CN1095481C - Process for preparing high-density high-molecular linear polyphenyl thioether - Google Patents
Process for preparing high-density high-molecular linear polyphenyl thioether Download PDFInfo
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- CN1095481C CN1095481C CN00120629A CN00120629A CN1095481C CN 1095481 C CN1095481 C CN 1095481C CN 00120629 A CN00120629 A CN 00120629A CN 00120629 A CN00120629 A CN 00120629A CN 1095481 C CN1095481 C CN 1095481C
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- 229920006389 polyphenyl polymer Polymers 0.000 title claims description 5
- 150000003568 thioethers Chemical class 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 11
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- 235000010265 sodium sulphite Nutrition 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 11
- 229940117389 dichlorobenzene Drugs 0.000 claims description 9
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical group CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims description 2
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 18
- 239000004734 Polyphenylene sulfide Substances 0.000 abstract description 17
- 229920000069 polyphenylene sulfide Polymers 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- -1 halogen aromatic compound Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 235000011008 sodium phosphates Nutrition 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000009156 water cure Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229920000412 polyarylene Polymers 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000013003 hot bending Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009818 secondary granulation Methods 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- 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
The present invention relates to a method for preparing high-density linear high molecular weight polyphenylene sulfide, which comprises the following steps: (1) a deep blue addition compound is generated at the temperature of 120 to 220DEG C, and the molar ratio of sulfide to phosphate to a solvent is 1.0: (0.2 to 0.3): (0.5 to 2.5); (2) a halogenated aromatic compound dissolved in the solvent is added to generate a prepolymer at the temperature of 160 to 240DEG C, and the time is from 10 to 30 minutes; (3) a high-density polymer is generated at the temperature of 240 to 280DEG C at the pressure of 0.05 to 0.6MPa. The present invention has the advantages of easy acquirement of raw materials, low cost, high molecular weight of molecules of the generated polymer, and narrow molecular weight distribution of the generated polymer. The density of the generated polymer reaches 1360 to 1430 kg/m. The present invention is suitable for the preparation of the polyphenylene sulfide on an industrial scale.
Description
The present invention is relevant with the method that low pressure prepares high-density high-molecular linear polyphenyl thioether.
CN1225106 A has described a kind of preparation method of sulfur-containing polymer, be that trihydrate with sodium sulphite is dissolved in the N-Methyl pyrrolidone (NMP), distill out condensation product, the dichlorobenzene (DCB) that will be dissolved in again among the NMP adds, carried out 1 hour 230 ℃ of pre-polymerizations, reactor returns normal pressure then, with the trihydrate adding of sodium sulphite, distillation water outlet, mixture heating up to 230 ℃, the DCB that will be dissolved in addition among the NMP adds, at 230 ℃, and polymerization of mixtures 1.5 hours.This method need be with low water cure sodium as the sulphur source, purity low (＜95%), particle is solid, is difficult for storing, and reactive behavior is low, particle sodium sulphite and halogen aromatic compound carry out the leading portion reaction and generate low molecular weight product, reaction times 1-6 hour, inhomogeneous reaction generated low molecular weight product, molecular weight differs greatly, for the hypomere polycondensation brings very big difficulty.Second-stage reaction carries out under normal pressure, and inhomogeneous reaction because the molecular weight of one section resultant of reaction differs greatly, differs greatly the molecular weight product of final acquisition fully, and aberration is big (white, grey, tawny), density 1150-1320kg/m
3, it is also very big that molecular weight differs.The about 7000-of molecular-weight average, 20000g/mol; Wherein molecular weight is lower than 1000 part and accounts for 15-25%.
CN1145376A has described a kind of method for preparing the high-molecular linear poly arylidene thio-ester, be to be the sulphur source with the industrial sodium sulfide, with the non-proton polar organic compound of high boiling point is solvent, adopt polycomponent composite catalyst or auxiliary agent, at normal pressure partial dehydration in of short duration still, directly carry out stage feeding polymerization, make the white granular polyarylene sulfide resin with many halogenated aromatic compounds.Polyreaction divides two sections to carry out, and fs temperature 100-210 ℃, time 0.5-6 hour, 200-280 ℃ of subordinate phase temperature, the time is 0.5-6 hour.Yield 92%, viscosity 1500 pools.There is the part shortcoming described in the epimere equally.
United States Patent (USP) 3354129,3919177, the clear 58-47026 of Japanese Patent, clear 58-125721, clear 61-7332 have described the method that is prepared (arylene sulfide) by aromatics, comprise the sulphur source, P-two halobenzenes, organic amide, alkali, alkali metal carboxylate form composition together, and the retaining part composition generates polymkeric substance under polymerizing condition at least.One of embodiment is for adding sodium sulphite, the NMP of sodium to the high pressure stirring tank, with mixture at N
2Be heated to 202 ℃ under the gas unhurried current, 2 hours time, distillate water, be cooled to 175 ℃, the 1.4-dichlorobenzene (DCB) that will be dissolved in NMP adds in the reactor, and heating is 20 minutes under 30Psig pressure, and temperature reaches 245 ℃, 3 hours postcooling of heating under the 80-220Psig gauge pressure, washing, the dry lead solid polyphenylene sulfide that gets.
In sum, the shortcoming of prior art is as follows:
1. prepare polyarylene sulfide, polyphenylene sulfide (PPS) the sulphur source of being adopted particularly, the described method of patent CN102664B, CN1172823A all is Sodium sulphate anhydrous, 99mins, the described method of patent CN1145376A is the moisture industrial sodium sulfide that contains 0.5-7 water molecules, and the described method of patent CN1225106A is the moisture sodium sulphite that contains 3 water moleculess.The sulphur sodium that technical scale prepares Sodium sulphate anhydrous, 99min or contains partial crystallization water is the production cost height not only, also there is problem such as aspects such as technology, equipment, storages, after the sodium sulphite of even more serious is crystal form at high temperature loses part or all of crystal water, color and luster deepens, even become sorrel, form solid amorphous pellets, can only carry out at particle surface with the reaction of halogeno-benzene, activity is very low.
2. synthetic polyarylene sulfide, particularly polyphenylene sulfide, reaction process is a heterogeneous process, generally adopts the two-section type reaction.In first section reaction, solid-state sodium sulphite particle and be dispersed in the halogeno-benzene reaction 2～12 hours that is drop (oil droplet) state in the strong polar organic solvent, it is extremely inhomogeneous to generate the molecular weight size, the performed polymer of viscosity 0.5～30Pa.S.The performed polymer that this molecular weight differs greatly, it is very bad entering the subordinate phase polycondensation, subordinate phase improves 20～60 ℃ of temperature of reaction, reacts 4～8 hours, makes to continue to take place polycondensation between the performed polymer particle.
3. owing to above-mentioned important reaction process of two steps is all carried out in heterogeneous state, particularly in the subordinate phase reaction process, the performed polymer surface reaction speed and the there was no significant difference of various molecular weight, the polyphenylene sulfide for preparing under the same processing condition in the laboratory, physical index differs several times to tens times, and molecular weight distribution is very wide, need carry out strict refinement treatment, account for resin total amount 15-25% to remove, molecular weight is lower than the oligopolymer of 10000 gram/moles.Open flat 6-192423 (1994) as the spy of Philips house journal, the spy opens flat 6-192423 (1994), and the spy opens flat 7-3022 described methods such as (nineteen ninety-fives).
4. because there are the problems referred to above in conventional art, and the polymkeric substance color and luster of preparation differs greatly (white, grey, tawny), and particle is inhomogeneous, mostly is Powdered, unit weight only reaches 115～280kg/m
3, density only reaches 1150～1320kg/m
3The polyphenylene sulfide density value is 1440kg/m
3, the gap of conventional art is very big.
5. the polyphenylene sulfide of method for preparing, no matter be granular substance or meal, its density very little, store transportation inconvenience, post-treatment is generally wanted to handle with the pre-granulation of twin screw extruder earlier, and then filler reinforcement, as add glass, and the charcoal fiber, inorganic materials etc. are carried out secondary granulation, prepare various constituents for technical scale, cost is very high, be bad.
The purpose of this invention is to provide a kind of raw material and be easy to get, inexpensive, product particle is even, and products molecule has linear structure, molecular weight height, and the preparation method of the high-density high-molecular linear polyphenyl thioether of narrow molecular weight distribution.
The present invention is achieved in that
The present invention prepares the method for high-density polyphenylene sulfide, comprises the steps:
(1) mol ratio of sodium sulphite, phosphoric acid salt and the solvent of adding reactor is: 1.0: 0.2-0.3: 0.5-2.5 generates avy blue addition mixture at temperature 120-220 ℃;
(2) adding the halogenated aromatic compound that is dissolved in solvent in the addition mixture, is 180-230 ℃ in temperature, and the time is that 10-30 divides inner reaction still internal reaction to generate prepolymer;
(3) temperature of reaction kettle is 240-280 ℃, and pressure is that 0.05-0.6MPa generates polymkeric substance.
Solvent of the present invention is HMPA HPT, and phosphoric acid salt is sodium phosphate, and sodium sulphite is to contain nine molecular water sodium sulphite xln.
The addition mixture in the step of the present invention (2) and the mol ratio of halogenated aromatic compound are 1.0: 0.3～0.6.
The mol ratio of addition mixture of the present invention and halogenated aromatic compound is 1.0: 0.40.6.
The mol ratio of sodium sulphite, phosphoric acid salt and solvent in the step of the present invention (1) is 1.0: 0.20～0.25: 1.2～1.8, and temperature of reaction is 150～190 ℃, and the temperature of step (2) is 180～230 ℃, and the pressure of step (3) is 0.1～0.6MPa.
Said halogenated aromatic compound is diiodo-benzene or dibromo-benzene or dichlorobenzene in the step of the present invention (2).
Dichlorobenzene of the present invention is the mixture of 1.4-santochlor and 1.3-Meta Dichlorobenzene, is 4 to the mol ratio of a benzene and a benzene: 1-9: 1.
The temperature of reaction of step of the present invention (2) is 190～220 ℃.
The present invention has following unusual effect:
1. having adopted the crystalline sodium sulfide that contains nine molecular waters is the sulphur source, and nine water cure sodium are prismatic crystal, and stable in properties is easy to store, and industrial preparation is simple, and is with low cost.
2. the addition mixture for preparing sodium sulphite and phosphoric acid salt and polar solvent, this is a key of the present invention.80～250 ℃ of scopes, sodium sulphite, sodium phosphate and solvent generate the addition mixture, take on a red color in 90～125 ℃ of scopes, are avy blue in 140～230 ℃ of scopes.Mixture is by forming of determining: Na
2S: HPT: (NaO)
3PO=1: 1: 0.2, under processing condition of the present invention, mixture was dissolved in the excessive polar solvent fully, is in metastable state, has very high reactive behavior.Because mixture is metastable, temperature effect is very big, when temperature is higher than 180 ℃, and mixture active good, very fast with the santochlor speed of response, generation prepolymer molecular size is even.When temperature was lower than 130 ℃, the activity of mixture was lower, and the prepolymerization reaction time is long, and the performed polymer molecular weight that generates differs greatly, and the yield of remarkably influenced sintetics and quality are disadvantageous.
3. the active sulphur in the halogenated aromatic compound (atomic little " oil droplet ") of high dispersing in polar solvent and the mixture is generated performed polymers 180～230 ℃ of reactions, because reaction process is carried out in homogeneous phase (or accurate homogeneous phase) system, speed of response is very fast, promptly accuses at 10～30 minutes and finishes.The performed polymer molecular size that the what is more important reaction is generated is basic identical, and this is significant for the simple linear polymer that further aggregates into molecular weight height, narrow distribution range.
4. another key element of the present invention is to adopt the halogenated aromatic mixture, when the consumption of 1.4-santochlor and 1.3-Meta Dichlorobenzene 3: 2-9: in 1 scope, preferably 4: 1-9: in 1 scope, the solubleness of performed polymer in the polar solvent HMPA obviously increases, and the more single use of the product performance index 1.4-santochlor that obtains by polycondensation significantly improves again.
5. the follow procedure heating mode is brought up to prepolymer system 240～280 ℃ of scopes rapidly and is carried out polycondensation, and processing condition are very stable.Because the performed polymer molecular size is basic identical, speed of response is very fast, promptly accuses in 1-4 hour to finish, and obtains the thread-like molecule structure and the molecular weight of expection, and the polymkeric substance concentrated of molecular weight distribution.The feature of polymkeric substance is the whiteness height, uniform particles, and particle diameter 〉=0.147 millimeter, unit weight reaches 450-700kg/m
3, density reaches 1360-1430kg/m
3The high-quality polyphenylene sulfide, can be directly used in the high strength injection-molded item, high tenacity membrane product and fibre product.
6. tree refers to that density reaches 1360-1430kg/m
3, be convenient to store transportation, handle without pre-granulation and promptly can easily add glass, charcoal fiber, inorganic materials and carry out reinforcement.
7. polyreaction is carried out under 0.1-0.6MPa low pressure, makes less demanding to reactor; Polyreaction is more stable than conventional art polymerization under atmospheric pressure condition; Adopt the mesohigh polymerizing condition than foreign patent, facility investment significantly reduces.Prepare polyphenylene sulfide for technical scale, this is good.
Following is embodiments of the invention:
Embodiment 1:
In 2500 liters of stainless steel reactors, add nine water crystallization sodium sulphite, 3.0 kilomols, sodium phosphate 0.66 kilomol, 800 kilograms of HMPA are warming up to 180 ℃ of reactions 2 hours under stirring, discharge excess water simultaneously, add 1.4-santochlor 2.75 kilomols, 1.3-Meta Dichlorobenzene 0.31 kilomol, 400 kilograms of HMPA, be warming up to 210 ℃ rapidly, reacted 10 minutes.Be rapidly heated again to 245 ℃ of reactions 3 hours, be cooled to below 80 ℃, the centrifugation granulated polymer, with 80 ℃ of hot washes to neutral, with 80 ℃ of deionized water wash 2 times, again through 120 ℃ of drying under reduced pressure 6 hours, get 311.5 kilograms of whole white granulated polymers, yield 96%, physical index sees Table 1, table 2.
Adopt nine water cure sodium method composite polymeric low pressure reaction novel procesies.Build up 200t/a polyphenylene sulfide (PPS) resin production plant.Reactor volume is 2 500 liters.Carry out the continuous dosing test run, reach following index:
Throughput: 800kg/ days, 200 tons/year (250 days/year)
Synthesis cycle: 6-8 hour/still
Single still charging capacity: 2000 kilograms (raw material, auxiliary agent, solvent)
The rate of recovery: 95-98%
Solvent consumption:＜200kg/ ton PPS resin (HMPA)
Quality product: fusing point 280-292 ℃.Melt turnover＜100g/316 ℃-5kg-10min, density 1360-1430kg/m
3
Resin outward appearance: whole white particulate state, particle diameter＞0.100 millimeter.
Virgin resin performance: molecular weight Mv61000-64000 tensile strength＞87MPa.Extension at break＞22%, flexural strength＞150MPa, cantilever notched Izod impact strength＞18J/m, hot bending shape temperature＞142 ℃, volume resistance 4.2 * 10
15Ω M, surface resistivity 6.2 * 10
14Ω.
Relatively see Table 3 with U.S. with Philips company product performance
Relatively see Table 4 with U.S. Philips company state of the art
Embodiment 2-6
Change processing parameter, press embodiment 1 operation, the results are shown in Table 1, table 2.
Comparative example 1:
In 5 liters of lining titanium reactors, add 5.0 moles in three water cure sodium, 1.0 moles of sodium phosphates, HMPA 1250 grams are warming up to 120 ℃ under stirring, and react 2.5 hours, discharge excess water simultaneously, add 4.4 moles of 1.4-santochlor, 0.5 mole of 1.3-Meta Dichlorobenzene is warming up to 220 ℃ rapidly, reacted 10 minutes, be rapidly heated again to 250 ℃, reacted 4 hours, be cooled to 80 ℃, suction filtration, take out with 80 ℃ of hot water and to be washed till neutrality, with 80 ℃ of deionized water wash 2 times, again through 120 ℃ of drying under reduced pressure 12 hours, get beige polymer powder 421 grams, yield 78%, physical index sees Table 1, table 2.
Comparative example 2-5
Change processing parameter, press comparative example 1 operation, the results are shown in Table 1, table 2.
Following is subordinate list: table 1:
| Compound | Pre-polymerization | |||||
| Temperature of reaction | Time (branch) | Color | Mixed dichlorobenzene (molecular ratio) | Temperature of reaction (℃) | Reaction times (branch) | |
| Embodiment 1 | 160 | 150 | Avy blue | 4∶1 | 220 | 10 |
| Embodiment 2 | 160 | 150 | Avy blue | 9∶1 | 210 | 15 |
| Embodiment 3 | 180 | 120 | Avy blue | 17∶3 | 225 | 20 |
| Embodiment 4 | 150 | 180 | Bright avy blue | 17∶3 | 195 | 30 |
| Embodiment 5 | 140 | 100 | Avy blue | 4∶1 | 200 | 15 |
| Embodiment 6 | 160 | 160 | Avy blue | 9∶1 | 215 | 10 |
| Comparative example 1 | 120 | 210 | Blue green | 3∶1 | 220 | 10 |
| Comparative example 2 | 190 | 120 | Blue green | 3∶1 | 210 | 15 |
| Comparative example 3 | 130 | 180 | Deep blue green | 19∶1 | 180 | 25 |
| Comparative example 4 | 210 | 120 | Blue purple | 210 | 10 | |
| Comparative example 5 | 230 | 90 | Blue green | 20∶1 | 180 | 30 |
| Polymerization | Product | ||||||
| Temperature of reaction (℃) | Time (branch) | Output (kg) | Yield (%) | Outward appearance | Particle diameter (μ) | Density kg/m3 | |
| Embodiment 1 | 275 | 240 | 311.5 | 96.0 | White particle | ≥147 | 1360 |
| Embodiment 2 | 240 | 150 | 310.1 | 95.7 | White particle | ≥147 | 1385 |
| Embodiment 3 | 250 | 90 | 312.0 | 96.3 | White particle | ≥175 | |
| Embodiment 4 | 265 | 210 | 308.0 | 95.0 | White particle | ≥240 | 1430 |
| Embodiment 5 | 245 | 120 | 300.8 | 92.8 | White particle | ≥175 | 1426 |
| Embodiment 6 | 255 | 60 | 310.5 | 95.8 | White particle | ≥147 | 1410 |
| Comparative example 1 | 250 | 240 | 421.0g | 78.0 | Beige | Powder | 1320 |
| Comparative example 2 | 245 | 280 | 440.0g | 81.5 | Beige | ＜74 | 1356 |
| Comparative example 3 | 250 | 240 | 450.0g | 83.4 | White | Powder | 1335 |
| Comparative example 4 | 245 | 210 | 450.5g | 83.4 | Beige | ＜74 | 1352 |
| Comparative example 5 | 255 | 220 | 443.0g | 82.0 | Beige | Powder | 1300 |
Table 2:
| Acetone solution thing % | Limiting viscosity ml/g | Tm ℃ | Melt flow rate (MFR) | Low shear viscosity Pa.S (303 ℃) | Thermostability % | Volume resistance (Ω .M * 10 15 | |
| Embodiment 1 | 1.68 | 45 | 291 | 26 | - | 11.0 | 6.2 |
| Embodiment 2 | 2.15 | 42 | 290 | 35 | - | 3.0 | 7.0 |
| Embodiment 3 | 0.54 | 45 | 282 | 57 | - | 3.6 | 5.3 |
| Embodiment 4 | 0.86 | 41 | 280 | 82 | - | 7.2 | 5.0 |
| Embodiment 5 | 3.21 | 37 | 278 | 95 | - | 8.5 | 7.8 |
| Embodiment 6 | 1.12 | 40 | 281 | 76 | - | 16 | 7.8 |
| Comparative example 1 | 15.7 | 16 | 275 | - | 15 | Decompose | - |
| Comparative example 2 | 6.2 | 22 | 280 | - | 91 | The slight decomposition | - |
| Comparative example 3 | 11.0 | 19 | 272 | - | 22 | Decompose | - |
| Comparative example 4 | 4.6 | 26 | 279 | - | 65 | The slight decomposition | - |
| Comparative example 5 | 12.1 | 17 | 269 | - | 12 | Decompose | - |
Annotate: 1. α-chloronaphthalene, 206 ℃ of 2. GB3682,316 ℃, 5kg, 10 minutes
3. 316 ℃, 5kg, 30 minutes
④GB/T1410
Table 3:
| Project | Philips company | This technology | |
| 1 | Molecular structure | Degree of crosslinking＞50% | No crosslinked |
| 2 | Density | 1.32g/cm3 | 1.43g/cm3 |
| 3 | Tap density | Patent data data＜0.3g/ml | ＞0.6g/cml |
| 4 | Heat-drawn wire | 94.8℃ | 142℃ |
| 5 | The disconnected elongation of attacking | 4％ | 22％ |
More than 5 important indicators be better than Philips company, other ten indexs are basic identical, but Philips PPS is by crosslinking Treatment, this is the difference of matter.
Table 4
| Project | Philips company | This technology | |
| 1 | Working pressure | 15-20kg/cm 2 | 1-6kg/cm 2(low pressure) |
| 2 | Polymerization cycle | 8-10h | 2-4h |
| 3 | Ton product solvent consumption | 400-500kg | 150-200kg |
| 4 | Three wastes treatment process | Complicated | Simply |
Annotate: present commercially available solvent 40-50 unit/kg, solvent consumption is the key of PPS cost.
Claims (9)
1, a kind of method for preparing high-density high-molecular linear polyphenyl thioether comprises the steps:
(1) mol ratio of sodium sulphite, phosphoric acid salt and the solvent of adding reactor is: 1.0: 0.2-0.3: 0.5-2.5 generates the addition mixture at temperature 120-220 ℃;
(2) adding the halogenated aromatic compound that is dissolved in solvent in the addition mixture, is 160-240 ℃ in temperature, and the time is that 10-30 divides inner reaction still internal reaction to generate prepolymer;
(3) temperature of reaction kettle is 240-280 ℃, and pressure is that 0.05-0.6MPa generates polymkeric substance.
2, method according to claim 1 is characterized in that solvent is a HMPA, and phosphoric acid salt is sodium phosphate, and sodium sulphite is to contain nine molecular water sodium sulphite xln.
3, method according to claim 1 is characterized in that the addition mixture in the step (2) and the mol ratio of halogenated aromatic compound are 1.0: 0.3～0.6.
4, method according to claim 3, the mol ratio that it is characterized in that addition mixture and halogenated aromatic compound are 1.0: 0.4～0.5.
5, method according to claim 1, the mol ratio that it is characterized in that sodium sulphite, sodium phosphate and solvent in the step (1) is 1.0: 0.20～0.25: 1.2～1.8, temperature of reaction is 150～190 ℃, the temperature of step (2) is 180～230 ℃, and the pressure of step (3) is 0.1～0.6MPa.
6,, it is characterized in that said halogenated aromatic compound is diiodo-benzene or dibromo-benzene or dichlorobenzene in the step (2) according to claim 1 or 2 or 3 or 4 or 5 described methods.
7, method according to claim 6 is characterized in that said dichlorobenzene is the mixture of 1.4-santochlor and 1.3-Meta Dichlorobenzene, is 3 to the mol ratio of a benzene and a benzene: 2-9: 1.
8, method according to claim 7 is characterized in that the mol ratio to a benzene and a benzene is 4: 1～9: 1.
9, method according to claim 5, the temperature of reaction that it is characterized in that step (2) is 190～220 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00120629A CN1095481C (en) | 2000-12-27 | 2000-12-27 | Process for preparing high-density high-molecular linear polyphenyl thioether |
| PCT/CN2001/001637 WO2002051910A1 (en) | 2000-12-27 | 2001-12-20 | The high-density high-molecular linear polyphenylene sulfide polymers and the processes of preparing the polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00120629A CN1095481C (en) | 2000-12-27 | 2000-12-27 | Process for preparing high-density high-molecular linear polyphenyl thioether |
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| Publication Number | Publication Date |
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| CN1309142A CN1309142A (en) | 2001-08-22 |
| CN1095481C true CN1095481C (en) | 2002-12-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00120629A Expired - Fee Related CN1095481C (en) | 2000-12-27 | 2000-12-27 | Process for preparing high-density high-molecular linear polyphenyl thioether |
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| Country | Link |
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| CN (1) | CN1095481C (en) |
| WO (1) | WO2002051910A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501106B (en) * | 2006-08-17 | 2011-11-09 | Dic株式会社 | Method for producing polyarylene sulfide resin |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328303C (en) * | 2005-12-29 | 2007-07-25 | 四川得阳科技股份有限公司 | Tech., for polymerizing fibre grade polyphenyl sulfoether resin |
| CN102676048B (en) * | 2012-06-07 | 2014-05-07 | 成都乐天塑料有限公司 | Modified polyphenylene sulfide coating and application thereof |
| CN103242528B (en) * | 2013-04-22 | 2015-08-19 | 中国石油化工股份有限公司 | A kind of synthetic method of high-molecular linear polyphenyl thioether |
| CN103642042A (en) * | 2013-09-22 | 2014-03-19 | 上海大学 | Synthetic method of polyphenylene sulfide |
| CN105085917A (en) * | 2015-08-05 | 2015-11-25 | 广州高八二塑料有限公司 | Film-grade polyphenylene sulfide resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60200808A (en) * | 1984-03-27 | 1985-10-11 | Dainippon Ink & Chem Inc | Production of sodium sulfide composition for arylene sulfide polymer and manufacture of said polymer |
| JPS61111329A (en) * | 1984-11-05 | 1986-05-29 | Dainippon Ink & Chem Inc | Production of arylene sulfide polymer |
| JPS6220528A (en) * | 1985-07-19 | 1987-01-29 | Asahi Glass Co Ltd | Production of high-molecular weight polyphenylene sulfide |
| CN85109096A (en) * | 1985-12-14 | 1987-06-24 | 四川大学 | A kind of synthetic method of linear polyphenylthioether of high molecular weight |
| JPS62190228A (en) * | 1986-02-17 | 1987-08-20 | Dainippon Ink & Chem Inc | Production of polyarylene sulfide |
| JPS62202529A (en) * | 1986-03-01 | 1987-09-07 | Toshiba Seiki Kk | Pellet mounting device |
| US5688908A (en) * | 1995-04-13 | 1997-11-18 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic sulfur-containing polymers |
| CN1172823A (en) * | 1997-02-05 | 1998-02-11 | 徐登顺 | Industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59221331A (en) * | 1983-05-31 | 1984-12-12 | Dainippon Ink & Chem Inc | Production of polyphenylene sulfide |
| CN85102664B (en) * | 1985-04-01 | 1987-08-26 | 四川大学 | Process for synthesis of linear polyphenylthioether of high molecular weight |
-
2000
- 2000-12-27 CN CN00120629A patent/CN1095481C/en not_active Expired - Fee Related
-
2001
- 2001-12-20 WO PCT/CN2001/001637 patent/WO2002051910A1/en not_active Application Discontinuation
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60200808A (en) * | 1984-03-27 | 1985-10-11 | Dainippon Ink & Chem Inc | Production of sodium sulfide composition for arylene sulfide polymer and manufacture of said polymer |
| JPS61111329A (en) * | 1984-11-05 | 1986-05-29 | Dainippon Ink & Chem Inc | Production of arylene sulfide polymer |
| JPS6220528A (en) * | 1985-07-19 | 1987-01-29 | Asahi Glass Co Ltd | Production of high-molecular weight polyphenylene sulfide |
| CN85109096A (en) * | 1985-12-14 | 1987-06-24 | 四川大学 | A kind of synthetic method of linear polyphenylthioether of high molecular weight |
| JPS62190228A (en) * | 1986-02-17 | 1987-08-20 | Dainippon Ink & Chem Inc | Production of polyarylene sulfide |
| JPS62202529A (en) * | 1986-03-01 | 1987-09-07 | Toshiba Seiki Kk | Pellet mounting device |
| US5688908A (en) * | 1995-04-13 | 1997-11-18 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic sulfur-containing polymers |
| CN1172823A (en) * | 1997-02-05 | 1998-02-11 | 徐登顺 | Industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501106B (en) * | 2006-08-17 | 2011-11-09 | Dic株式会社 | Method for producing polyarylene sulfide resin |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002051910A1 (en) | 2002-07-04 |
| CN1309142A (en) | 2001-08-22 |
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