in vacuum at 70°C After 12 hours, sulfonated polyphenylene sulfide with a particle size ranging from 10 to 50 μm was obtained; b. Dissolve polyoxyethylene ether functionalized octadecadecyl tertiary amine in deionized water to prepare a water dispersion of polyoxyethylene ether functionalized octadecadecyl tertiary amine with a mass concentration of 10wt% to 50wt%, and sulfonated polyphenylene Add sulfide into deionized water, heat up to 70°C, and stir mechanically for 30 minutes to obtain an aqueous dispersion of sulfonated polyphenylene sulfide with a mass fraction of 5 wt%, and then disperse the water dispersion of polyoxyethylene ether functionalized octadecadec tertiary amine liquid and the aqueous dispersion of sulfonated polyphenylene sulfide, and the mass ratio of polyoxyethylene ether functionalized octadecyl tertiary amine to sulfonated polyphenylene sulfide is 0.5-1:1 to obtain sulfonated polyphenylene sulfide/ The mixed solution of polyoxyethylene ether functionalized octadecadecyl tertiary amine was mechanically stirred at a constant temperature at 70°C for 2 hours, and then dialyzed for 3 to 5 days. The polyphenylene sulfide modified material having fluidity under the condition of temperature above 45° C. is obtained.