CN108948355A - A method of polyphenylene sulfide is prepared using benzene and sulphur as raw material - Google Patents
A method of polyphenylene sulfide is prepared using benzene and sulphur as raw material Download PDFInfo
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- CN108948355A CN108948355A CN201810837783.7A CN201810837783A CN108948355A CN 108948355 A CN108948355 A CN 108948355A CN 201810837783 A CN201810837783 A CN 201810837783A CN 108948355 A CN108948355 A CN 108948355A
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- polyphenylene sulfide
- benzene
- sulphur
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 82
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 82
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000005864 Sulphur Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002994 raw material Substances 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000012043 crude product Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 27
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical class ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims 1
- 229910000431 copper oxide Inorganic materials 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 8
- 238000004064 recycling Methods 0.000 description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- -1 polyphenylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 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
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
-
- 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
-
- 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
- C08G75/0263—Preparatory processes using elemental sulfur
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 invention discloses a kind of methods for preparing polyphenylene sulfide as raw material using benzene and sulphur, the following steps are included: (1) sequentially adds solvent, inorganic salt catalyst in reaction kettle, stirring is opened, sulphur is then added, continues stirring until and forms uniform suspension in reaction kettle；(2) it is added benzene into suspension, adjusts reactor temperature to 60~100 DEG C, 0.5~1.5h of isothermal reaction；(3) reactor temperature is adjusted to 120~170 DEG C, 2~6h of isothermal reaction；(4) reactor temperature is adjusted to being lower than 40 DEG C, is separated by solid-liquid separation, is obtained polyphenylene sulfide crude product；(5) poly-p-phenylene sulfide ether resin crude product is washed, is dried, and obtains polyphenylene sulfide.Benzene of the present invention synthesizes noncrystalline polyphenylene sulfide with sulfur reaction, it is not easy to be processed at film or fiber because of crystallinity height to solve the problems, such as existing polyphenylene sulfide, and product purity is high, solvent is easily recycled, and production cost is low, substantially reduces " three wastes ".
Description
Technical field
The invention belongs to the technical field of producing of polyphenylene sulfide, and in particular to a kind of to prepare using benzene and sulphur as raw material
The method of polyphenylene sulfide.
Background technique
Polyphenylene sulfide full name is polyphenylene thioether, is the thermoplastic resin that thiophenyl is had in molecular backbone, unstretched
Fiber have biggish amorphous region (crystallinity is about 5%), stretch fiber generate crystallization during stretching, crystallinity can
Up to 60-80%.The synthetic method of polyphenylene sulfide mainly has sodium sulfide method, sulfur solution route, hydrogen sulfide method, oxidative polymerization method, right
The polyphenylene sulfide of halogenated benzenethiol condensation methods etc., the synthesis of these methods has excellent thermal property and electric property, in short term may be used
Resistance to 260 DEG C, and can be used for a long time at 200~240 DEG C, compared with other engineering material, the dielectric constant of polyphenylene sulfide and Jie
It is all relatively low at value is cut that power consumption damages angle, and changes less in biggish frequency, temperature and temperature range, also, polyphenylene sulfide
One of the feature of ether maximum is that chemical corrosion resistance is good, to big polyacid, ester, copper, phenol and fat warp, fragrance warp, chloro through etc. it is steady
It is fixed.
Although polyphenylene sulfide has many advantages, pure polyphenylene sulfide is rarely employed because performance is crisp, practical application
Polyphenylene sulfide is usually its transformed lines show, such as glass fiber reinforcement, inorganic fill, fibre reinforced, can not fundamentally be changed
Become the high essence of its crystallinity, and the polyphenylene sulfide that strand regularity is strong, crystallinity is high is not easy to be processed at film or fiber, limit
The application field and use scope of polyphenylene sulfide are made.
In addition, large quantity of exhaust gas (hydrogen sulfide gas and NMP steam etc.) can be generated in the synthesis process of traditional polyphenylene sulfide, given up
Liquid (dehydration liquid, water lotion etc.) and useless solid (by-product salt and the polyphenylene sulfide of low molecular weight etc.), causes serious environmental pollution,
Also, solvent-oil ratio is big, and catalyst recycling is difficult, and high production cost, obtained polyphenylene sulfide purity is low, contains more nothing
Machine salt leads to the easy moisture absorption of resin, influences the performances such as its moisture-proof, electrical resistance and mouldability.
Summary of the invention
It is an object of the invention to: for above-mentioned existing polyphenylene sulfide because crystallinity height is without being easily processed into film or fibre
The problem of tieing up, its application field and use scope is caused to be restricted, the present invention provide a kind of using benzene and sulphur as raw material preparation
The method of polyphenylene sulfide.
The technical solution adopted by the invention is as follows:
A method of polyphenylene sulfide is prepared using benzene and sulphur as raw material, comprising the following steps:
(1) solvent, inorganic salt catalyst are sequentially added in reaction kettle, opens stirring, sulphur is then added, it is lasting to stir
Uniform suspension is formed in reaction kettle；
(2) benzene is added in the suspension formed to step (1), adjust reactor temperature to 60~100 DEG C, isothermal reaction
0.5~1.5h；
(3) reactor temperature is adjusted to 120~170 DEG C, 2~6h of isothermal reaction；
(4) reactor temperature is adjusted to being lower than 40 DEG C, and material in reactor is separated by solid-liquid separation, polyphenylene sulfide is obtained
Resin crude product；
(5) the polyphenylene sulfide crude product obtained to step (4) is washed, is dried, and obtains polyphenylene sulfide.
Further, in step (1), the molar ratio of solvent and inorganic salt catalyst is 1:(0.03~0.05), inorganic salts
The molar ratio of catalyst and sulphur is (0.015~0.05): 1.
Further, in step (1), solvent 1,2,4- trichloro-benzenes.
Further, in step (1), inorganic salt catalyst is nanometer lithium chloride, nanometer magnesium chloride, nanometer aluminium chloride, receives
Rice zinc chloride, nano cupric oxide, nano copper iodide, nano Pd particle (OAc) 2, Ni nanoparticle (OAc) one of 2 or a variety of.Nanoscale
Catalyst surface area it is bigger, catalyst atoms are easier to bombard phenyl ring and form active site, to improve the anti-of benzene and sulphur
Answer activity.
Further, in step (2), the molar ratio of benzene and sulphur is (1~1.05): 2.
Further, in step (2), reactor temperature is adjusted with the heating rate of 5~6 DEG C/min.
Further, in step (3), reactor temperature is adjusted with the heating rate of 5~6 DEG C/min.
Further, in step (4), the liquid after separation of solid and liquid is sent to mother liquor temporary tank.
Further, in step (5), the method for polyphenylene sulfide crude product washing are as follows: send polyphenylene sulfide crude product
Enter in washing kettle, be 1:(3~5 according to solid-to-liquid ratio) ratio be added methanol into washing kettle, open stirring, adjust in washing kettle
Temperature is 40~60 DEG C, then 0.5~1h of constant temp is separated by solid-liquid separation, obtains polyphenylene sulfide.
Further, in step (5), polyphenylene sulfide crude product washing after liquid be sent into methanol temporary tank, it is subsequent again
It send to rectifying column and is separated.
Further, in step (5), dry method are as follows: the polyphenylene sulfide after washing is sent into vacuum oven,
It is dried under reduced pressure at 50~100 DEG C to moisture percentage≤0.3% of polyphenylene sulfide.
Further, it is separated by solid-liquid separation using equipment for separating liquid from solid, equipment for separating liquid from solid is centrifuge, filter press or pumping
Filter.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1. the present invention replaces traditional paracide with benzene, amorphous polyphenylene sulfide is synthesized with sulfur reaction, is overcome
The polyphenylene sulfide of existing production technology preparation is because strand regularity is strong, crystallinity is high and not easy to be processed at film or fiber
Problem, greatly extends the application field and use scope of polyphenylene sulfide, and the reaction process of benzene and sulphur is as follows:
2. conventionally employed can generate small-molecule substance and by-product salt when using paracide as raw material during the reaction,
Increase post-processing difficulty, polyphenylene sulfide purity is low, also, the heated easily gasification of paracide, and easily crystallization, synthetic reaction finish to the cold
Afterwards, not having the paracide of fully reacting can crystallize in kettle wall, it is difficult to and it clears up, directly affects the material proportion of next kettle, the present invention
Using benzene and sulphur as Material synthesis polyphenylene sulfide, small-molecule substance and by-product salt will not be generated in synthesis process, obtained polyphenyl
Thioether purity is high, can avoid completely by-product salt from having an adverse effect the performances such as its moisture-proof, electrical resistance and mouldability, also,
Benzene will not remain on kettle wall；
3. the present invention is solvent using 1,2,4- trichloro-benzenes, the boiling point of 1,2,4- trichloro-benzenes is 221 DEG C, in reaction temperature model
In enclosing, 1,2,4- trichloro-benzenes will not evaporate to form exhaust gas, and be washed using methanol poly-p-phenylene sulfide ether resin crude product, replace and pass
System washing, due to inorganic salt catalyst and 1,2,4- trichloro-benzenes are soluble in hot methanol, and therefore, washing times are few, improve production
Efficiency, can also save water resource, not will form washing waste liquid, in addition, methanol and 1, the boiling point of 2,4- trichloro-benzenes differs greatly, and
The two is not easy to form azeotropic mixture, and therefore, the rate of recovery of 1,2,4- trichloro-benzenes and inorganic salt catalyst is high, it can be achieved that solvent and inorganic
The recycling of salt catalyst effectively reduces the production cost of polyphenylene sulfide, meanwhile, and 1,2,4- trichloro-benzenes and inorganic
Methanol after salt catalyst separation can be repeatedly used for washing or used for other purposes；
4. polyphenylene sulfide synthetic route environmental protection of the present invention, not will form waste liquid, gives up admittedly, and reduce exhaust gas, significantly
The human and material resources and financial resources, the market competitiveness that reduction processing " three wastes " needs to put into are strong.
Specific embodiment
All features disclosed in this specification can be with any other than mutually exclusive feature and/or step
Mode combines.
Embodiment 1
A method of polyphenylene sulfide is prepared using benzene and sulphur as raw material, comprising the following steps:
(1) 1,2,4- trichloro-benzenes of 1mol, 0.04mol nano cupric oxide are sequentially added in reaction kettle, opens stirring, so
1mol sulphur is added afterwards, continues stirring until and forms uniform suspension in reaction kettle；
(2) 0.51mol benzene is added in the suspension formed to step (1), is adjusted with the heating rate of 5~6 DEG C/min anti-
Answer temperature in the kettle to 80 DEG C, isothermal reaction 1.5h；
(3) reactor temperature is adjusted to 130 DEG C with the heating rate of 5~6 DEG C/min, isothermal reaction 4h；
(4) reactor temperature is adjusted to being lower than 40 DEG C, and material in reactor is sent to centrifuge and is separated by solid-liquid separation, is obtained
To polyphenylene sulfide crude product, the liquid after separation is sent to mother liquor temporary tank, for recycling；
(5) polyphenylene sulfide crude product is sent into washing kettle, is added according to the ratio that solid-to-liquid ratio is 1:3 into washing kettle
Methanol opens stirring, and adjusting washing temperature in the kettle is 50 DEG C, constant temp 40min, is then sent to centrifuge and carries out solid-liquid point
From polyphenylene sulfide after being washed, the liquid after separation is sent into methanol temporary tank, and subsequent send again to rectifying column is divided
From；Polyphenylene sulfide after washing is sent into vacuum oven, is dried under reduced pressure at 50 DEG C to polyphenylene sulfide
Moisture percentage≤0.3% obtains polyphenylene sulfide.
Embodiment 2
A method of polyphenylene sulfide is prepared using benzene and sulphur as raw material, comprising the following steps:
(1) 1,2,4- trichloro-benzenes of 1mol, 0.03mol nanometers of aluminium chloride are sequentially added in reaction kettle, opens stirring, so
1mol sulphur is added afterwards, continues stirring until and forms uniform suspension in reaction kettle；
(2) 0.51mol benzene is added in the suspension formed to step (1), is adjusted with the heating rate of 5~6 DEG C/min anti-
Answer temperature in the kettle to 90 DEG C, isothermal reaction 1.5h；
(3) reactor temperature is adjusted to 150 DEG C with the heating rate of 5~6 DEG C/min, isothermal reaction 4h；
(4) reactor temperature is adjusted to being lower than 40 DEG C, and material in reactor is sent to centrifuge and is separated by solid-liquid separation, is obtained
To polyphenylene sulfide crude product, the liquid after separation is sent to mother liquor temporary tank, for recycling；
(5) polyphenylene sulfide crude product is sent into washing kettle, is added according to the ratio that solid-to-liquid ratio is 1:4 into washing kettle
Methanol opens stirring, and adjusting washing temperature in the kettle is 50 DEG C, constant temp 40min, is then sent to centrifuge and carries out solid-liquid point
From polyphenylene sulfide after being washed, the liquid after separation is sent into methanol temporary tank, and subsequent send again to rectifying column is divided
From；Polyphenylene sulfide after washing is sent into vacuum oven, is dried under reduced pressure at 50 DEG C to polyphenylene sulfide
Moisture percentage≤0.3% obtains polyphenylene sulfide.
Embodiment 3
A method of polyphenylene sulfide is prepared using benzene and sulphur as raw material, comprising the following steps:
(1) 1,2,4- trichloro-benzenes of 1mol, 0.05mol nano copper iodide are sequentially added in reaction kettle, opens stirring, so
1mol sulphur is added afterwards, continues stirring until and forms uniform suspension in reaction kettle；
(2) 0.52mol benzene is added in the suspension formed to step (1), is adjusted with the heating rate of 5~6 DEG C/min anti-
Answer temperature in the kettle to 95 DEG C, isothermal reaction 1.5h；
(3) reactor temperature is adjusted to 160 DEG C with the heating rate of 5~6 DEG C/min, isothermal reaction 4h；
(4) reactor temperature is adjusted to being lower than 40 DEG C, and material in reactor is sent to centrifuge and is separated by solid-liquid separation, is obtained
To polyphenylene sulfide crude product, the liquid after separation is sent to mother liquor temporary tank, for recycling；
(5) polyphenylene sulfide crude product is sent into washing kettle, is added according to the ratio that solid-to-liquid ratio is 1:5 into washing kettle
Methanol opens stirring, and adjusting washing temperature in the kettle is 50 DEG C, constant temp 40min, is then sent to centrifuge and carries out solid-liquid point
From polyphenylene sulfide after being washed, the liquid after separation is sent into methanol temporary tank, and subsequent send again to rectifying column is divided
From；Polyphenylene sulfide after washing is sent into vacuum oven, is dried under reduced pressure at 50 DEG C to polyphenylene sulfide
Moisture percentage≤0.3% obtains polyphenylene sulfide.
Embodiment 4
The polyphenylene sulfide prepared to embodiment 1- embodiment 3 detects, wherein the examination criteria of ash content is GB/
T9345.1-2008, the examination criteria of moisture percentage are GB/T6284-2006, and the examination criteria of whiteness is GB2913-1982, fusing point
Examination criteria be GB/T19466.3-2004, the examination criteria of melt flow rate (MFR) is GB/T 3682-2000, be the results are shown in Table
1.The result shows that the polyphenylene sulfide that the present invention is prepared using benzene and sulphur as raw material, ash content is lower, and whiteness is higher, and
Fusing point and melt sulfuric acid rate are relatively stable.
1 polyphenylene sulfide testing result of table
It is as described above the embodiment of the present invention.The present invention is not limited to the above-described embodiments, anyone should learn that
The structure change made under the inspiration of the present invention, the technical schemes that are same or similar to the present invention each fall within this
Within the protection scope of invention.
Claims (9)
1. a kind of method for preparing polyphenylene sulfide as raw material using benzene and sulphur, which comprises the following steps:
(1) solvent, inorganic salt catalyst are sequentially added in reaction kettle, opens stirring, sulphur is then added, continued stirring until anti-
It answers and forms uniform suspension in kettle；
(2) benzene is added in the suspension formed to step (1), adjust reactor temperature to 60~100 DEG C, isothermal reaction 0.5
~1.5h；
(3) reactor temperature is adjusted to 120~170 DEG C, 2~6h of isothermal reaction；
(4) reactor temperature is adjusted to being lower than 40 DEG C, and material in reactor is separated by solid-liquid separation, polyphenylene sulfide is obtained
Crude product；
(5) the polyphenylene sulfide crude product obtained to step (4) is washed, is dried, and obtains polyphenylene sulfide.
2. a kind of method for preparing polyphenylene sulfide as raw material using benzene and sulphur according to claim 1, which is characterized in that institute
State in step (1), the molar ratio of solvent and inorganic salt catalyst is 1:(0.03~0.05), inorganic salt catalyst and sulphur rub
You are than being (0.015~0.05): 1.
3. a kind of method for preparing polyphenylene sulfide as raw material using benzene and sulphur according to claim 1 or 2, feature exist
In, in the step (1), solvent 1,2,4- trichloro-benzenes.
4. a kind of method for preparing polyphenylene sulfide as raw material using benzene and sulphur according to claim 1 or 2, feature exist
In in the step (1), inorganic salt catalyst is nanometer lithium chloride, nanometer magnesium chloride, nanometer aluminium chloride, nanometer zinc chloride, receives
Rice copper oxide, nano copper iodide, nano Pd particle (OAc) 2, Ni nanoparticle (OAc) one of 2 or a variety of.
5. a kind of method for preparing polyphenylene sulfide as raw material using benzene and sulphur according to claim 1, which is characterized in that institute
It states in step (2), the molar ratio of benzene and sulphur is (1~1.05): 2.
6. a kind of method for preparing polyphenylene sulfide as raw material using benzene and sulphur according to claim 1, which is characterized in that institute
It states in step (2), reactor temperature is adjusted with the heating rate of 5~6 DEG C/min.
7. a kind of method for preparing polyphenylene sulfide as raw material using benzene and sulphur according to claim 1, which is characterized in that institute
It states in step (3), reactor temperature is adjusted with the heating rate of 5~6 DEG C/min.
8. a kind of method for preparing polyphenylene sulfide as raw material using benzene and sulphur according to claim 1, which is characterized in that institute
It states in step (5), the method for polyphenylene sulfide crude product washing are as follows: polyphenylene sulfide crude product is sent into washing kettle, according to
Solid-to-liquid ratio is 1:(3~5) ratio be added methanol into washing kettle, open stirring, adjusting washing temperature in the kettle is 40~60 DEG C,
0.5~1h of constant temp, is then separated by solid-liquid separation, and polyphenylene sulfide is obtained.
9. a kind of method for preparing polyphenylene sulfide as raw material using benzene and sulphur according to claim 1, which is characterized in that institute
State in step (5), dry method are as follows: by after washing polyphenylene sulfide be sent into vacuum oven, at 50~100 DEG C into
Row is dried under reduced pressure to moisture percentage≤0.3% of polyphenylene sulfide.
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