CN103467741A - Polyphenylene sulfide and preparation method thereof - Google Patents

Abstract

The invention discloses a _polyarylene sulfide and a preparation method thereof. Parts of alkali and 1-100 parts of catalyst are added to the reactor, and after being replaced with nitrogen, the reactor is sealed and reacted at a temperature of 100-180°C for 0.5-2h, at a temperature of 180-260°C for 0.5-4h, and then at a temperature of 190- Keep at 280°C for 0.5-4h, cool down to 80-160°C, pour the reaction product into water, separate the crude polymer product, wash the crude product with tap water, dry it, then wash it with deionized water and acetone respectively, and put it at 100°C Dry at -120°C with a vacuum degree of 0.08-0.095 MPa for 1-24 hours to obtain a purified polyarylene sulfide resin.

Description

A kind of polyarylene sulfide and preparation method thereof

technical field

The invention relates to a polyarylene sulfide and a preparation method thereof, belonging to the field of polymer synthesis.

Background technique

Polyarylene sulfide such as polyphenylene sulfide, polyphenylene sulfide ketone, and polyphenylene sulfide sulfone are widely used in automobiles, aerospace and aviation due to their high temperature resistance, corrosion resistance, excellent electrical properties, mechanical properties and dimensional stability and electronic technology. In industrialized production, the current main method of polyarylene sulfide production is: using a composite catalytic system to dehydrate aqueous sodium sulfide at high temperature, and then carry out solution polycondensation with dihalogenated aromatic compounds at high temperature and high pressure, such as Philips (US33544129) and Deyang Technology Co., Ltd. (CN1793202A) was prepared by dehydrating sodium sulfide trihydrate and then reacting with p-dichlorobenzene in nitrogen and polar solvent NMP under pressure. This method consumes a lot of energy and consumes The time is long (about 4-6h, or even longer), and the cost is high. Chinese patent CN1143652A reports that tough polyphenylene sulfide resin is synthesized by using sulfur as a raw material in a polar solvent under pressure. The reaction process requires the use of a reducing agent, the process is relatively complicated, there are many reaction by-products, and the product is not easy to purify.

Contents of the invention

The object of the present invention is to provide a kind of high-efficiency, rapid production method of polyarylene sulfide in view of the deficiencies in the prior art, which is characterized in that anhydrous sodium sulfide and dihalogenated aromatic compounds are used as raw materials, and a single polyarylene sulfide is used in a polar solvent The catalytic system prepares high-performance polyarylene sulfide resin through solution polycondensation reaction. The dehydration process of sodium sulfide is omitted in the whole reaction, which greatly reduces the reaction time, improves the reaction efficiency, and reduces energy consumption; at the same time, the reaction The one-pot method adopted is easier to operate than the previous two-step method, and the reaction is easier to control. The product is always reacted under airtight conditions, is not easy to oxidize, has stable quality and high molecular weight.

The object of the present invention is achieved by the following technical measures, wherein the parts of raw materials are parts by weight unless otherwise specified.

The starting material of polyarylene sulfide consists of the following components:

Among them, the general structural formula of dihalogenated aromatic compounds is X-Ar-X

X=F or Cl,

中的任一种；

any of

The base is any one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate or potassium bicarbonate.

The preparation method of described polyarylene sulfide comprises the following steps:

Add 78 parts of Na ₂ S, 1-50 parts of dispersant, 114-287 parts of dihalogenated aromatic compound, 100-800 parts of solvent, 0.1-40 parts of alkali and 1-100 parts of catalyst into the reactor, and replace it with nitrogen, Close the reaction kettle, react at a temperature of 100-180°C for 0.5-2h, react at a temperature of 180-260°C for 0.5-4h, and then keep at a temperature of 190-280°C for 0.5-4h, then cool down to 80-160°C, and the reaction product Pour it into water, separate the crude product of the polymer, wash the crude product with tap water, dry it, wash it with deionized water and acetone respectively, and dry it at a temperature of 100-120°C and a vacuum of 0.08-0.095MPa for 1-24h to obtain a purified polymer Arylsulfide resin.

The dispersant is sodium dodecylbenzenesulfonate, sodium p-toluenesulfonate, sodium p-aminobenzenesulfonate, tetrabutylammonium bromide, tetrabutylammonium chloride, cetyltrimethyl Ammonium Bromide, Lauryltrimethylammonium Chloride, Triethylbenzylammonium Chloride, Water, Caprolactam, Sodium Acetate, Sodium Oxalate, Lithium Acetate, Lithium Oxalate, Sodium Adipate, Lithium Adipate, Lithium p-toluenesulfonate, 1-methyl-3-propylimidazolium bromide, 1-methyl-3-isopropylimidazolium bromide, 1,3-dipropylimidazolium bromide and 1 - at least one of butyl-3-methylimidazolium borofluoride.

The solvent is N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, acetamide, N-methylpyrrolidone, dimethyl Either of sulfoxide or hexamethylphosphoric triamide.

The catalyst is cuprous oxide, cuprous chloride, triphenylphosphine, sodium glycolate, sodium terephthalate, sodium phosphate, calcium glycolate, calcium terephthalate, calcium formate, calcium acetate, calcium oxalate, chlorine At least one of calcium chloride, calcium phosphate, polyethylene glycol-400, polyethylene glycol-600 and polyethylene glycol-800.

Structural characterization and performance testing:

1. The structure of the polyarylene sulfide resin prepared by the present invention has been confirmed by infrared spectroscopy, as shown in FIG. 1 .

2. Prepare polyarylene sulfide resins with different viscosities by adjusting the concentration of reactants, material ratio and reaction temperature, and use a melt indexer to measure the melt index of polyphenylene sulfide (PPS) (temperature: 316°C, load: 5kg ); prepare a solution with a certain concentration, and measure the intrinsic viscosity of the polymer with an Ubbelohde viscometer:

Polyphenylene sulfide-PPS (solvent: α-chloronaphthalene, concentration: 0.4g/dl, test temperature 208.0±0.1°C)

Polyphenylene sulfide ketone-PPSK (solvent: concentrated sulfuric acid, concentration: 0.5g/dl, test temperature 30.0±0.1℃)

Polyphenylene sulfone sulfone-PPSS (solvent: NMP, concentration: 0.5g/dl, test temperature 30.0±0.1℃)

3. Differential scanning calorimetry (DSC) was used to test the glass transition temperature and melting point of polyarylene sulfide resin, and the results are shown in Figure 2.

The present invention has the following advantages:

1. In the process of using anhydrous sodium sulfide and dihalogenated aromatic compounds to synthesize polyarylene sulfide resin, the dehydration process of sodium sulfide is omitted, the reaction time is greatly reduced, the reaction efficiency is improved, and the production energy consumption is reduced .

2. The use of anhydrous sodium sulfide as raw material does not require dehydration, and the product is always reacted under airtight conditions, which overcomes the problem that hydrogen sulfide gas is easily generated during the dehydration process to pollute the environment in the commonly used method of producing polyphenylene sulfide from sodium sulfide trihydrate.

3. The use of anhydrous sodium sulfide as raw material does not require dehydration at a higher temperature, which further optimizes the types and prices of solvents that can be selected in the process of preparing polyphenylene sulfide, and overcomes the solvent selection in the process of producing polyphenylene sulfide Single, high cost and other defects.

4. The one-pot method used in the reaction is easier to operate than the previous two-step method, and the reaction is easier to control. The reaction is carried out under closed conditions, and the product is not easily oxidized, with stable quality and high molecular weight.

5. This type of polymer has the advantages of high temperature resistance, radiation resistance, corrosion resistance, good mechanical properties and easy processing, and has a wider application prospect.

Description of drawings

Fig. 1 is the structure infrared spectrogram of polyarylene sulfide resin

Figure 2 is the differential scanning calorimetry (DSC) diagram of polyarylene sulfide resin

Detailed ways

The present invention is specifically described below through the examples, it is necessary to point out that the present examples are only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention, those skilled in the art can according to the above-mentioned present invention The content of the invention makes some non-essential improvements and adjustments.

Example 1

Add 78g Na ₂ S, 1g sodium dodecylbenzenesulfonate, 147g p-dichlorobenzene, 100g N,N-dimethylformamide, 1g sodium hydroxide and 100g cuprous oxide into the reaction kettle, replace with nitrogen Finally, close the reactor, react at a temperature of 180°C for 0.5h, react at a temperature of 260°C for 4h, then keep at a temperature of 280°C for 4h, cool down to 160°C, pour the reaction product into water, separate the crude polymer product, and After washing and drying, it was purified with deionized water and acetone, and dried at a temperature of 120°C under a vacuum of 0.08 MPa for 24 hours to obtain polyphenylene sulfide resin (PPS). The yield is 94%, the intrinsic viscosity [η]=0.33, and the melt index is 45g/10min. The infrared characterization is shown in Figure 1 in detail: 3066 and 1568, 1468, and 1382cm ^-1 are the CH stretching vibration and skeleton stretching vibration absorption peaks of the benzene ring respectively, and 1088cm ^-1 is the CS stretching vibration absorption peak, indicating that the obtained resin structure is consistent with expectations ; DSC analysis is shown in Figure 2: its melting point is 291.4 ° C, indicating that it has good thermal properties.

Example 2

Add 78g Na ₂ S, 20g sodium adipate, 114g p-difluorobenzene, 300g hexamethylphosphoric triamide, 30g potassium carbonate, 20g sodium glycolate, 30g polyethylene glycol-600 into the reaction kettle, and use nitrogen gas After the replacement, close the reactor, react at a temperature of 180°C for 3 hours, react at a temperature of 200°C for 2 hours, then keep at a temperature of 280°C for 2 hours, cool down to 100°C, pour the reaction product into water, and separate the crude polymer product. After washing and drying, it was purified with deionized water and acetone, and dried at a temperature of 110° C. under a vacuum of 0.090 MPa for 12 hours to obtain a polyphenylene sulfide resin. Its productive rate is 89%, intrinsic viscosity number [η]=0.22, melt index 143g/10min.

Example 3

Add 78g Na ₂ S, 50g triethylbenzyl ammonium chloride, 218g 4,4'-difluorobenzophenone, 800g N-methylpyrrolidone, 10g potassium hydroxide and 50g sodium terephthalate into the reaction kettle, After replacing with nitrogen, close the reactor, react at 100°C for 2h, react at 180°C for 0.5h, then keep at 250°C for 0.5h, cool down to 80°C, pour the reaction product into water, and separate the crude polymer product , the crude product was washed, dried, purified with deionized water and acetone, and dried at a temperature of 100°C and a vacuum of 0.095 MPa for 12 hours to obtain polyphenylene sulfide ketone resin (PPSK). Its yield rate is 91%, intrinsic viscosity number [η]=0.56, infrared characterization is shown in Fig. 1 for details: 3054 and 1585, 1485, 1396cm ^-1 are the CH stretching vibration of benzene ring and skeleton stretching vibration absorption peak respectively, 1654cm ^-1 is the vibration absorption peak of -CO-, and 1081cm ^-1 is the CS stretching vibration absorption peak, indicating that the obtained resin structure is consistent with expectations; DSC analysis is shown in Figure 2: its melting point is 343.5 ° C, indicating that it has good thermal conductivity performance.

Example 4

Add 78g _Na2S , 25g 1,3-dipropylimidazolium bromide, 3g water, 251g 4,4'-dichlorobenzophenone, 400g N-methylformamide, 5g sodium bicarbonate and 25g sodium phosphate In the reaction kettle, after replacing with nitrogen, close the reaction kettle, react at a temperature of 140°C for 2h, react at a temperature of 180°C for 0.5h, then keep at a temperature of 190°C for 4h, cool down to 120°C, pour the reaction product into water, separate and polymerize The crude product was washed, dried, purified with deionized water and acetone, and dried at a temperature of 110°C and a vacuum of 0.095 MPa for 12 hours to obtain polyphenylene sulfide ketone resin (PPSK). The yield was 93%, and the intrinsic viscosity [η] = 0.62.

Example 5

Add 78g Na ₂ S, 10g tetrabutylammonium bromide, 287g 4,4'-dichlorodiphenylsulfone, 500g N,N-dimethylacetamide, 40g sodium carbonate and 1g triphenylphosphine into the reaction kettle, After replacing with nitrogen, close the reactor, react at 160°C for 1 hour, react at 190°C for 2 hours, then keep at 260°C for 0.5h, cool down to 100°C, pour the reaction product into water, separate the crude polymer product, The crude product was washed, dried, purified with deionized water and acetone, and dried at a temperature of 110°C and a vacuum of 0.090 MPa for 10 hours to obtain polyphenylene sulfone sulfone resin (PPSS). Its yield rate is 93%, intrinsic viscosity number [η]=0.59, and infrared characterization is shown in Figure 1 for details: 3085 and 1572, 1471, 1389cm ^-1 are respectively the CH stretching vibration of benzene ring and skeleton stretching vibration absorption peak, 1319 , 1156cm ^-1 is the vibration absorption peak of -SO ₂ -, and 1072cm ^-1 is the CS stretching vibration absorption peak, indicating that the obtained resin structure is consistent with expectations; DSC analysis is shown in Figure 2: its glass transition temperature is 221.4 ° C, indicating that its Has good thermal performance.

Example 6

Add 78g Na ₂ S, 40g lithium oxalate, 254g 4,4'-difluorodiphenyl sulfone, 600g acetamide, 40g lithium carbonate, 3g cuprous chloride, 16g polyethylene glycol-800 into the reaction kettle, replace with nitrogen Finally, close the reactor, react at a temperature of 120°C for 1 hour, react at a temperature of 160°C for 2 hours, then keep at a temperature of 190°C for 2 hours, cool down to 120°C, pour the reaction product into water, separate the crude polymer product, and pass the crude product through After washing and drying, it was purified with deionized water and acetone, and dried at a temperature of 120°C and a vacuum of 0.090 MPa for 24 hours to obtain polyphenylene sulfone sulfone resin (PPSS). The yield was 91%, and the intrinsic viscosity [η] = 0.48.

Claims (5)

1. A polyarylene sulfide is characterized in that the starting material of the polyarylene sulfide is made up of the following components, by weight:

Among them, the general structural formula of dihalogenated aromatic compounds is X-Ar-X X=F or Cl,

any of The base is any one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate or potassium bicarbonate. 2. according to the preparation method of polyarylene sulfide described in claim 1, it is characterized in that this method comprises the following steps: Add 78 parts of Na ₂ S, 1-50 parts of dispersant, 114-287 parts of dihalogenated aromatic compound, 100-800 parts of solvent, 0.1-40 parts of alkali and 1-100 parts of catalyst into the reactor, and replace it with nitrogen, Close the reaction kettle, react at a temperature of 100-180°C for 0.5-2h, react at a temperature of 180-260°C for 0.5-4h, and then keep at a temperature of 190-280°C for 0.5-4h, then cool down to 80-160°C, and the reaction product Pour it into water, separate the crude product of the polymer, wash the crude product with tap water, dry it, wash it with deionized water and acetone respectively, and dry it at a temperature of 100-120°C and a vacuum of 0.08-0.095MPa for 1-24h to obtain a purified polymer Arylsulfide resin. 3. according to the preparation method of the described polyarylene sulfide of claim 2, it is characterized in that dispersant is sodium dodecylbenzenesulfonate, sodium p-toluenesulfonate, sodium p-aminobenzenesulfonate, tetrabutyl bromide Ammonium Chloride, Tetrabutylammonium Chloride, Cetyltrimethylammonium Bromide, Lauryltrimethylammonium Chloride, Triethylbenzylammonium Chloride, Water, Caprolactam, Sodium Acetate, Sodium Oxalate , lithium acetate, lithium oxalate, sodium adipate, lithium adipate, lithium p-toluenesulfonate, 1-methyl-3-propylimidazolium bromide, 1-methyl-3-isopropylimidazole At least one of bromide salt, 1,3-dipropylimidazolium bromide salt and 1-butyl-3-methylimidazolium borofluoride. 4. according to the preparation method of the described polyarylene sulfide of claim 1 or 2, it is characterized in that solvent is N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, Any of N-methylacetamide, acetamide, N-methylpyrrolidone, dimethylsulfoxide, or hexamethylphosphoric triamide. 5. according to the preparation method of the described polyarylene sulfide of claim 1 or 2, it is characterized in that the catalyst is cuprous oxide, cuprous chloride, triphenylphosphine, sodium glycolate, sodium terephthalate, sodium phosphate, hydroxyl At least one of calcium acetate, calcium terephthalate, calcium formate, calcium acetate, calcium oxalate, calcium chloride, calcium phosphate, polyethylene glycol-400, polyethylene glycol-600 and polyethylene glycol-800 .

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