WO2002051910A1 - Polymeres de sulfure de polyphenylene lineaires a poids moleculaire eleve et haute densite, et procedes de preparation de ces polymeres - Google Patents

Polymeres de sulfure de polyphenylene lineaires a poids moleculaire eleve et haute densite, et procedes de preparation de ces polymeres Download PDF

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Publication number
WO2002051910A1
WO2002051910A1 PCT/CN2001/001637 CN0101637W WO02051910A1 WO 2002051910 A1 WO2002051910 A1 WO 2002051910A1 CN 0101637 W CN0101637 W CN 0101637W WO 02051910 A1 WO02051910 A1 WO 02051910A1
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Prior art keywords
polyphenylene sulfide
molecular weight
minutes
preparing
density
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PCT/CN2001/001637
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English (en)
Chinese (zh)
Inventor
Qigao Gu
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Qigao Gu
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Publication of WO2002051910A1 publication Critical patent/WO2002051910A1/fr

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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0254—Preparatory processes using metal sulfides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0259—Preparatory processes metal hydrogensulfides

Definitions

  • the invention relates to a polyphenylene sulfide and a preparation method thereof, and more particularly to a high-density linear high molecular weight polyphenylene sulfide having a regular linear structure and a narrow molecular weight distribution, and a preparation method thereof.
  • a method for preparing a sulfur-containing polymer is described in Chinese patent CN-1225106A, which comprises dissolving sodium sulfide trihydrate in N-methylpyrrolidone (NMP), distilling off the condensate, and then dissolving it in Dichlorobenzene (DCB) in N-methylpyrrolidinone was added, and prepolymerized at 230 ° C for 1 hour, and then the reaction kettle was returned to normal pressure.
  • Sodium sulfide trihydrate was added, water was distilled off, and the mixture was heated to 230 ° C. 5 ⁇
  • dichlorobenzene dissolved in N-methylpyrrolidone was added, at 230 ° C, the mixture was polymerized for 1.5 hours.
  • the polymerization was carried out in two stages, the first stage temperature was 100 ⁇ 210 ° C, time 0.5 ⁇ 6 hours, the second stage temperature was 200 ⁇ 280 ° C, time 0.5 ⁇ 6 hours, yield 92%, The viscosity is 1500 poise.
  • Industrial scale production of anhydrous sulfur sulfide or sodium sulfide containing partially crystallized water not only has high production costs, but also has problems such as process, equipment, storage, and more serious.
  • Crystalline sodium sulfide loses some or all of it at high temperatures After crystallizing water, the color becomes darker and even red Brown, forming solid amorphous particles.
  • the reaction with halobenzene can only take place on the surface of the particles, and the activity is very low.
  • the reaction process is a heterogeneous process.
  • a two-stage reaction is used: In the first stage of the reaction, solid sodium sulfide particles and a halogenated state in the form of droplets (oil beads) dispersed in a strongly polar organic solvent Benzene reaction for 2 ⁇ 12 hours, the formation of prepolymers with extremely uneven molecular weights and a viscosity of 0.5 ⁇ 30P.
  • the prepared polymers differ greatly in color and luster (white, gray, tan), and the particles are not uniform. 'Most of them are powdery, with a bulk density of only 115 to 280 kg / m3 and a density of only It reaches 1150 ⁇ 1320 kg / m3 .
  • the post-processing should be pre-pelletized with a twin-screw extruder, and then filled. Strong, such as adding glass fiber, carbon fiber, inorganic materials, etc. for secondary granulation, for industrial scale preparation of various compositions, the cost is very high.
  • the object of the present invention is to provide a high-density linear high-molecular-weight polyphenylene sulfide, which has readily available raw materials, is inexpensive, has uniform particles, has a linear molecular structure, has a high molecular weight, and has a narrow molecular weight distribution.
  • Another object of the present invention is to provide a method for preparing a high-density linear high-molecular-weight polyphenylene sulfide.
  • the high-density linear high molecular weight polyphenylene sulfide of the present invention has a melting point of 280 ⁇ 298 ° C and a melt flow rate of
  • the high-density linear high-molecular-weight polyphenylene sulfide of the present invention has a melting point of 280 to 298 ° C, and a melt flow rate of 20 to 200 g / 316 ° C-5 kg to 10 minutes, and the particle size More than 0.1 mm, average molecular weight is 45000 ⁇ 72000, molecular weight can be controlled, density is 1360 ⁇ 1430 kg / m3 , and it has a regular linear structure.
  • the high-density linear high molecular weight polyphenylene sulfide of the present invention has a melting point of 280 ⁇ 298 ° C, a melt flow rate of 50 ⁇ 100 g / 316 ⁇ -5 kg for 10 minutes, and a particle size greater than 0. 1 mm, average molecular weight is 55,000 ⁇ 64000, molecular weight can be controlled, density is 1360 ⁇ 1430 kg / m3 , and it has a regular linear structure.
  • the high-density linear high molecular weight polyphenylene sulfide of the present invention has a tensile strength greater than 100 MPa, a breaking elongation greater than 32%, a flexural strength greater than 160 MPa, and a notched Izod impact strength greater than 12 kg / m.
  • a crystal of sodium sulfide containing nine molecules of water is used as a sulfur source. Further, a crystal of sodium sulfide containing nine molecules of water can be used as a sulfur source.
  • the high-density linear high-molecular-weight polyphenylene sulfide of the present invention can be prepared according to the following method, including the following steps:
  • the molar ratio of sulfide, phosphate and solvent is: 1. 0: (0. 2 ⁇ 0. 3): (0. 5 ⁇ 2. 5), at a temperature of 120 ⁇
  • the high-density linear high-molecular-weight polyphenylene sulfide of the present invention can be prepared by the following method, including the following steps ⁇
  • the molar ratio of sulfide, phosphonate and solvent is: 1. 0: (0. 2 ⁇ 0. 25): (1. 0 ⁇ 1. 8), at a temperature of 150 ⁇
  • the high-density linear high-molecular-weight polyphenylene sulfide of the present invention can be prepared by the following method, including the following steps:
  • the molar ratio of sulfide, phosphate and solvent is: 1. 0: (0. 2 ⁇ 0. 25): (1. 2 ⁇ 1. 6), at a temperature of 150 ⁇ Reaction at 220 ° C for 90 ⁇ 120 minutes, complexes are formed, and excess low boiling point substances are discharged at the same time;
  • the molar ratio of the complex to the halogenated aromatic compound is 1.0: (0. 3 ⁇ 0. 6), more It is good that the molar ratio of the complex to the halogenated aromatic compound is 1.0: (0.4 to 0.5); the molar ratio of the solvent to the halogenated aromatic compound is 1: (0.2 to 0 5).
  • the phosphate is sodium phosphate, and the solvent hexamethylphosphoryl triamine;
  • the halogenated aromatic compound is dichlorobenzene, and the dichlorobenzene is 1.4-Xinch dichlorobenzene and 1 .
  • the mixture of 3-dichlorobenzene, the molar ratio of p-dichlorobenzene and m-dichlorobenzene is 3: 2 ⁇ 19: 1, the molar ratio of p-dichlorobenzene and m-dichlorobenzene is 9: 1 ⁇ 16: lo
  • DMF dimethylformamide
  • NMP N-methylpyrrolidone
  • HPT hexamethylphosphoryltriamine
  • dihalobenzenes including diiodobenzene, Dibromobenzene partially (more than 10%) or completely replace dichlorobenzene
  • sodium phosphate other phosphates can be used, including phosphites, metaphosphates, and hypophosphites. Besides sodium, potassium, lithium, etc. can also be used.
  • the raw materials of the product of the invention are easily available, the cost is low, the polymer produced has a high molecular weight, a narrow molecular weight distribution, and a density of 1360 to 1430 kg / m 3 , which is suitable for industrial scale preparation of polyphenylene sulfide.
  • crystalline sodium sulfide containing nine molecules of crystalline water is used as a sulfur source. Because sodium sulfide nine hydrate is a prism-shaped crystal, it has stable properties, easy storage, simple industrial preparation, and low cost. Of course, if necessary, crystalline sodium sulfide containing not nine molecules may be used as the sulfur source, including sodium sulfide using six molecules or three molecules of crystal water as the sulfur source.
  • a complex of sodium sulfide and phosphate with a polar solvent is prepared.
  • sodium sulfide, sodium phosphate and solvent form complexes, which are red in the range of 80 ⁇ 125 ° C and dark blue in the range of 140 ⁇ 230 ° C.
  • the complex is in a metastable state and has a high reactivity. Since the complex is metastable, the temperature has a great influence on it. When the temperature is higher than 180 ° C, the complex has good activity.
  • the reaction speed of benzene mixture is very fast, and the size of the prepolymer produced is uniform; when the temperature is lower than 130 ⁇ , the activity of the complex is low, the prepolymerization reaction time is long, and the molecular weight of the prepolymer produced is greatly different, which significantly affects the synthesis product.
  • the yield and quality are unfavorable.
  • a halogenated aromatic compound which is highly dispersed in a polar solvent is reacted with active sulfur in the complex at 180 ⁇ 230 ° C to form a prepolymer.
  • the reaction speed is very fast, can be completed in 5 to 30 minutes. What's more important is that the molecular size of the prepolymers produced by the reaction is basically the same, which is of great significance for further polymerization into linear polymers with high molecular weight and narrow distribution range.
  • a halogenated aromatic mixture is used, when the amount of 1.4 pairs of dichlorobenzene and 1.3-m-dichlorobenzene is in the range of 3: 2 ⁇ 19 : 1, and preferably 9: 1 ⁇ 16: 1: 1 range, the solubility of the prepolymer in a polar solvent (such as hexamethylphosphoryl triamine) is very large, and then the product performance indicators obtained through polycondensation are significantly improved compared to the single use of 1.4 pairs of dichlorobenzene .
  • the prepolymer system was rapidly increased to 180 ⁇ 28 (TC range for polycondensation in accordance with the program temperature increase method, and the process conditions were extremely stable.
  • the polymer with the expected linear molecular structure and molecular weight and concentrated molecular weight distribution is obtained.
  • the polymer is characterized by high whiteness, uniform particles, particle size of 1 mm, bulk density of 450 ⁇ 700 kg / m3 , and density of 1360-1430.
  • Kg / m3 high-quality polyphenylene sulfide resin can be directly used in high-strength injection products, high-toughness film products, fiber products and electrical components with excellent performance.
  • the resin density of the invention reaches 1360 ⁇ 1430 kg / m3 , which is convenient for storage and transportation, and can be easily added with glass fiber, carbon fiber, and inorganic materials for reinforcement without pre-granulation treatment.
  • the polymerization reaction of the present invention is carried out at a low pressure of 0.1 to 0.6 MPa, which does not have high requirements for reactor manufacture.
  • the polymerization reaction is more stable than the atmospheric polymerization conditions of the prior art, and the medium and high pressure polymerization conditions are adopted compared to foreign patents.
  • the equipment investment is significant. Lower, which is good for preparing polyphenylene sulfide on an industrial scale.
  • Figure 1 is an infrared spectrum of a product of the present invention.
  • Figure 2 is an infrared spectrum of another product of the present invention.
  • Figure 3 is the infrared spectrum of a famous foreign company's products.
  • FIG. 1 and FIG. 2 and FIG. 3 show that the molecular structure of the product of the present invention is regular.
  • Tables 1 and 2 compare the products of the present invention with those of a foreign company. Table 1
  • the temperature was further increased to 225 ° C, and the reaction was allowed to proceed for 2 hours, and then cooled
  • the granulated polymer was centrifuged below 80 ° C, washed with 80 ° C hot water to neutrality, then washed twice with 80 ° C deionized water, and then dried under reduced pressure at 12CTC for 6 hours to obtain all white granular polymerization. 311.5 kg, yield 96%, see Table 1 and Table 2 for polymer performance index.
  • Feeding capacity of a single kettle 2000 kg (raw materials, additives, solvents)
  • Resin appearance All white granules, particle size 0.1 mm.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

Cette invention se rapporte à des polymères de sulfure de polyphénylène linéaires à poids moléculaire élevé et à haute densité et aux procédés de préparation de ces polymères. Les points de fusion de ces polymères de sulfure de polyphénylène sont compris entre 280 °C et 298 °C, les indices de fluidité sont compris entre 20 et 700 g/316 °C-5 kg - 10 min, les diamètres des particules sont supérieurs à 0,1 mm, le poids moléculaire moyen est compris entre 28 000 et 64 000, la densité est comprise entre 1360 et 1430 kg/m3 et le poids moléculaire moyen de ces polymères est modulable et ces polymères ont une structure linéaire régulière. Cette invention consiste à utiliser du Na¿2?S9H2O comme source de soufre, à mélanger la source de soufre avec un additif et du solvant pour produire un composé complexe et à utiliser la polymérisation par condensation avec du chlorobenzène pour aboutir au produit final. Les avantages de cette invention sont un matériau brut facilement disponible, un faible coût et un poids moléculaire élevé avec une répartition étroite.
PCT/CN2001/001637 2000-12-27 2001-12-20 Polymeres de sulfure de polyphenylene lineaires a poids moleculaire eleve et haute densite, et procedes de preparation de ces polymeres WO2002051910A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN00120629.X 2000-12-27
CN00120629A CN1095481C (zh) 2000-12-27 2000-12-27 制备高密度线型高分子量聚苯硫醚的方法

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WO2002051910A1 true WO2002051910A1 (fr) 2002-07-04

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Families Citing this family (6)

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Publication number Priority date Publication date Assignee Title
CN1328303C (zh) * 2005-12-29 2007-07-25 四川得阳科技股份有限公司 纤维级聚苯硫醚树脂聚合工艺
CN101501106B (zh) * 2006-08-17 2011-11-09 Dic株式会社 聚芳硫醚树脂的制造方法
CN102676048B (zh) * 2012-06-07 2014-05-07 成都乐天塑料有限公司 聚苯硫醚改性涂料及其应用
CN103242528B (zh) * 2013-04-22 2015-08-19 中国石油化工股份有限公司 一种线型高分子量聚苯硫醚的合成方法
CN103642042A (zh) * 2013-09-22 2014-03-19 上海大学 聚苯硫醚的合成方法
CN105085917A (zh) * 2015-08-05 2015-11-25 广州高八二塑料有限公司 薄膜级聚苯硫醚树脂及其制备方法

Citations (5)

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JPS59221331A (ja) * 1983-05-31 1984-12-12 Dainippon Ink & Chem Inc ポリフエニレンスルフイドの製造法
JPS60200808A (ja) * 1984-03-27 1985-10-11 Dainippon Ink & Chem Inc アリ−レンスルフイドポリマ−用硫化ソ−ダ組成物の製造法及びポリマ−の製造法
JPS61111329A (ja) * 1984-11-05 1986-05-29 Dainippon Ink & Chem Inc アリ−レンスルフイドポリマ−の製造方法
CN85102664A (zh) * 1985-04-01 1986-09-24 四川大学 一种高分子量线型聚苯硫醚的合成方法
JPS62190228A (ja) * 1986-02-17 1987-08-20 Dainippon Ink & Chem Inc ポリアリ−レンスルフイドの製造方法

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JPS6220528A (ja) * 1985-07-19 1987-01-29 Asahi Glass Co Ltd 高分子量ポリフエニレンスルフイドの製造方法
CN85109096B (zh) * 1985-12-14 1988-09-21 四川大学 一种高分子量线型聚苯硫醚的合成方法
JPH0779111B2 (ja) * 1986-03-01 1995-08-23 東芝精機株式会社 ペレツト装着装置
DE19513479A1 (de) * 1995-04-13 1996-10-17 Hoechst Ag Verfahren zur Herstellung von Polyarylensulfid
CN1075529C (zh) * 1997-02-05 2001-11-28 徐登顺 线型高分子量聚苯硫醚工业合成工艺

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59221331A (ja) * 1983-05-31 1984-12-12 Dainippon Ink & Chem Inc ポリフエニレンスルフイドの製造法
JPS60200808A (ja) * 1984-03-27 1985-10-11 Dainippon Ink & Chem Inc アリ−レンスルフイドポリマ−用硫化ソ−ダ組成物の製造法及びポリマ−の製造法
JPS61111329A (ja) * 1984-11-05 1986-05-29 Dainippon Ink & Chem Inc アリ−レンスルフイドポリマ−の製造方法
CN85102664A (zh) * 1985-04-01 1986-09-24 四川大学 一种高分子量线型聚苯硫醚的合成方法
JPS62190228A (ja) * 1986-02-17 1987-08-20 Dainippon Ink & Chem Inc ポリアリ−レンスルフイドの製造方法

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CN1095481C (zh) 2002-12-04

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