CN109293922A - A method of low polymer in removal Polythioetherimide resin - Google Patents
A method of low polymer in removal Polythioetherimide resin Download PDFInfo
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- CN109293922A CN109293922A CN201811138367.4A CN201811138367A CN109293922A CN 109293922 A CN109293922 A CN 109293922A CN 201811138367 A CN201811138367 A CN 201811138367A CN 109293922 A CN109293922 A CN 109293922A
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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
- C08G75/0204—Polyarylenethioethers
- C08G75/0277—Post-polymerisation treatment
- C08G75/0281—Recovery or purification
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Abstract
The present invention provides a kind of methods of low polymer in removal Polythioetherimide resin, comprising: the Polythioetherimide toner that weight fraction is 15~60% is added in reaction kettle；To carried out nitrogen displacement after reaction kettle in be added mass fraction be 40~95% aprotic polar solvent；Mixture in reaction kettle is stirred；After the Polythioetherimide resin is completely dissolved transparent solution, cooling processing is carried out to mixture；When temperature is down to 40 DEG C or less, it is slowly added to a certain amount of nonpolar solvent or weak polar solvent in the mixture, after a certain amount of toner is precipitated, stops that the nonpolar solvent or weak polar solvent is added；Sampling, is tested after filtering, carries out blowing to reaction kettle after molecular weight distribution reaches target value, and carry out centrifugal filtration under nitrogen protection.The method effectively removes the polymer of the low molecular weight in Polythioetherimide resin, improves the physical property of Polythioetherimide resin.
Description
Technical field
The present invention relates to the preparation method fields of Polythioetherimide resin, and in particular to a kind of removal polythiaether acyl is sub-
The method of low polymer in polyimide resin.
Background technique
Polythioetherimide resin is a kind of very promising thermoplasticity heat-proof macromolecule material.Pass through disubstituted phthaloyl
The Polythioetherimide that imines is synthesized with vulcanized sodium or NaHS or sulphur is that polyimides manufacturing cost is effectively reduced in one kind
Synthetic method, which has important impetus to the application popularization of polyimides.
It is found by the applicant that at least there is following technical problem in the prior art: being closed using above-mentioned nucleophilic displacement of fluorine etherification reaction
Have as following drawbacks at the method for Polythioetherimide: often there is the molecular weight point of Polythioetherimide in the synthesis process
The wider situation of cloth, molecular weight distribution width is greater than 4 in many cases, physical mechanical of the so wide molecular weight distribution to material
Performance is affected, and is affected especially for the impact strength of material.Therefore, if Polythioetherimide tree can be removed
The polymer of low molecular weight is in rouge to control the dispersion of distribution of Polythioetherimide resin middle-molecular-weihydroxyethyl, to be remarkably improved
The physical mechanical property of material.But the method due to being used for different high molecular materials removal low polymer in the prior art
It is all different, for Polythioetherimide resin at present still be in the technological development stage, there is no it is any can remove it is poly-
The method of low polymer in thioether imide resin is based on this, and the invention proposes one kind to effectively remove polythiaether acyl Asia
The method of low polymer in polyimide resin.
Summary of the invention
The purpose of the present invention is to provide a kind of method of low polymer in removal Polythioetherimide resin, this sides
Method can effectively remove low polymer in Polythioetherimide resin, to reduce molecule in Polythioetherimide resin
The dispersion of distribution of amount improves the physical mechanical property of Polythioetherimide resin material.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of method for removing low polymer in Polythioetherimide resin comprising:
The Polythioetherimide toner that weight fraction is 15~60% is added in reaction kettle；
To carried out nitrogen displacement after reaction kettle in be added mass fraction be 40~95% aprotic polar solvent；
Mixture in reaction kettle is stirred；
After the Polythioetherimide resin is completely dissolved transparent solution, cooling processing is carried out to mixture；
When temperature is down to 40 DEG C or less, it is slowly added to a certain amount of nonpolarity in the mixture under quick stirring
Solvent or weak polar solvent after a certain amount of toner is precipitated stop that the nonpolar solvent or weak polar solvent is added；
Sampling, is tested after filtering, carries out blowing to reaction kettle after molecular weight distribution reaches target value, and protect in nitrogen
Shield is lower to carry out centrifugal filtration.
A preferred embodiment of the invention, the method also includes: for the filter cake use after centrifugal filtration
It after ethyl alcohol is washed, then washes, the polythiaether acyl for being dried in vacuo to obtain required target value molecular weight at 180 DEG C is sub-
Polyimide resin.
A preferred embodiment of the invention, the method also includes: for the filtrate use after centrifugal filtration
Simultaneously recycling design is cooled to 50 DEG C hereinafter, being then placed in ethyl alcohol or water after it is concentrated into certain viscosity for distilling apparatus concentration
It is precipitated, washed, filtering crushes, obtains low molecular weight Polythioetherimide toner after drying.
The step of a preferred embodiment of the invention, the mixture in reaction kettle is stirred, is also
It include: to heat while being stirred to mixture to mixture.
A preferred embodiment of the invention, the method also includes: line will be stirred under quick stirring
Speed control is in 0.5~0.8m/s.
A preferred embodiment of the invention, the aprotic polar solvent include one of following components or
It is several: dimethylformamide, dimethyl acetamide, dimethyl pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide or diethyl two
Diethylene glycol dimethyl ether.
A preferred embodiment of the invention, the nonpolar solvent or weak polar solvent include in following components
One or more: benzene,toluene,xylene, chlorobenzene, hexane, heptane, octane or nonane.
A preferred embodiment of the invention, the aprotic polar solvent and nonpolar solvent or low pole are molten
Mass ratio between agent is 90:10~10:90.
A preferred embodiment of the invention, the Polythioetherimide resin be have the following structure it is poly-
Thioether acid imide:
Wherein, the position of substitution of thioether bond on phenyl ring is 3,3 '-positions, 4,4 '-positions or 3,4 '-positions；
Wherein, Ar and Ar ' is one kind of following aromatic diamines: p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-benzidines, 2,
2 '--4,4 '-benzidines of dimethyl, 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, 4,4 '-diamino diphenyl sulfides
Ether, 3,4 '-diaminodiphenyl sulfides, 4,4 '-diamino benzophenone, 3,3 '-diamino benzophenone, 4,4' diaminodiphenyl sulfone,
Bis- (4- amino-benzene oxygen) benzene of 3,3 '-diaminodiphenylsulfones, 4,4 '-diaminodiphenylmethane, 1,3-, bis- (the 4- aminobenzenes of 1,4-
Oxygroup) benzene, bis- (3- amino-benzene oxygen) benzene of 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,4-, 4,4 '-bis- (3- amino-benzene oxygens) connection
Benzene, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl sulphone (DPS)s, 2,2 '-bis- [(4- amino-benzene oxygen) phenyl] propane, the bis- (γ-amine third of 1,3-
Base) -1,1 ', bis- [(4- amino-benzene oxygen) benzoyl] benzene of 3,3 '-tetramethyl disiloxanes, 1,3- or bis- [(the 3- amino of 1,3-
Phenoxy group) benzoyl] benzene.
A preferred embodiment of the invention, low polymer is point in the Polythioetherimide resin
Son amount is less than the polymer of 5000g/mol.
Based on the above-mentioned technical proposal, the side for removing low polymer in Polythioetherimide resin of the embodiment of the present invention
The beneficial effect of method is: can be hydrogenated by means of the present invention with effective solution in disubstituted phthalimide and vulcanized sodium or sulphur
The problem of sodium or the Polythioetherimide resin middle-molecular-weihydroxyethyl wider distribution of sulphur synthesis, effectively remove Polythioetherimide
The polymer of low molecular weight in resin improves the physical mechanical property of Polythioetherimide resin.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The method of the embodiment of the present invention is specifically described below.
The method of the embodiment of the present invention is using copolymerization thioether imide resin macromolecular and small molecule in aprotonic polar
The in the mixed solvent dissolubility difference of solvent and nonpolar solvent (or weak polar solvent) realizes the removal of small molecule.With isomery
The Polythioetherimide of thioether dianhydride structure has preferable dissolubility in the aprotic polar solvents such as DMAC, non-in toluene etc.
It is then fairly insoluble in polarity or weak polar solvent, and the polarity dissolved each other at two kinds and nonpolar in the mixed solvent also have it is certain molten
Xie Du, and the small big molecule of Polythioetherimide molecular proportion molecular weight of molecular weight has bigger solubility.When nonpolarity is molten
When the ratio of in the mixed solvent reaches critical value, resin starts to be precipitated for agent or weak polar solvent, and is that molecular weight is big and gathers
Thioether acid imide molecule is preferentially precipitated.Polythiaether can be controlled by the additional amount of control nonpolar solvent or weak polar solvent
The amount of precipitation of acid imide analysis.
It is dissolved first with solubility of the Polythioetherimide resin in aprotic polar solvent, then in strength
It is slowly added to a certain amount of nonpolar solvent under shear agitation state or weak polar solvent forms a kind of mixed solvent, with non-pole
The increase of property solvent or weak polar solvent, the biggish resin of molecular weight is preferably precipitated, and the relatively small resin analysis of molecular weight
It is also dissolved in the mixed solvent at this time, is then filtered, washed and dried, the resin after the small molecule that is removed resin.Tool
Body method is as follows:
The method of low polymer in a kind of removal Polythioetherimide resin provided by the invention comprising:
Step 1: the Polythioetherimide toner that weight fraction is 15~60% is added in reaction kettle；
Preferably, the Polythioetherimide toner of 15~60 mass fractions is added in step 1 has forced shears
It cuts in the reaction kettle of stirring.
Step 2: to carried out nitrogen displacement after reaction kettle in be added mass fraction be 40~95% aprotonic polar
Solvent.
Preferably, aprotic polar solvent of the invention includes one or more of following components: dimethylformamide
(DMF), dimethyl acetamide (DMAC), dimethyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), hexamethyl phosphoramide
(HMP) or diethylene glycol dimethyl ether.
Step 3: the mixture in reaction kettle is stirred.
Preferably, the step of mixture in reaction kettle is stirred further include: stirred to mixture
Mixture is heated while mixing, i.e., opens heating quickening resin while reaction kettle is opened and stirred and gradually dissolves.Or
Person is not turned on heating so that resin gradually dissolves while reaction kettle is opened and stirred.
Step 4: after the Polythioetherimide resin is completely dissolved transparent solution, mixture is carried out at cooling
Reason；
Preferably, after Polythioetherimide resin is completely dissolved transparent solution, so that reaction kettle is stopped heating, maintain to stir
It mixes.
Step 5: it when temperature is down to 40 DEG C or less, is slowly added in the mixture under quick stirring a certain amount of
Nonpolar solvent or weak polar solvent after a certain amount of toner is precipitated stop that the nonpolar solvent or weak is added
Polar solvent；
Preferably, nonpolar solvent of the invention or weak polar solvent include one or more of following components: benzene, first
Benzene, dimethylbenzene, chlorobenzene, hexane, heptane, octane or nonane.Wherein, dimethylbenzene includes ortho-xylene, paraxylene or diformazan
Benzene.
Preferably, when temperature is down to 40 DEG C or less, under quick stirring, be slowly added to above-mentioned nonpolar solvent or
One or more of weak polar solvent, after a certain amount of nonpolar solvent or weak polar solvent is added, molecular weight is biggish
Powder is gradually precipitated into resin, wait precipitate into it is a certain amount of after, stop be added.Preferably, line will be stirred under quick stirring
Speed control is in 0.5~0.8m/s.
Step 6: sampling is tested after filtering, carries out blowing to reaction kettle after molecular weight distribution reaches target value, and
Centrifugal filtration is carried out under nitrogen protection.
Preferably, the above method further include: after being washed for the filter cake after centrifugal filtration using ethyl alcohol, it is preferred that
It ethanol washing 4 times, then washes, it is preferred that washing 2 times.Then it is dried in vacuo to obtain required target value point at 180 DEG C
The Polythioetherimide resin of son amount.
Preferably, for the filtrate after centrifugal filtration using distilling apparatus concentration and recycling design, it is preferred that by filtrate plus
Enter into the reaction kettle with stirring and vacuum condensing unit, is evaporated, after it is concentrated into certain viscosity, it is preferred that one
As viscosity less than 2000 centipoise when, be cooled to 50 DEG C and be precipitated hereinafter, being then placed in ethyl alcohol or water, it is washed, filtering, crush,
Low molecular weight Polythioetherimide toner is obtained after drying.Low molecular weight Polythioetherimide resin can be used for coating or
Direct hydrolysis recycles thioether dianhydride and diamines.
Preferably, in the method for the embodiment of the present invention aprotic polar solvent and nonpolar solvent or weak polar solvent it
Between mass ratio be 90:10~10:90.
Preferably, Polythioetherimide resin of the present invention refers to the Polythioetherimide having the following structure:
Wherein, the position of substitution of thioether bond on phenyl ring is 3,3 '-positions, 4,4 '-positions or 3,4 '-positions.
Wherein, Ar and Ar ' is one kind of following aromatic diamines: p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-benzidines, 2,
2 '--4,4 '-benzidines of dimethyl, 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, 4,4 '-diamino diphenyl sulfides
Ether, 3,4 '-diaminodiphenyl sulfides, 4,4 '-diamino benzophenone, 3,3 '-diamino benzophenone, 4,4' diaminodiphenyl sulfone,
Bis- (4- amino-benzene oxygen) benzene of 3,3 '-diaminodiphenylsulfones, 4,4 '-diaminodiphenylmethane, 1,3-, bis- (the 4- aminobenzenes of 1,4-
Oxygroup) benzene, bis- (3- amino-benzene oxygen) benzene of 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,4-, 4,4 '-bis- (3- amino-benzene oxygens) connection
Benzene, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl sulphone (DPS)s, 2,2 '-bis- [(4- amino-benzene oxygen) phenyl] propane, the bis- (γ-amine third of 1,3-
Base) -1,1 ', bis- [(4- amino-benzene oxygen) benzoyl] benzene of 3,3 '-tetramethyl disiloxanes, 1,3- or bis- [(the 3- amino of 1,3-
Phenoxy group) benzoyl] benzene.
Preferably, low polymer is that molecular weight is less than 5000g/ in Polythioetherimide resin of the present invention
The polymer of mol.
Method and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
After the displacement three times of 2000ml nitrogen is added in the Polythioetherimide Resin A 200g that intrinsic viscosity is 0.35dl/g
Reaction flask in, be added 800ml DMAC, start and be stirred and heated to 60 DEG C, after resin is completely dissolved into clear solution, stop
It only heats, maintains stirring.Toluene is slowly added under quick stirring when temperature is reduced to 40 DEG C or less, is added a certain amount of
It has resin later and is slowly precipitated, it is the biggish resin of molecular weight that resin is precipitated at this time, and when toluene to be added close to 400ml stops
It is added.Blowing, and carry out filtered off with suction.Filter cake 4 times removing toluene of ethanol washing and remnants DMAC, then it is washed with distilled water 2
It is 4 hours dry at 180 DEG C in heated-air circulation oven after removing residual ethanol.Resin A intrinsic viscosity after test is dry is
0.38dl/g.Illustrate that method of the invention can effectively improve the Polythioetherimide resin molecular weight dispersion of distribution, improves
The physical mechanical property of resin.
Remaining small molecule filtrate is added in the reaction kettle with stirring and vacuum condensing unit, is evaporated, dense to its
It after being reduced to certain viscosity, is cooled to 50 DEG C and is precipitated hereinafter, being then placed in ethyl alcohol or water, washed, filtering crushes, after drying
Obtain low molecular weight Polythioetherimide toner.
Embodiment 2
2000ml nitrogen is added in the Polythioetherimide Resin A 200g that intrinsic viscosity in embodiment 1 is 0.35dl/g
In reaction flask after displacement three times, 800mlDMAC is then added, opens and stirs and be added to 60 DEG C, be completely dissolved into resin
After clear solution, stop heating, maintains stirring.Slowly add under quick stirring when being reduced to 40 DEG C or less to temperature
Enter toluene, have resin after addition is a certain amount of and be slowly precipitated, the resin being precipitated at this time is the biggish resin of molecular weight, to be added
Stop being added when 500ml toluene.Blowing, and filtered under nitrogen protection.Wherein filter cake 4 times removing toluene of ethanol washing
And remaining DMAC, then be dried in hot-air oven at 180 DEG C after being washed with distilled water 2 times removing residual ethanols.It surveys
Resin properties viscosity number after examination is dry is 0.36dl/g.
By the test result of embodiment 1 and embodiment 2 it is found that the increase small molecule resin with nonpolar solvent can be continuous
It is precipitated, therefore, the additional amount of nonpolar solvent need to be adjusted according to the solubility property of resin to obtain the resin of required molecular weight.
Embodiment 3
2000ml nitrogen is added in the Polythioetherimide Resin A 200g that intrinsic viscosity in embodiment 1 is 0.35dl/g
In reaction flask after displacement three times, 800mlDMSO is added, unlatching is stirred and heated to 60 DEG C, is completely dissolved into resin transparent
After solution, stop heating, maintains stirring.First is slowly added under quick stirring when being reduced to 40 DEG C or less to temperature
Benzene has resin after addition is a certain amount of and is slowly precipitated, and it is the biggish resin of molecular weight that resin is precipitated at this time, and 500ml to be added faces
Stop being added when dimethylbenzene.Blowing, and filtered under nitrogen protection.The wherein filter cake adjacent diformazan of 4 times removings of ethanol washing
Benzene and remnants DMSO, then be dried in hot-air oven at 180 DEG C after being washed with distilled water 2 times removing ethyl alcohol.Test is dry
Resin properties viscosity number after dry is 0.39dl/g.Illustrate that method of the invention can effectively improve Polythioetherimide molecular weight
The dispersion of distribution.
By the test result of embodiment 2 and embodiment 3 it is found that using DMSO as aprotic polar solvent, using neighbour two
Toluene as nonpolar solvent relative to using DMAC as aprotic polar solvent, it is made as nonpolar solvent using toluene
Standby Polythioetherimide resin has smaller molecular weight distribution width.
Embodiment 4
2000ml is added in the Polythioetherimide Resin A 200g that intrinsic viscosity obtained in embodiment 1 is 0.38dl/g
With in the reaction flask after nitrogen displacement three times, it is added in 800ml NMP, starts and be stirred and heated to 60 DEG C, it is completely molten to resin
After solution is at clear solution, stop heating, maintains stirring.Delay under quick stirring when being reduced to 40 DEG C or less to temperature
It is slow that chlorobenzene is added, resin is had after addition is a certain amount of and is slowly precipitated, and it is the biggish tree of resin middle-molecular-weihydroxyethyl that resin is precipitated at this time
Rouge stops being added when 500ml chlorobenzene is added.Blowing, and filtered under nitrogen protection.Filter cake is removed with ethanol washing 4 times
Toluene and remnants NMP, then be dried in hot-air oven at 180 DEG C after being washed with distilled water twice of removing residual ethanol.
Resin properties viscosity number is 0.41dl/g after test is dry.
Embodiment 5
2000ml is added in the Polythioetherimide Resin A 200g that intrinsic viscosity obtained in embodiment 1 is 0.38dl/g
In reaction flask after nitrogen displacement three times, it is added in 800ml diethylene glycol dimethyl ether, starts and be stirred and heated to 60 DEG C, wait set
After rouge is completely dissolved into clear solution, stop heating, maintains stirring.It is quickly being stirred when being reduced to 40 DEG C or less to temperature
It is slowly added to heptane under state, has resin after addition is a certain amount of and is slowly precipitated, it is resin middle-molecular-weihydroxyethyl that resin is precipitated at this time
Biggish resin stops being added when being added close to 400ml heptane.Blowing, and carry out filtered off with suction.Filter cake is with ethanol washing 4 times
Toluene and remaining diethylene glycol dimethyl ether are removed, then is washed with distilled water after twice of removing residual ethanol in heated-air circulation oven
It is 4 hours dry at 180 DEG C.Resin A intrinsic viscosity is 0.42dl/g after test is dry.
In conclusion can there is the method for low polymer in the removal Polythioetherimide resin of the embodiment of the present invention
Molecular weight polymers in the removal resin of effect, effectively reduce the molecular weight distribution width of resin, improve the physical machine of resin
Tool performance improves the impact strength of Polythioetherimide resin.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of method of low polymer in removal Polythioetherimide resin, characterized in that it comprises:
The Polythioetherimide toner that weight fraction is 15~60% is added in reaction kettle；
To carried out nitrogen displacement after reaction kettle in be added mass fraction be 40~95% aprotic polar solvent；
Mixture in reaction kettle is stirred；
After the Polythioetherimide resin is completely dissolved transparent solution, cooling processing is carried out to mixture；
When temperature is down to 40 DEG C or less, it is slowly added to a certain amount of nonpolar solvent in the mixture under quick stirring
Or weak polar solvent after a certain amount of toner is precipitated stops that the nonpolar solvent or weak polar solvent is added；
Sampling, is tested after filtering, carries out blowing to reaction kettle after molecular weight distribution reaches target value, and under nitrogen protection
Carry out centrifugal filtration.
2. the method according to claim 1, wherein the method also includes: for the filter cake after centrifugal filtration
It after being washed using ethyl alcohol, then washes, is dried in vacuo to obtain the polythiaether of required target value molecular weight at 180 DEG C
Imide resin.
3. the method according to claim 1, wherein the method also includes: for the filtrate after centrifugal filtration
Using distilling apparatus concentration and recycling design, after it is concentrated into certain viscosity, be cooled to 50 DEG C hereinafter, be then placed in ethyl alcohol or
It is precipitated in water, washed, filtering crushes, obtains low molecular weight Polythioetherimide toner after drying.
4. method according to claim 1 to 3, which is characterized in that the mixture in reaction kettle carries out
The step of stirring further include: mixture is heated while being stirred to mixture.
5. the method according to claim 1, wherein the method also includes: will stir under quick stirring
Wire velocity control is mixed in 0.5~0.8m/s.
6. the method according to claim 1, wherein the aprotic polar solvent includes one in following components
Kind is several: dimethylformamide, dimethyl acetamide, dimethyl pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide or two
Glycol dimethyl ether.
7. according to the method described in claim 6, it is characterized in that, the nonpolar solvent or weak polar solvent include with the following group
One or more of point: benzene,toluene,xylene, chlorobenzene, hexane, heptane, octane or nonane.
8. the method according to the description of claim 7 is characterized in that the aprotic polar solvent and nonpolar solvent or weak pole
Property solvent between mass ratio be 90:10~10:90.
9. the method according to claim 1, wherein the Polythioetherimide resin is to have the following structure
Polythioetherimide:
Wherein, the position of substitution of thioether bond on phenyl ring is 3,3 '-positions, 4,4 '-positions or 3,4 '-positions；
Wherein, Ar and Ar ' is one kind of following aromatic diamines: p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-benzidines, 2,2 '-two
Methyl -4,4 '-benzidine, 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, 4,4 '-diaminodiphenyl sulfides, 3,
4 '-diaminodiphenyl sulfides, 4,4 '-diamino benzophenone, 3,3 '-diamino benzophenone, 4,4' diaminodiphenyl sulfone, 3,3 '-
Bis- (4- amino-benzene oxygen) benzene of diaminodiphenylsulfone, 4,4 '-diaminodiphenylmethane, 1,3-, 1,4- bis- (4- amino-benzene oxygens)
Bis- (3- amino-benzene oxygen) benzene of benzene, 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,4-, 4,4 '-bis- (3- amino-benzene oxygen) biphenyl, 4,
4 '-bis- (3- amino-benzene oxygen) diphenyl sulphone (DPS)s, 2,2 '-bis- [(4- amino-benzene oxygen) phenyl] propane, 1,3- bis- (γ-amine propyl)-
Bis- [(4- amino-benzene oxygen) benzoyl] benzene of 1,1 ', 3,3 '-tetramethyl disiloxanes, 1,3- or bis- [(the 3- aminobenzene oxygen of 1,3-
Base) benzoyl] benzene.
10. the method according to claim 1, wherein low molecule polymerize in the Polythioetherimide resin
Object is the polymer that molecular weight is less than 5000g/mol.
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Cited By (3)
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| CN110029405A (en) * | 2019-04-08 | 2019-07-19 | 东华大学 | A kind of preparation method of high uniformity p-aramid fiber |
| CN113180286A (en) * | 2021-04-28 | 2021-07-30 | 江苏中烟工业有限责任公司 | Separation and purification method of macromolecular dephenolic acids in tree moss extract |
| CN115785446A (en) * | 2022-11-30 | 2023-03-14 | 山东海科创新研究院有限公司 | Method for purifying sulfone polymer |
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| CN110029405A (en) * | 2019-04-08 | 2019-07-19 | 东华大学 | A kind of preparation method of high uniformity p-aramid fiber |
| CN113180286A (en) * | 2021-04-28 | 2021-07-30 | 江苏中烟工业有限责任公司 | Separation and purification method of macromolecular dephenolic acids in tree moss extract |
| CN113180286B (en) * | 2021-04-28 | 2022-04-29 | 江苏中烟工业有限责任公司 | Separation and purification method of macromolecular dephenolic acids in tree moss extract |
| CN115785446A (en) * | 2022-11-30 | 2023-03-14 | 山东海科创新研究院有限公司 | Method for purifying sulfone polymer |
| CN115785446B (en) * | 2022-11-30 | 2024-04-05 | 山东海科创新研究院有限公司 | Purification method of sulfone polymer |
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