CN110256674A - A kind of synthetic method of high molecular weight poly arylidene thio-ester sulfone - Google Patents
A kind of synthetic method of high molecular weight poly arylidene thio-ester sulfone Download PDFInfo
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- CN110256674A CN110256674A CN201910639839.2A CN201910639839A CN110256674A CN 110256674 A CN110256674 A CN 110256674A CN 201910639839 A CN201910639839 A CN 201910639839A CN 110256674 A CN110256674 A CN 110256674A
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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
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
Abstract
The present invention relates to a kind of synthetic methods of high molecular weight poly arylidene thio-ester sulfone, by 4,4-dichlorodiphenyl sulfone (DCDPS), anhydrous sodium sulfide (Na2S), catalyst, solvent are put into reaction kettle together, nitrogen displaced air, pressurising 0.3-1Mpa；140 DEG C~190 DEG C are first warming up to, prepolymerization reaction 2h~4h is carried out；It is warming up to 230 DEG C~270 DEG C again, carries out polycondensation reaction 1h~3h；After polycondensation, N-Methyl pyrrolidone (NMP) solution of end-capping reagent is added in reaction kettle, then react 0.5h~1h；Then it is down to room temperature discharging, is separated by solid-liquid separation, solid washing is dried to obtain polyaryl thioether sulfone product.The polyaryl thioether sulfone weight average molecular weight of this method synthesis is all 40000 or more, and for yield all 92% or more, synthesis pressure is low, and simple process is easier to industrialized production.
Description
Technical field
The present invention relates to polymeric material fields, specifically relate to a kind of synthesis side of high molecular weight poly arylidene thio-ester sulfone
Method.
Background technique
Polyaryl thioether sulfone (PASS) is the structurally-modified product of polyphenylene sulfide (PPS), not only maintains special engineering plastics
Polyphenylene sulfide (PPS) excellent heat-resisting, corrosion resistance and excellent mechanical property, and due to having virtue in its molecular chain structure
Base sulfone structure, so that this polymer has anti-impact more superior than polyphenylene sulfide (PPS), bending resistance and mechanical behavior under high temperature.It is poly-
The performance ratio PPS of aromatic sulfide sulfone (PASS) is greatly improved, and purposes is also greatly extended, polyaryl thioether sulfone (PASS)
Although price and cost than polyphenylene sulfide (PPS) resin height, well below polyether-ether-ketone (PEEK), polyimides (PI) etc.
Other special engineering plastics are entirely capable of being acceptable to the market.PASS market orientation is in filling up between PPS resin and PEEK resin
Vacancy.Domestic polyaryl thioether sulfone (PASS) depends on import at present, and output in domestic is considerably less, the factory of large-scale production
Family is less, due to polyaryl thioether sulfone (PASS) in terms of military project using relatively more, so external manufacturer is to Chinese supply
There are many limitation.
The synthetic method of polyaryl thioether sulfone is all aqueous vulcanized sodium mostly at present and dichloro diphenyl sulfone is the autoclave of monomer
Synthetic system.Aqueous vulcanized sodium Na is used in patent CN1034677432S.XH2O and dichloro diphenyl sulfone are raw material, and chloronaphthalene is as anti-
Solvent is answered, in the case where lithium bromide is catalyst, prepares the polyaryl thioether sulfone of high molecular weight.Dichloro is used in patent CN104292463A
Diphenyl sulphone (DPS) and diphenyl ether and vulcanized sodium and dehydrating agent catalyst prepare polyaryl thioether sulfone, wherein catalyst in polar solvent
For the mixture of sulfuric acid trisodium and sodium acetate, the flexible group of high-content is introduced in this patent, overcomes polyaryl thioether sulfone note
The shortcomings that moulding processing difficulties.CN107501555A provides a kind of method of quickly synthesis in low temperature polyaryl thioether sulfone, catalysis used
Agent is the mixture of lithium chloride and lithium acetate, and synthesis temperature is lower, and generated time is relatively short.But above method needs sternly mostly
Lattice control each proportioning materials ratio, control dehydrating amount, and above method used catalyst amount is big, and a large amount of catalyst recycling are very tired
Difficulty, so that the production cost increases；In addition the polyaryl thioether sulfone molecular weight that such method obtains is low, comprehensive performance be difficult and it is external into
Mouth product compares favourably.
Summary of the invention
The object of the present invention is to provide a kind of synthetic methods of high molecular weight poly arylidene thio-ester sulfone, by using anhydrous sodium sulfide
For raw material, and that innovates uses rare earth catalyst, substantially reduces catalyst amount, saves production cost, and such method is closed
It is much higher at the polyaryl thioether sulfone molecular weight gone out, product comprehensive performance is greatly improved, industrial amplification production is conducive to.
Specific technical solution is as follows:
A kind of synthetic method of high molecular weight poly arylidene thio-ester sulfone, steps are as follows:
(1) by 4,4-dichlorodiphenyl sulfone (DCDPS), anhydrous sodium sulfide (Na2S), catalyst, solvent put into reaction kettle together
In, nitrogen displaced air, pressurising 0.3-1Mpa；
(2) 140 DEG C~190 DEG C are first warming up to, prepolymerization reaction 2h~4h is carried out；
(3) it is warming up to 230 DEG C~270 DEG C again, carries out polycondensation reaction 1h~3h；
(4) after polycondensation, end-capping reagent N-Methyl pyrrolidone (NMP) solution is added in reaction kettle, then react 0.5h
~1h；
(5) it is then down to room temperature discharging, is separated by solid-liquid separation, solid washing is dried to obtain polyaryl thioether sulfone product.
4,4-dichlorodiphenyl sulfone (DCDPS) of the present invention and anhydrous sodium sulfide (Na2S) molar ratio is 1:0.9~1:
1.1。
Catalyst of the present invention is one kind of rare earth catalyst cerium chloride or caddy；4, the 4- dichloro
The molar ratio of sulfone (DCDPS) and catalysts are as follows: 1:0.1~1:0.01.
The molar ratio of 4,4-dichlorodiphenyl sulfone (DCDPS) of the present invention and solvent N-methyl pyrilidone be 1:10~
1:25.
End-capping reagent of the present invention is one of paracide or m-dichlorobenzene, the 4,4-dichlorodiphenyl sulfone
(DCDPS) with the molar ratio of end-capping reagent are as follows: 1:0.1~1:0.01.
The inherent viscosity of usual PASS is the resin of low molecular weight less than 0.29, and inherent viscosity is medium in 0.29-0.35
The resin of molecular weight, inherent viscosity are greater than 0.35 for the resin of high molecular weight, and the polyaryl thioether sulfone of the method for the present invention synthesis is height
Molecular weight polyaryl thioether sulfone, and show the polyaryl thioether sulfone weight average molecular weight of this method synthesis all through high temperature GPC test result
40000 or more.
The present invention has effect below:
1. the present invention uses anhydrous sodium sulfide for raw material, rare earth catalyst, the polyaryl thioether sulfone tree that the method synthesizes
Not only molecular weight is big for rouge, but also yield is also high, and product comprehensive performance is more excellent.
2. the method provided by the present invention for preparing polyaryl thioether sulfone, synthesis pressure is low, simple process, is easier to industrial metaplasia
It produces.
3. the yield of herein described method is all 92% or more, high income.
Specific embodiment:
Embodiment 1:
In a kettle, by 4,4-dichlorodiphenyl sulfone (DCDPS), anhydrous sodium sulfide (Na2S), cerium chloride, N- methylpyrrole
Alkanone is put into reaction kettle together, molar ratio DCDPS:Na2S: cerium chloride: N-Methyl pyrrolidone 1:1:0.02:
10, nitrogen displaced air, pressurising 0.3Mpa.140 DEG C are warming up to, prepolymerization reaction 4h is carried out.It is warming up to 270 DEG C again, carries out polycondensation
React 1h.After polycondensation, N-Methyl pyrrolidone (NMP) solution of end-capping reagent paracide is slowly added in reaction kettle,
The molar ratio of end-capping reagent paracide and 4,4-dichlorodiphenyl sulfone (DCDPS) are 0.02:1, then react 0.5h.Then it is down to room temperature
Discharging, is separated by solid-liquid separation, and solid washing is dried to obtain polyaryl thioether sulfone product.
Embodiment 2:
In a kettle, by 4,4-dichlorodiphenyl sulfone (DCDPS), anhydrous sodium sulfide (Na2S), caddy, N- methylpyrrole
Alkanone is put into reaction kettle together, molar ratio DCDPS:Na2S: cerium chloride: N-Methyl pyrrolidone 1:0.9:0.1:
15, nitrogen displaced air, pressurising 0.5Mpa.160 DEG C are warming up to, prepolymerization reaction 3.5h is carried out.It is warming up to 255 DEG C again, contracts
Poly- reaction 2h.After polycondensation, N-Methyl pyrrolidone (NMP) solution of end-capping reagent m-dichlorobenzene is added in reaction kettle, envelope
Holding the molar ratio of agent m-dichlorobenzene and 4,4-dichlorodiphenyl sulfone (DCDPS) is 0.01:1, then reacts 0.6h.Then room temperature is down to go out
Material, is separated by solid-liquid separation, and solid washing is dried to obtain polyaryl thioether sulfone product.
Embodiment 3:
It in a kettle, will be to 4,4-dichlorodiphenyl sulfone (DCDPS), anhydrous sodium sulfide (Na2S), cerium chloride, N- methyl pyrrole
Pyrrolidone is put into reaction kettle together, molar ratio DCDPS:Na2S: cerium chloride: N-Methyl pyrrolidone are as follows: 1:0.95:
0.04:18, nitrogen displaced air, pressurising 0.5Mpa.170 DEG C are warming up to, prepolymerization reaction 3h is carried out.It is warming up to 250 DEG C again, carries out
Polycondensation reaction 2.5h.After polycondensation, reaction kettle is added in N-Methyl pyrrolidone (NMP) solution of end-capping reagent paracide
In, the molar ratio of end-capping reagent paracide and 4,4-dichlorodiphenyl sulfone (DCDPS) are 0.03:1, then react 0.8h.Then it is down to
Room temperature discharging, is separated by solid-liquid separation, and solid washing is dried to obtain polyaryl thioether sulfone product.
Embodiment 4:
In a kettle, by 4,4-dichlorodiphenyl sulfone (DCDPS), anhydrous sodium sulfide (Na2S), caddy, N- methylpyrrole
Alkanone is put into reaction kettle together, molar ratio DCDPS:Na2S: caddy: N-Methyl pyrrolidone 1:1.1:
0.06:20, nitrogen displaced air, pressurising 0.8Mpa.180 DEG C are warming up to, prepolymerization reaction 2.5h is carried out.It is warming up to 240 DEG C again, into
Row polycondensation reaction 3h.After polycondensation, reaction kettle is added in N-Methyl pyrrolidone (NMP) solution of end-capping reagent m-dichlorobenzene
In, the molar ratio of end-capping reagent m-dichlorobenzene and 4,4-dichlorodiphenyl sulfone (DCDPS) are 0.06:1, then react 0.7h.Then it is down to
Room temperature discharging, is separated by solid-liquid separation, and solid washing is dried to obtain polyaryl thioether sulfone product.
Embodiment 5
In a kettle, by 4,4-dichlorodiphenyl sulfone (DCDPS), anhydrous sodium sulfide (Na2S), cerium chloride, N- methylpyrrole
Alkanone is put into reaction kettle together, molar ratio DCDPS:Na2S: cerium chloride: N-Methyl pyrrolidone 1:1.04:
0.08:25, nitrogen displaced air, pressurising 0.4Mpa.190 DEG C are warming up to, prepolymerization reaction 2h is carried out.It is warming up to 230 DEG C again, carries out
Polycondensation reaction 3h.After polycondensation, reaction kettle is added in the solution of the N-Methyl pyrrolidone (NMP) of end-capping reagent paracide
In, the molar ratio of end-capping reagent paracide and 4,4-dichlorodiphenyl sulfone (DCDPS) are 0.05:1, then react 0.6h.Then it is down to
Room temperature discharging, is separated by solid-liquid separation, and solid washing is dried to obtain polyaryl thioether sulfone product.
Embodiment 6
In a kettle, by 4,4-dichlorodiphenyl sulfone (DCDPS), anhydrous sodium sulfide (Na2S), caddy, N- methylpyrrole
Alkanone is put into reaction kettle together, molar ratio DCDPS:Na2S: caddy: N-Methyl pyrrolidone 1:1.08:
0.01:25, nitrogen displaced air, pressurising 1.0Mpa.170 DEG C are warming up to, prepolymerization reaction 3.5h is carried out.It is warming up to 265 DEG C again, into
Row polycondensation reaction 1.5h.After polycondensation, reaction kettle is added in N-Methyl pyrrolidone (NMP) solution of end-capping reagent m-dichlorobenzene
In, the molar ratio of end-capping reagent m-dichlorobenzene and 4,4-dichlorodiphenyl sulfone (DCDPS) are 0.1:1, then react 1h.Then it is down to room temperature
Discharging, is separated by solid-liquid separation, and solid washing is dried to obtain polyaryl thioether sulfone product.
Test result is as follows for each embodiment sintetics:
Find out from above embodiments sample tests and prior art products performance comparison, described in technical scheme
The method of synthesis polyaryl thioether sulfone has obtained polyaryl thioether sulfone, and inherent viscosity is higher, is reported according to pertinent literature, the spy of PASS
Property viscosity less than 0.29 be low molecular weight resin, inherent viscosity 0.29-0.35 be intermediate molecular weight resin, inherent viscosity
Greater than 0.35 it is the resin of high molecular weight, so the polyaryl thioether sulfone for having reason to illustrate the method for the present invention synthesis is high-molecular-weight poly
Aromatic sulfide sulfone, and show the polyaryl thioether sulfone weight average molecular weight of this method synthesis all 40000 through high temperature GPC test result
More than.In addition, the yield of herein described method is all 92% or more, high income.
Claims (7)
1. a kind of synthetic method of high molecular weight poly arylidene thio-ester sulfone, it is characterised in that: the synthetic method the following steps are included:
(1) by 4,4-dichlorodiphenyl sulfone (DCDPS), anhydrous sodium sulfide (Na2S), catalyst, solvent are put into reaction kettle together, nitrogen
Gas displaced air, pressurising 0.3-1Mpa；
(2) 140 DEG C~190 DEG C are first warming up to, prepolymerization reaction 2h~4h is carried out；
(3) it is warming up to 230 DEG C~270 DEG C again, carries out polycondensation reaction 1h~3h；
(4) after polycondensation, end-capping reagent N-Methyl pyrrolidone (NMP) solution is added in reaction kettle, then react 0.5h~1h；
(5) it is then down to room temperature discharging, is separated by solid-liquid separation, solid washing is dried to obtain polyaryl thioether sulfone product.
2. a kind of synthetic method of high molecular weight poly arylidene thio-ester sulfone according to claim 1, it is characterised in that: 4,4- dichloros
Diphenyl sulphone (DPS) (DCDPS) and anhydrous sodium sulfide (Na2S) molar ratio is 1:0.9~1:1.1.
3. according to the method described in claim 1, it is characterized by: catalysts are one kind of cerium chloride or caddy.
4. according to the method described in claim 1, it is characterized by: 4,4-dichlorodiphenyl sulfone (DCDPS) and catalysts
Molar ratio are as follows: 1:0.1~1:0.01.
5. according to the method described in claim 1, it is characterized by: 4,4-dichlorodiphenyl sulfone (DCDPS) and Solvents N-methyl pyrrole
The molar ratio of pyrrolidone are as follows: 1:10~1:25.
6. according to the method described in claim 1, it is characterized by: end-capping reagent is one of paracide or m-dichlorobenzene.
7. according to the method described in claim 1, it is characterized by: mole of 4,4-dichlorodiphenyl sulfone (DCDPS) and end-capping reagent
Than are as follows: 1:0.1~1:0.01.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301274A (en) * | 1980-01-29 | 1981-11-17 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
| CN1461763A (en) * | 2002-05-31 | 2003-12-17 | 四川大学 | Polyaryl thioether sulfone and its preparation method |
| CN103467741A (en) * | 2013-09-22 | 2013-12-25 | 四川大学 | Polyphenylene sulfide and preparation method thereof |
| CN105778095A (en) * | 2016-03-21 | 2016-07-20 | 成都大诺工程技术咨询有限公司 | Low-oxygen polyarylene sulfide sulfone synthetic technology |
-
2019
- 2019-07-16 CN CN201910639839.2A patent/CN110256674A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301274A (en) * | 1980-01-29 | 1981-11-17 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
| CN1461763A (en) * | 2002-05-31 | 2003-12-17 | 四川大学 | Polyaryl thioether sulfone and its preparation method |
| CN103467741A (en) * | 2013-09-22 | 2013-12-25 | 四川大学 | Polyphenylene sulfide and preparation method thereof |
| CN105778095A (en) * | 2016-03-21 | 2016-07-20 | 成都大诺工程技术咨询有限公司 | Low-oxygen polyarylene sulfide sulfone synthetic technology |
Non-Patent Citations (1)
| Title |
|---|
| 王华东 等: "高性能结构材料聚苯硫醚砜", 《高分子材料科学与工程》 * |
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Application publication date: 20190920 |