CN109134862A - A method of using acylate as catalyst preparation branched chain type polyphenylene sulfide - Google Patents
A method of using acylate as catalyst preparation branched chain type polyphenylene sulfide Download PDFInfo
- Publication number
- CN109134862A CN109134862A CN201810825048.4A CN201810825048A CN109134862A CN 109134862 A CN109134862 A CN 109134862A CN 201810825048 A CN201810825048 A CN 201810825048A CN 109134862 A CN109134862 A CN 109134862A
- Authority
- CN
- China
- Prior art keywords
- polyphenylene sulfide
- acylate
- branched chain
- chain type
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
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 technical field of polymer materials, and in particular to a method of using acylate as catalyst preparation branched chain type polyphenylene sulfide.For the problem that linear polyphenylthioether molecular weight is not high, production cost is higher and polyphenylene sulfide crystallinity is excessively high in the technology of existing sodium sulfide method production polyphenylene sulfide, technical solution of the present invention has abandoned existing domestic mainstream using lithium chloride as the polyphenylene sulfide preparation process of catalyst, using the acylate of low cost as catalyst, capability and performance stabilization and lower-cost polyphenylene sulfide are prepared；The degree of polymerization of polyphenylene sulfide not only can be improved in this method, synthesize the polyphenylene sulfide of branched chain type, also overcome that traditional processing technology polyphenylene sulfide products molecule chain regularity is strong, crystallinity is high, is not easy the problems such as being processed to film or fiber, the performance for greatly improving polyphenylene sulfide product extends the application field and use scope of polyphenylene sulfide.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to one kind is using acylate as catalyst preparation branched chain type
The method of polyphenylene sulfide.
Background technique
Polyphenylene sulfide (PPS) realized industrialization by the oil company Phillips of the U.S. in 1973 first, and with trade name
" Ryton " is launched, and obtains the favor of users.Polyphenylene sulfide (PPS) main manufacturer has the U.S. in the world at present
The oil company Phillips, Fortron company, Bayer A.G, toray-Phillips, Wu Yu chemical industry are public
Department, Tosoh-Bao Shi paddy company, big Japanese ink chemical company, eastern burning petroleum chemical industrial company etc..PPS synthetic route is main
There are three types of: sodium sulfide method, sulfur solution route and oxidative polymerization method, the industrialized production of PPS mostly uses greatly sodium sulfide method at present.
Sodium sulfide method generally uses crystalline sodium sulfide for sulphur source, using LiCl as catalyst, using NaOH as auxiliary agent, has in polarity
In solvent N-Methyl pyrrolidone (NMP) with paracide (P-DCB) polymerization outgoing-line type PPS.Since the method synthesizes
PPS molecular weight out is not high, substantially reduces its performance, greatly limits the application of PPS product.In addition, due to
Li belongs to scarce resource, in addition the fast development of domestic electronics industry (such as battery), Li consumption also increase increasingly in recent years
Greatly, the price of Li is caused to soar all the way, so that the production cost of PPS is high, this once made PPS manufacturing enterprise of China
In verge of bankruptcy.Further, since line style PPS strand regularity is strong, crystallinity is high, it is not easy to be processed to film or fibre
Dimension.Simultaneously as branched chain type PPS is in photoresist, temperature sensor, macromolecule alkylation reaction reagent and ion exchange resin
The continuous expansion of equal fields application, demand of the market to branched chain type PPS are also growing day by day.It can be seen that synthesizing branch without lithium method
Chain high molecular weight PPS resin has been increasingly becoming the research emphasis of domestic and international PPS manufacturing enterprise.
Summary of the invention
The not high, production cost for linear polyphenylthioether molecular weight in the technology of existing sodium sulfide method production polyphenylene sulfide
Problem higher and that polyphenylene sulfide crystallinity is excessively high, the present invention provide one kind using acylate as catalyst preparation branched chain type
The method of polyphenylene sulfide, its object is to: it is original with aqueous vulcanized sodium, paracide using inexpensive acylate as catalyst
Material, using N-Methyl pyrrolidone as solvent, using sodium hydroxide as reaction promoter, prepares branched chain type polyphenylene sulfide.
The technical solution adopted by the invention is as follows:
A method of using acylate as catalyst preparation branched chain type polyphenylene sulfide, comprising the following steps:
[1] N-Methyl pyrrolidone, sodium hydroxide, organic acid and water are added in reaction kettle, are heated up under nitrogen protection
And constant temperature is dehydrated, and obtains the N-Methyl pyrrolidone solution of acylate；
[2] in the solution for obtaining N-Methyl pyrrolidone, aqueous vulcanized sodium and sodium hydroxide addition step [1], in nitrogen
Continue heating and constant temperature dehydration under gas shielded, obtains the N-Methyl pyrrolidone mixed solution of vulcanized sodium and acylate；
[3] greenhouse cooling of the mixed solution of step [2] processing will be passed through in reaction kettle to 140 DEG C hereinafter, then will be right
The solution of dichloro-benzenes and N-Methyl pyrrolidone is slowly uniformly added dropwise in reaction kettle, obtains reaction solution；
[4] temperature for the reaction solution for obtaining step [3] increases, and polycondensation reaction occurs；
[5] it will cool down by the reaction solution after the polycondensation reaction of step [4], discharging, and obtain branched chain type polyphenylene sulfide product.
After the technical solution, using aqueous vulcanized sodium, paracide as raw material, using N-Methyl pyrrolidone as solvent,
Using sodium hydroxide as reaction promoter, using acylate as catalyst carries out polycondensation reaction and produces to obtain polyphenylene sulfide.Due to having
The LiCl catalyst price that the price of machine hydrochlorate uses more in the prior art is lower, it is thus possible to reduce sodium sulfide method production polyphenyl
The cost of thioether.And acylate can make the phenyl ring in polymer generate branch as catalyst, thus, using this technology
The polyphenylene sulfide that scheme produces is branched chain type polyphenylene sulfide, overcomes the linear polyphenylthioether point produced in the prior art
Son measures the not high and excessively high problem of polyphenylene sulfide crystallinity.
Preferably, the detailed process of heating described in step [1] and constant temperature dehydration are as follows: under nitrogen protection with 2 DEG C/min
Heating rate be warming up to 100-160 DEG C, isothermal reaction 30-90min；After completion of the reaction again with the heating rate liter of 2 DEG C/min
For temperature to 160-200 DEG C, constant temperature is dehydrated 30min.
It is further preferred that described in step [2] heating and constant temperature dehydration detailed process are as follows: under nitrogen protection with
The heating rate of 1.5 DEG C/min is to slowly warm up to 204 DEG C, continues the water in the system of sloughing, until N- crassitude in solution
The mass fraction of ketone reaches 97.5%.
Preferably, the detailed process of step [4] are as follows: be to slowly warm up to the reaction solution that step [3] obtains in 120min
210-230 DEG C, constant temperature pre-polymerization 40-90min；240-270 DEG C is to slowly warm up in 60min, constant temperature polycondensation 140-200min.
Preferably, organic acid described in step [1] be one of benzoic acid, caproic acid, 2 Ethylbutanoic acid or valeric acid or
It is a variety of.
Preferably, water described in step [1] is one of tap water, distilled water or ultrapure water.
Preferably, in the reaction solution that step [3] obtains, the molar ratio of sodium hydroxide and acylate is 1.01-1.06:1；
The molar ratio of sodium hydroxide and water is 0.15-0.20:1；The molar ratio of vulcanized sodium and paracide is 1.0-1.05:1；N- methyl
The molar ratio of pyrrolidones and paracide is 4.5-5.7:1.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
[1] present invention has abandoned existing domestic mainstream work on the basis of conventional vulcanized sodium method produces polyphenylene sulfide
The chlorination lithium catalyst that skill uses, using the acylate of low cost as catalyst, prepare that capability and performance is stable and cost compared with
Low polyphenylene sulfide；
[2] present invention uses new synthesis technology, improves the degree of polymerization of polyphenylene sulfide, solves traditional handicraft product point
Son amount is not high, and the low problem of physics, chemical property substantially increases the performance of polyphenylene sulfide product.
[3] present invention can synthesize branched chain type polyphenylene sulfide, overcome traditional processing technology polyphenylene sulfide product point
Subchain regularity is strong, and crystallinity is high, it is not easy to which the problems such as being processed to film or fiber greatly expands the application of polyphenylene sulfide
Field and use scope.
Specific embodiment
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
A method of using acylate as catalyst preparation branched chain type polyphenylene sulfide, with aqueous vulcanized sodium, paracide
For raw material, using N-Methyl pyrrolidone as solvent, using sodium hydroxide as reaction promoter, using acylate as catalyst, specific work
Skill step are as follows:
(1) N-Methyl pyrrolidone, sodium hydroxide, organic acid and water are added in reaction kettle, under nitrogen protection with 2
DEG C/heating rate of min is warming up to 100-160 DEG C, isothermal reaction 30-90min；
(2) it is warming up to 160-200 DEG C with the heating rate of 2 DEG C/min again after completion of the reaction, constant temperature is dehydrated 30min；
(3) N-Methyl pyrrolidone, aqueous vulcanized sodium, sodium hydroxide are added in reaction kettle, under nitrogen protection with 1.5
DEG C/heating rate of min is to slowly warm up to 204 DEG C, continue the water in the system of sloughing, until N-Methyl pyrrolidone in solution
Mass fraction reaches 97.5%；
(4) it opens cooling water and reactor temperature is cooled to 140 DEG C hereinafter, by paracide and N-Methyl pyrrolidone
Solution slowly and be uniformly added dropwise in reaction kettle；
(5) 210-230 DEG C is to slowly warm up in 120min, constant temperature pre-polymerization 40-90min；240- is to slowly warm up in 60min
270 DEG C, constant temperature polycondensation 140-200min；
(6) lead to cooling water temperature to 100 DEG C hereinafter, discharging.
Preferably, the molar ratio of sodium hydroxide and acylate is 1.01-1.06:1；The molar ratio of sodium hydroxide and water is
0.15-0.20:1；The molar ratio of vulcanized sodium and paracide is 1.0-1.05:1；N-Methyl pyrrolidone and paracide rub
You are than being 4.5-5.7:1.
Preferably, step (1) described acylate can be sodium benzoate, sodium n-caproate, 2 Ethylbutanoic acid sodium, natrium valericum
Deng.
Preferably, step (1) described water can be tap water, distilled water and ultrapure water.
It is illustrated below by preferred embodiment of the specific embodiment to above-mentioned technical proposal.
Embodiment 1
(1) 1676.05g N-Methyl pyrrolidone, 298.72g sodium hydroxide, 200.14g valeric acid and 697.01g are distilled
Water is added in reaction kettle, is warming up to 100-160 DEG C under nitrogen protection with the heating rate of 2 DEG C/min, isothermal reaction 30-
90min；
(2) it is warming up to 160-200 DEG C with the heating rate of 2 DEG C/min again after completion of the reaction, constant temperature is dehydrated 30min；
(3) 824g N-Methyl pyrrolidone, the aqueous vulcanized sodium of 982.32g, 3.75g sodium hydroxide are added in reaction kettle,
204 DEG C are to slowly warm up to the heating rate of 1.5 DEG C/min under nitrogen protection, continues the water in the system of sloughing, until solution
The mass fraction of middle N-Methyl pyrrolidone reaches 97.5%；
(4) it opens cooling water and reactor temperature is cooled to 140 DEG C hereinafter, by 820g paracide and 635gN- methyl pyrrole
The solution of pyrrolidone is slowly uniformly added dropwise in reaction kettle；
(5) 210-230 DEG C is to slowly warm up in 120min, constant temperature pre-polymerization 40-90min；240- is to slowly warm up in 60min
270 DEG C, constant temperature polycondensation 140-200min；
(6) lead to cooling water temperature to 100 DEG C hereinafter, discharging.
It is repeated 3 times according to above-mentioned steps, measures its whiteness, fusing point, glass transition temperature, melt flow rate (MFR), molecule
Its yield is measured and calculated, the results are shown in Table 1.
1 embodiment of table, 1 polyphenylene sulfide product testing result
The cost of one ton of polyphenylene sulfide is produced using the scheme of the present embodiment are as follows: 3.37 ten thousand yuan/ton；And use the prior art
In sodium sulfide method produce one ton of polyphenylene sulfide cost are as follows: 4.5 ten thousand yuan/ton.As it can be seen that the scheme of the present embodiment can significantly drop
The production cost of oligomeric diphenyl sulfide.
Embodiment 2
(1) 1700g N-Methyl pyrrolidone, 155.11g sodium hydroxide, 450.32g benzoic acid and 361.92g are distilled
Water is added in reaction kettle, is warming up to 100-160 DEG C under nitrogen protection with the heating rate of 2 DEG C/min, isothermal reaction 30-
90min；
(2) it is warming up to 160-200 DEG C with the heating rate of 2 DEG C/min again after completion of the reaction, constant temperature is dehydrated 30min；
(3) reaction kettle is added in 1000g N-Methyl pyrrolidone, the aqueous vulcanized sodium of 982.32g, 3.75g sodium hydroxide
In, 204 DEG C are to slowly warm up to the heating rate of 1.5 DEG C/min under nitrogen protection, continues the water in the system of sloughing, until molten
The mass fraction of N-Methyl pyrrolidone reaches 97.5% in liquid；
(4) it opens cooling water and reactor temperature is cooled to 140 DEG C hereinafter, by 820g paracide and 635gN- methyl pyrrole
The solution of pyrrolidone is slowly uniformly added dropwise in reaction kettle；
(5) 210-230 DEG C is to slowly warm up in 120min, constant temperature pre-polymerization 40-90min；240- is to slowly warm up in 60min
270 DEG C, constant temperature polycondensation 140-200min；
(6) lead to cooling water temperature to 100 DEG C hereinafter, discharging.
It is repeated 3 times according to above-mentioned steps, measures its whiteness, fusing point, glass transition temperature, melt flow rate (MFR), molecule
Its yield is measured and calculated, the results are shown in Table 2.
2 embodiment of table, 2 polyphenylene sulfide product testing result
The cost of one ton of polyphenylene sulfide is produced using the scheme of the present embodiment are as follows: 3.32 ten thousand yuan/ton；And use the prior art
In sodium sulfide method produce one ton of polyphenylene sulfide cost are as follows: 4.5 ten thousand yuan/ton.As it can be seen that the scheme of the present embodiment can significantly drop
The production cost of oligomeric diphenyl sulfide.
Embodiment 3
(1) 1676.05g N-Methyl pyrrolidone, 137.87g sodium hydroxide, 400.28g caproic acid and 321.7g are distilled
Water is added in reaction kettle, is warming up to 100-160 DEG C under nitrogen protection with the heating rate of 2 DEG C/min, isothermal reaction 30-
90min；
(2) it is warming up to 160-200 DEG C with the heating rate of 2 DEG C/min again after completion of the reaction, constant temperature is dehydrated 30min；
(3) by the distillation of 824g N-Methyl pyrrolidone, 982.32g aqueous vulcanized sodium, 3.75g sodium hydroxide and 200g
Water is added in reaction kettle, is to slowly warm up to 204 DEG C under nitrogen protection with the heating rate of 1.5 DEG C/min, continues the system of sloughing
In water, until the mass fraction of N-Methyl pyrrolidone reaches 97.5% in solution；
(4) it opens cooling water and reactor temperature is cooled to 140 DEG C hereinafter, by 820g paracide and 635gN- methyl pyrrole
The solution of pyrrolidone is slowly uniformly added dropwise in reaction kettle；
(5) 210-230 DEG C is to slowly warm up in 120min, constant temperature pre-polymerization 40-90min；240- is to slowly warm up in 60min
270 DEG C, constant temperature polycondensation 140-200min；
(6) lead to cooling water temperature to 100 DEG C hereinafter, discharging.
It is repeated 3 times according to above-mentioned steps, measures its whiteness, fusing point, glass transition temperature, melt flow rate (MFR), molecule
Its yield is measured and calculated, the results are shown in Table 3.
3 embodiment of table, 3 polyphenylene sulfide product testing result
The cost of one ton of polyphenylene sulfide is produced using the scheme of the present embodiment are as follows: 3.4 ten thousand yuan/ton；And use the prior art
In sodium sulfide method produce one ton of polyphenylene sulfide cost are as follows: 4.5 ten thousand yuan/ton.As it can be seen that the scheme of the present embodiment can significantly drop
The production cost of oligomeric diphenyl sulfide.
As can be seen from the above embodiments, one kind of the present invention is using acylate as catalyst preparation branched chain type polyphenylene sulfide
The method of ether, for the polyphenylene sulfide being prepared by 3 repeated experiments, average weight-average molecular weight is higher and relatively stable,
It is repeatable high.In addition, the yield of herein described method minimum 88.12%, high conversion rate.
The specific embodiment of the application above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
The limitation to the application protection scope therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, under the premise of not departing from technical scheme design, various modifications and improvements can be made, these belong to this
The protection scope of application.
Claims (7)
1. a kind of using acylate as the method for catalyst preparation branched chain type polyphenylene sulfide, which comprises the following steps:
[1] N-Methyl pyrrolidone, sodium hydroxide, organic acid and water are added in reaction kettle, under nitrogen protection heating and perseverance
Temperature dehydration, obtains the N-Methyl pyrrolidone solution of acylate；
[2] it in the solution for obtaining N-Methyl pyrrolidone, aqueous vulcanized sodium and sodium hydroxide addition step [1], is protected in nitrogen
Continue heating and constant temperature dehydration under shield, obtains the N-Methyl pyrrolidone mixed solution of vulcanized sodium and acylate；
[3] greenhouse cooling of the mixed solution of step [2] processing will be passed through in reaction kettle to 140 DEG C hereinafter, then will be to dichloro
The solution of benzene and N-Methyl pyrrolidone is slowly uniformly added dropwise in reaction kettle, obtains reaction solution；
[4] temperature for the reaction solution for obtaining step [3] increases, and polycondensation reaction occurs；
[5] it will cool down by the reaction solution after the polycondensation reaction of step [4], discharging, and obtain branched chain type polyphenylene sulfide product.
2. it is described in accordance with the claim 1 a kind of using acylate as the method for catalyst preparation branched chain type polyphenylene sulfide, it is special
Sign is that heat up the detailed process that simultaneously constant temperature is dehydrated described in step [1] are as follows: under nitrogen protection with the heating speed of 2 DEG C/min
Rate is warming up to 100-160 DEG C, isothermal reaction 30-90min；160- is warming up to the heating rate of 2 DEG C/min again after completion of the reaction
200 DEG C, constant temperature is dehydrated 30min.
3. it is a kind of using acylate as the method for catalyst preparation branched chain type polyphenylene sulfide according to claim 2, it is special
Sign is that heat up the detailed process that simultaneously constant temperature is dehydrated described in step [2] are as follows: under nitrogen protection with the heating of 1.5 DEG C/min
Rate is to slowly warm up to 204 DEG C, continues the water in the system of sloughing, until the mass fraction of N-Methyl pyrrolidone reaches in solution
97.5%.
4. it is described in accordance with the claim 1 a kind of using acylate as the method for catalyst preparation branched chain type polyphenylene sulfide, it is special
Sign is, the detailed process of step [4] are as follows: the reaction solution that step [3] obtains is to slowly warm up to 210-230 DEG C in 120min,
Constant temperature pre-polymerization 40-90min；240-270 DEG C is to slowly warm up in 60min, constant temperature polycondensation 140-200min.
5. it is described in accordance with the claim 1 a kind of using acylate as the method for catalyst preparation branched chain type polyphenylene sulfide, it is special
Sign is: organic acid described in step [1] is one of benzoic acid, caproic acid, 2 Ethylbutanoic acid or valeric acid or a variety of.
6. it is described in accordance with the claim 1 a kind of using acylate as the method for catalyst preparation branched chain type polyphenylene sulfide, it is special
Sign is: water described in step [1] is one of tap water, distilled water or ultrapure water.
7. it is described in accordance with the claim 1 a kind of using acylate as the method for catalyst preparation branched chain type polyphenylene sulfide, it is special
Sign is: in the reaction solution that step [3] obtains, the molar ratio of sodium hydroxide and acylate is 1.01-1.06:1；Sodium hydroxide
Molar ratio with water is 0.15-0.20:1；The molar ratio of vulcanized sodium and paracide is 1.0-1.05:1；N-Methyl pyrrolidone
Molar ratio with paracide is 4.5-5.7:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810825048.4A CN109134862A (en) | 2018-07-25 | 2018-07-25 | A method of using acylate as catalyst preparation branched chain type polyphenylene sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810825048.4A CN109134862A (en) | 2018-07-25 | 2018-07-25 | A method of using acylate as catalyst preparation branched chain type polyphenylene sulfide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109134862A true CN109134862A (en) | 2019-01-04 |
Family
ID=64797690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810825048.4A Pending CN109134862A (en) | 2018-07-25 | 2018-07-25 | A method of using acylate as catalyst preparation branched chain type polyphenylene sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109134862A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0778334A1 (en) * | 1995-06-16 | 1997-06-11 | Tonen Corporation | Heat-resistant lubricating oil composition |
| CN102977369A (en) * | 2012-11-21 | 2013-03-20 | 江苏格兰德投资发展有限公司 | Process for synthesizing polyphenylene sulfide resin |
| CN103897187A (en) * | 2012-12-26 | 2014-07-02 | 浙江新和成特种材料有限公司 | Synthesis method of fiber-grade polyphenylene sulfide (PPS) resin |
-
2018
- 2018-07-25 CN CN201810825048.4A patent/CN109134862A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0778334A1 (en) * | 1995-06-16 | 1997-06-11 | Tonen Corporation | Heat-resistant lubricating oil composition |
| CN102977369A (en) * | 2012-11-21 | 2013-03-20 | 江苏格兰德投资发展有限公司 | Process for synthesizing polyphenylene sulfide resin |
| CN103897187A (en) * | 2012-12-26 | 2014-07-02 | 浙江新和成特种材料有限公司 | Synthesis method of fiber-grade polyphenylene sulfide (PPS) resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073720B (en) | A kind of method of synthesizing low-color high-purity fiber-grade polyphenylene sulfide resin | |
| CN103897187B (en) | Synthesis method of fiber-grade polyphenylene sulfide (PPS) resin | |
| CN106893102B (en) | A method of polyphenylene sulfide is prepared with synthesis mother liquid | |
| CN105860030B (en) | Glycidyl amine type epoxy resin of structure containing Cardo and preparation method thereof | |
| CN104744698A (en) | Method for synthesizing linear high molecular weight polyphenylene sulfide | |
| CN102675640B (en) | Method for controlling process conditions for production and synthesis of polyphenylene sulfide | |
| CN109134862A (en) | A method of using acylate as catalyst preparation branched chain type polyphenylene sulfide | |
| CN104955877B (en) | The manufacture method of cyclic polyarylene sulfide | |
| CN104402784B (en) | Oxy-compound, sulfhydryl compound and preparation method thereof, composition of mercaptans for the preparation of optical resin | |
| CN106750302B (en) | A kind of preparation method of heat-resisting, corrosion resistant high molecular weight poly arylidene thio-ester sulfone | |
| CN109776798A (en) | Macromolecular weight poly benzene thioether resin and its preparation method and application | |
| CA1107446A (en) | Aromatic sulfide/sulfone polymer production | |
| CN105331080A (en) | Method for preparing fiber reinforced polyether sulphone resin | |
| CN103601887B (en) | A kind of method of adding compound accelerant synthon level polyphenylene sulfide in stage casing | |
| CN106243356A (en) | A kind of manufacture method of high molecular weight polyphenylene sulfide sulfone ketone | |
| CN106832283B (en) | A method of preparing polyaryl thioether sulfone | |
| CN113667123A (en) | Polyarylene sulfide compound with ultraviolet fluorescent tracing function and preparation method thereof | |
| CN105175714B (en) | A kind of process for preparing cyano group ketone-grouped resin | |
| JP2021507035A (en) | A method for producing a polyphenylene sulfide resin, and a polyphenylene sulfide resin produced by the method. | |
| CN102491951B (en) | Production process of triallyl cyanurate | |
| CN107337799A (en) | A kind of preparation method of polyarylene sulfide ketone | |
| JP3023924B2 (en) | Method for producing carboxyl group-containing arylene sulfide copolymer | |
| CN110204722A (en) | A kind of synthetic method of polyphenylene sulfide | |
| CN105085918B (en) | A kind of aromatic compound that adds is the method that solvent synthesizes polyphenylene sulfide | |
| CN115304745B (en) | Resveratrol and isovanillin based bio-based composite epoxy resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190104 |