CN107337799A - A kind of preparation method of polyarylene sulfide ketone - Google Patents
A kind of preparation method of polyarylene sulfide ketone Download PDFInfo
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- CN107337799A CN107337799A CN201710625267.3A CN201710625267A CN107337799A CN 107337799 A CN107337799 A CN 107337799A CN 201710625267 A CN201710625267 A CN 201710625267A CN 107337799 A CN107337799 A CN 107337799A
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- polyarylene sulfide
- sulfide ketone
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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
- C08G75/10—Polythioethers from sulfur or sulfur-containing compounds and aldehydes or ketones
Abstract
The present invention discloses a kind of preparation method of polyarylene sulfide ketone, comprises the following steps：(1) by N methyl pyrrolidones, aqueous vulcanized sodium, sodium hydroxide, composite catalyst input dehydrating kettle, dehydration, dehydrated material is obtained；(2) dehydrated material is transferred to polymeric kettle, 4,4 ' the dichloro benzophenone solution prepared using N methyl pyrrolidones as solvent is added dropwise in polymeric kettle, prepolymerization 1~3 hour, obtain prepolymer；(3) prepolymer is cooled to 140~160 DEG C, the trichloro-benzenes of constant pressure dropping 1,2,4, after being added dropwise, is warming up to 250~290 DEG C, constant temperature 2~6h of polycondensation reaction, obtains the solidliquid mixture containing polyarylene sulfide ketone；(4) by solidliquid mixture it is scrubbed, dry after obtain polyarylene sulfide ketone product.The method polymerizeing using prepolymerization and again, by chain-extension polymerization, can reach the higher degree of polymerization at low pressures, and the polyarylene sulfide ketone molecular resin amount being prepared is higher, can greatly shorten synthesis cycle, saves energy consumption, is advantageous to industrial amplification production.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of preparation method of polyarylene sulfide ketone.
Background technology
At present, one of important topic of high polymer material research is research and development novel fire resistant, corrosion-resisting resin.Existing
Poly- carbonic acid acid, polyphenyl acid, polyformaldehyde, polyimide, polytetrafluoroethylene (PTFE), polyphenylene sulfide etc. are respectively provided with excellent resistance in some resins
It is hot, but long-term use of temperature is below 200~260 DEG C.
Polyarylene sulfide ketone (PASK) is a kind of new high temperature resistant, corrosion resistant high polymer material, the same with PPS, all for
Crystalline resin, but due to the rigid heteroaryl structure in molecular backbone structure and highly polar carbonyl (- CO-), make its fusing point high
Up to 310~340 DEG C, heat resistance greatly increases than PPS, but cost is relatively low, is a kind of excellent heat-proof macromolecule material.The tree
Fat great advantage is that heat endurance is good, can carry out traditional processing and forming, may also be fabricated which PASK fibers and film, there is good answer
With prospect, the external existing many reports of this respect.The U.S., Japan also obtain in industrial aspect at present exists compared with ten-strike, Japan
Nineteen ninety, existing industrial goods were launched.
The synthetic method of PASK resins, is divided according to reactant type, mainly have alkali metal sulphide method, dithiol with
Double halo arone condensation methods, halo thiophenol are from condensation methods, sulfur solution route, phosgenation etc..PASK because its in building-up process easily
Separated out from solvent and make it that its molecular weight is difficult to grow up, Indian Journal of Chemistry (21,501,1982) and day
This patent JP-A-60-58435 reports synthesizes polyarylene sulfide ketone using high pressure sodium sulfide method, and the viscosity of resulting polymers is not
More than 0.3dl/g (H2SO4, 0.5g/dl, 28 DEG C), and United States Patent (USP) US005097003A is using the synthesis of high temperature sodium hydrosulfide
The viscosity of polyarylene sulfide ketone (not through Overheating Treatment) is 0.5dl/g (H2SO4,0.5g/dl, 30 DEG C).These patents use
High-pressure process synthesizes polyarylene sulfide ketone, it is necessary to the condition such as HTHP, and the polyarylene sulfide ketone molecular weight of non-pressure process synthesis is universal not
It is high.
The domestic research for PASK materials at present is still within the starting stage, and the synthesis for high-performance PASK resins is also
Need to be goed deep into, particularly also have larger gap in terms of industrialization, such as occur during large-scale industrial production PASK
The problems such as product yield is low, and molecular weight is not high, and performance is unstable, and production cost is high, so it is domestic also without the big of PASK resins
The enterprise of technical scale metaplasia production.
The content of the invention
In view of this, the application provides a kind of preparation method of polyarylene sulfide ketone, the method polymerizeing using prepolymerization and again,
By chain-extension polymerization, the higher degree of polymerization is can reach at low pressures, and the polyarylene sulfide ketone molecular resin amount being prepared is more
Height, synthesis cycle can be greatly shortened, save energy consumption, be advantageous to industrial amplification production.
To solve above technical problem, technical scheme provided by the invention is a kind of preparation method of polyarylene sulfide ketone, institute
Preparation method is stated to comprise the following steps：
(1) 1-METHYLPYRROLIDONE, aqueous vulcanized sodium, sodium hydroxide, composite catalyst are put into dehydrating kettle, in nitrogen
Under protection and stirring action, dehydrating kettle temperature is increased to 150~200 DEG C, after moisture reaches requirement in system, dehydration
Terminate, obtain dehydrated material；
(2) step (1) described dehydrated material is transferred to polymeric kettle, 1-METHYLPYRROLIDONE will be used to be prepared as solvent
4,4 '-dichloro benzophenone solution is added dropwise in polymeric kettle, and logical nitrogen is sufficiently displaced from kettle after air, closed polymeric kettle,
Polymeric kettle temperature is increased to 200~250 DEG C, prepolymerization 1~3 hour, obtains prepolymer；
(3) step (2) described prepolymer is cooled to 140~160 DEG C, constant pressure dropping 1,2,4- trichloro-benzenes, dripped
Bi Hou, by polymerization kettle temperature raising to 250~290 DEG C, constant temperature 2~6h of polycondensation reaction, obtain the solid-liquid mixing containing polyarylene sulfide ketone
Thing；
(4) by step (3) described solidliquid mixture it is scrubbed, dry after obtain polyarylene sulfide ketone product.
By above technical scheme, using aqueous vulcanized sodium, 4,4 '-dichloro benzophenone is primary raw material, with N- methyl
Pyrrolidones is solvent, and sodium hydroxide is auxiliary agent, and 1,2,4- trichloro-benzenes is the preparation that chain extender carries out polyarylene sulfide ketone, and it is prepared
Principle is：Raw aqueous vulcanized sodium and 4,4 '-dichloro benzophenone first pass through prepolymerization preparation under solvent and catalyst action
Go out the line style poly arylidene thio-ester ketone resin of low molecule amount, then add the trichloro-benzenes of crosslinking agent 1,2,4- with 3 active sites, pass through
Polyarylene sulfide ketone tree of the polymerization process by the line style polyarylene sulfide ketone resin crosslinks of low molecule amount described above into HMW again
Fat, whole preparation process includes dehydration, prepolymerization, the process for polymerizeing again, post-processing, in preparation process, using prepolymerization
The method polymerizeing again, the higher degree of polymerization is just can reach under lower pressure, the polyarylene sulfide ketone molecular resin amount being prepared
Higher, combination property is more excellent；In addition, again in polymerization procedure, using the method for chain-extension polymerization, in obtained identical characteristic
In the case of viscosity number poly arylidene thio-ester ketone resin, it is time-consuming shorter, is more easy to realize, is substantially shorter synthesis cycle, and energy consumption reduces.
Preferably, step (2) described 4, the compound method of 4 '-dichloro benzophenone solution are：By 1-METHYLPYRROLIDONE
With 4, in 4 '-dichloro benzophenone input dissolution kettle, under nitrogen protection and stirring action, dissolution kettle temperature is increased to 150
~180 DEG C, until 4,4 '-dichloro benzophenone is dissolved completely in 1-METHYLPYRROLIDONE, produces described 4,4 '-dichloro first
Ketone solution.
Preferably, in the preparation method, the molfraction of each component is respectively：Aqueous 1.0~1.05 parts of vulcanized sodium, 4,
1.0~1.05 parts of 4 '-dichloro benzophenone, 0.1~0.6 part of composite catalyst, 0.02~0.08 part of sodium hydroxide, N- methyl pyrroles
10~15 parts of pyrrolidone, 1,2,4- 0.02~0.2 part of trichloro-benzenes.
Preferably, step (1) described composite catalyst is the mixture of lithium chloride and lithium acetate.Using lithium chloride and acetic acid
Two kinds of catalyst complex of lithium use, and pass through the synergy of two kinds of components of lithium chloride and lithium acetate, it is possible to increase catalytic activity, make
Properties of product stabilization, favorable reproducibility, high income.
Preferably, the percetage by weight content of vulcanized sodium is 30~65% in step (1) the aqueous vulcanized sodium.
Preferably, when step (1) the system moisture reaches 0~2%, dehydration terminates.
Preferably, step (2) described 4, the dropping temperature of 4 '-dichloro benzophenone solution are not less than 150 DEG C.Less than 150
DEG C when have 4,4 '-dichloro benzophenone crystal separates out from solvent, destroy polymerisation stability, reduce product yield, together
When the polyarylene sulfide ketone molecular weight that can make to obtain it is not high.
Preferably, step (3) described 1, the dropping temperature of 2,4- trichloro-benzenes are not less than 130 DEG C.Temperature is less than 130 DEG C, nothing
Method completes chain extending reaction, therefore dropping temperature control can quickly be realized and polymerize again more than 130 DEG C, reaches higher and gathers
It is right, the molecular weight of polyarylene sulfide ketone is improved, and then improve the combination property of polyarylene sulfide ketone.
Preferably, the temperature of step (4) described drying is not higher than 105 DEG C.Drying temperature can cause poly- virtue when being higher than 105 DEG C
The oxidation stain of sulfide ketone.
Wherein, step (2) 4, the dropwise addition of 4 '-dichloro benzophenone solution and step (3) 1, the dropwise addition of 2,4- trichloro-benzenes
It is to be slowly added dropwise, rate of addition is 1~2 drop/s.It is slow that process control is added dropwise, the stability of course of reaction can be ensured, kept away
Exempt from the precipitation of 4,4 '-dichloro benzophenone.
Based on above-mentioned elaboration, compared with prior art, its advantage is technical scheme：
(1) synthesis condition using HTHP is avoided, energy consumption and production cost is reduced, realizes and produced under normal temperature and pressure
HMW polyarylene sulfide ketone resin, is advantageous to industrial amplification production；
(2) prepolymerization and the method polymerizeing again are used, the higher degree of polymerization is just can reach under lower pressure, is prepared
Polyarylene sulfide ketone molecular resin amount is higher, and combination property is more excellent；
(3) method for using chain-extension polymerization, in the case where identical intrinsic viscosity poly arylidene thio-ester ketone resin is made, take more
It is short, it is more easy to realize, be substantially shorter synthesis cycle, energy consumption reduces；
(4) lithium chloride and lithium acetate are used as composite catalyst, active higher, the obtained polyarylene sulfide ketone of catalyst
Can stabilization, favorable reproducibility, high income.
Embodiment
In order that those skilled in the art more fully understands technical scheme, with reference to specific embodiment pair
The present invention is described in further detail.
Embodiment 1
A kind of preparation method of polyarylene sulfide ketone described in the present embodiment, comprises the following steps：
(1) based on molfraction, by 8.8 parts of 1-METHYLPYRROLIDONEs, 1.02 parts of aqueous vulcanized sodium (water content 30wt%),
In 0.05 part of sodium hydroxide, 0.3 part of composite catalyst (mixture of lithium chloride and lithium acetate) input dehydrating kettle, protected in nitrogen
Under stirring action, dehydrating kettle temperature is increased to 180 DEG C, when moisture is below 1% in system, dehydration terminates, and obtains
Dehydrated material；
(2) step (1) described dehydrated material is transferred to polymeric kettle, under the temperature conditionss not less than 150 DEG C, will used
1-METHYLPYRROLIDONE prepared as solvent 4,4 '-dichloro benzophenone solution is added dropwise in polymeric kettle, and logical nitrogen is fully put
Change in kettle after air, closed polymeric kettle, polymeric kettle temperature is increased to 220 DEG C, prepolymerization 2 hours, obtains prepolymerization
Thing；
(3) step (2) described prepolymer is cooled to 150 DEG C, 0.1 part 1 of constant pressure dropping, 2,4- trichloro-benzenes, dripped
Bi Hou, by polymerization kettle temperature raising to 270 DEG C, constant temperature polycondensation reaction 4h, obtain the solidliquid mixture containing polyarylene sulfide ketone；
(4) by step (3) described solidliquid mixture it is scrubbed, dry after obtain polyarylene sulfide ketone product, wherein dry
Temperature is not higher than 105 DEG C.
Wherein, step (2) described 4, the compound method of 4 '-dichloro benzophenone solution are：Based on molfraction, by 3.2
Part 1-METHYLPYRROLIDONE and 1.02 part 4, in 4 '-dichloro benzophenone input dissolution kettle, under nitrogen protection and stirring action,
Dissolution kettle temperature is increased to 165 DEG C, until 4,4 '-dichloro benzophenone is dissolved completely in 1-METHYLPYRROLIDONE, produces institute
State 4,4 '-dichloro benzophenone solution.
It is repeated 3 times according to above-mentioned steps, determines its average intrinsic viscosity, glass transition temperature, fusing point, starting thermal decomposition
Temperature, weightless 50% temperature, molecular weight, and its yield is calculated, it the results are shown in Table 1.
The polyarylene sulfide ketone Product checking result of 1 embodiment of table 1
Embodiment 2
A kind of preparation method of polyarylene sulfide ketone described in the present embodiment, comprises the following steps：
(1) based on molfraction, by 7.3 parts of 1-METHYLPYRROLIDONEs, 1.0 parts of aqueous vulcanized sodium (water content 44wt%),
In 0.02 part of sodium hydroxide, 0.1 part of composite catalyst (mixture of lithium chloride and lithium acetate) input dehydrating kettle, protected in nitrogen
Under stirring action, dehydrating kettle temperature is increased to 150 DEG C, when moisture is below 1% in system, dehydration terminates, and obtains
Dehydrated material；
(2) step (1) described dehydrated material is transferred to polymeric kettle, under the temperature conditionss not less than 150 DEG C, will used
1-METHYLPYRROLIDONE prepared as solvent 4,4 '-dichloro benzophenone solution is added dropwise in polymeric kettle, and logical nitrogen is fully put
Change in kettle after air, closed polymeric kettle, polymeric kettle temperature is increased to 200 DEG C, prepolymerization 3 hours, obtains prepolymerization
Thing；
(3) step (2) described prepolymer is cooled to 140 DEG C, 0.02 part 1 of constant pressure dropping, 2,4- trichloro-benzenes, dripped
Bi Hou, by polymerization kettle temperature raising to 250 DEG C, constant temperature polycondensation reaction 6h, obtain the solidliquid mixture containing polyarylene sulfide ketone；
(4) by step (3) described solidliquid mixture it is scrubbed, dry after obtain polyarylene sulfide ketone product, wherein dry
Temperature is not higher than 105 DEG C.
Wherein, step (2) described 4, the compound method of 4 '-dichloro benzophenone solution are：Based on molfraction, by 2.7
Part 1-METHYLPYRROLIDONE and 1.0 part 4, in 4 '-dichloro benzophenone input dissolution kettle, under nitrogen protection and stirring action,
Dissolution kettle temperature is increased to 150 DEG C, until 4,4 '-dichloro benzophenone is dissolved completely in 1-METHYLPYRROLIDONE, produces institute
State 4,4 '-dichloro benzophenone solution.
It is repeated 3 times according to above-mentioned steps, determines its average intrinsic viscosity, glass transition temperature, fusing point, starting thermal decomposition
Temperature, weightless 50% temperature, and its yield is calculated, it the results are shown in Table 2.
The polyarylene sulfide ketone Product checking result of 2 embodiment of table 2
Embodiment 3
A kind of preparation method of polyarylene sulfide ketone described in the present embodiment, comprises the following steps：
(1) based on molfraction, by 11 parts of 1-METHYLPYRROLIDONEs, 1.05 parts of aqueous vulcanized sodium (water content 60wt%),
In 0.08 part of sodium hydroxide, 0.6 part of composite catalyst (mixture of lithium chloride and lithium acetate) input dehydrating kettle, protected in nitrogen
Under stirring action, dehydrating kettle temperature is increased to 200 DEG C, when moisture is below 2% in system, dehydration terminates, and obtains
Dehydrated material；
(2) step (1) described dehydrated material is transferred to polymeric kettle, under the temperature conditionss not less than 150 DEG C, will used
1-METHYLPYRROLIDONE prepared as solvent 4,4 '-dichloro benzophenone solution is added dropwise in polymeric kettle, and logical nitrogen is fully put
Change in kettle after air, closed polymeric kettle, polymeric kettle temperature is increased to 250 DEG C, prepolymerization 1 hour, obtains prepolymerization
Thing；
(3) step (2) described prepolymer is cooled to 160 DEG C, 0.2 part 1 of constant pressure dropping, 2,4- trichloro-benzenes, dripped
Bi Hou, by polymerization kettle temperature raising to 290 DEG C, constant temperature polycondensation reaction 2h, obtain the solidliquid mixture containing polyarylene sulfide ketone；
(4) by step (3) described solidliquid mixture it is scrubbed, dry after obtain polyarylene sulfide ketone product, wherein dry
Temperature is not higher than 105 DEG C.
Wherein, step (2) described 4, the compound method of 4 '-dichloro benzophenone solution are：Based on molfraction, by 4 parts
1-METHYLPYRROLIDONE and 1.05 part 4,, will under nitrogen protection and stirring action in 4 '-dichloro benzophenone input dissolution kettle
Dissolution kettle temperature is increased to 180 DEG C, until 4,4 '-dichloro benzophenone is dissolved completely in 1-METHYLPYRROLIDONE, produces described
4,4 '-dichloro benzophenone solution.
It is repeated 3 times according to above-mentioned steps, determines its average intrinsic viscosity, glass transition temperature, fusing point, starting thermal decomposition
Temperature, weightless 50% temperature, molecular weight, and its yield is calculated, it the results are shown in Table 3.
The polyarylene sulfide ketone Product checking result of 3 embodiment of table 3
As can be seen from the above embodiments, the polyarylene sulfide ketone that preparation method described in technical scheme is prepared,
By 3 repeated experiments, its average intrinsic viscosity is higher, illustrates that its molecular weight is high and relatively stable, its stable mechanical property
Property it is good, repeatability is high.In addition, the yield of herein described method minimum 84.9%, high conversion rate.
It the above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
The limitation of the present invention, protection scope of the present invention should be defined by claim limited range.For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, some improvements and modifications can also be made, these change
Enter and retouch and also should be regarded as protection scope of the present invention.
Claims (9)
- A kind of 1. preparation method of polyarylene sulfide ketone, it is characterised in that：The preparation method comprises the following steps：(1) by 1-METHYLPYRROLIDONE, aqueous vulcanized sodium, sodium hydroxide, composite catalyst input dehydrating kettle, protected in nitrogen Under stirring action, dehydrating kettle temperature is increased to 150~200 DEG C, after moisture reaches requirement in system, dehydration knot Beam, obtain dehydrated material；(2) step (1) described dehydrated material is transferred to polymeric kettle, 4 will prepared using 1-METHYLPYRROLIDONE as solvent, 4 '-dichloro benzophenone solution is added dropwise in polymeric kettle, and logical nitrogen is sufficiently displaced from kettle after air, closed polymeric kettle, will be poly- Close kettle temperature degree and be increased to 200~250 DEG C, prepolymerization 1~3 hour, obtain prepolymer；(3) step (2) described prepolymer is cooled to 140~160 DEG C, constant pressure dropping 1,2,4- trichloro-benzenes, after being added dropwise, By polymerization kettle temperature raising to 250~290 DEG C, constant temperature 2~6h of polycondensation reaction, the solidliquid mixture containing polyarylene sulfide ketone is obtained；(4) by step (3) described solidliquid mixture it is scrubbed, dry after obtain polyarylene sulfide ketone product.
- A kind of 2. preparation method of polyarylene sulfide ketone according to claim 1, it is characterised in that：Step (2) described 4,4 '- The compound method of dichloro benzophenone solution is：By 1-METHYLPYRROLIDONE and 4,4 '-dichloro benzophenone is put into dissolution kettle, Under nitrogen protection and stirring action, dissolution kettle temperature is increased to 150~180 DEG C, until 4,4 '-dichloro benzophenone is complete 1-METHYLPYRROLIDONE is dissolved in, produces described 4,4 '-dichloro benzophenone solution.
- A kind of 3. preparation method of polyarylene sulfide ketone according to claim 1, it is characterised in that：In the preparation method, The molfraction of each component is respectively：Aqueous 1.0~1.05 parts of vulcanized sodium, 4,1.0~1.05 parts of 4 '-dichloro benzophenone is multiple Close 0.1~0.6 part of catalyst, 0.02~0.08 part of sodium hydroxide, 10~15 parts of 1-METHYLPYRROLIDONE, 1,2,4- trichloro-benzenes 0.02~0.2 part.
- A kind of 4. preparation method of polyarylene sulfide ketone according to claim 1, it is characterised in that：Step (1) is described compound Catalyst is the mixture of lithium chloride and lithium acetate.
- A kind of 5. preparation method of polyarylene sulfide ketone according to claim 1, it is characterised in that：Step (1) is described aqueous The percetage by weight content of vulcanized sodium is 30~65% in vulcanized sodium.
- A kind of 6. preparation method of polyarylene sulfide ketone according to claim 1, it is characterised in that：Step (1) described system When moisture reaches 0~2%, dehydration terminates.
- A kind of 7. preparation method of polyarylene sulfide ketone according to claim 1, it is characterised in that：Step (2) described 4,4 '- The dropping temperature of dichloro benzophenone solution is not less than 150 DEG C.
- A kind of 8. preparation method of polyarylene sulfide ketone according to claim 1, it is characterised in that：Step (3) described 1,2, The dropping temperature of 4- trichloro-benzenes is not less than 130 DEG C.
- A kind of 9. preparation method of polyarylene sulfide ketone according to claim 1, it is characterised in that：Step (4) described drying Temperature be not higher than 105 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087906A (en) * | 2021-04-07 | 2021-07-09 | 四川轻化工大学 | Preparation method of polyphenylene sulfide ketone and product thereof |
| CN113150279A (en) * | 2021-06-16 | 2021-07-23 | 杨宾科 | Preparation method of polyphenylene sulfide ketone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0450635A2 (en) * | 1990-04-06 | 1991-10-09 | Phillips Petroleum Company | Process for preparing branched poly(arylene sulfide ketone) |
| CN1145376A (en) * | 1995-09-13 | 1997-03-19 | 四川联合大学 | Method for atmospheric prep. of polyarylthio-ether by using industrial sodium sulfide |
-
2017
- 2017-07-27 CN CN201710625267.3A patent/CN107337799A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0450635A2 (en) * | 1990-04-06 | 1991-10-09 | Phillips Petroleum Company | Process for preparing branched poly(arylene sulfide ketone) |
| CN1145376A (en) * | 1995-09-13 | 1997-03-19 | 四川联合大学 | Method for atmospheric prep. of polyarylthio-ether by using industrial sodium sulfide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087906A (en) * | 2021-04-07 | 2021-07-09 | 四川轻化工大学 | Preparation method of polyphenylene sulfide ketone and product thereof |
| CN113087906B (en) * | 2021-04-07 | 2022-07-01 | 四川轻化工大学 | Preparation method of polyphenylene sulfide ketone and product thereof |
| CN113150279A (en) * | 2021-06-16 | 2021-07-23 | 杨宾科 | Preparation method of polyphenylene sulfide ketone |
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Application publication date: 20171110 |