CN108976421A - A kind of preparation method of film-grade PPS resin - Google Patents
A kind of preparation method of film-grade PPS resin Download PDFInfo
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- CN108976421A CN108976421A CN201810836735.6A CN201810836735A CN108976421A CN 108976421 A CN108976421 A CN 108976421A CN 201810836735 A CN201810836735 A CN 201810836735A CN 108976421 A CN108976421 A CN 108976421A
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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
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
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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
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
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Abstract
The invention discloses a kind of preparation methods of film-grade PPS resin, this method is with N-Methyl pyrrolidone (NMP) for solvent, 1,4- is raw material to dichloro, aqueous vulcanized sodium, 1,2,4- trichloro-benzenes is chain extender, under the effect of the catalyst, through dehydration, pre-polymerization, polycondensation, separation, wash, be dried to obtain film-grade PPS resin product.The film-grade PPS resin that this method obtains has many advantages, such as that particle is uniform, molecular weight is high, narrow molecular weight distribution, high income, while the mechanical property of resin and viscosity have and significantly promoted.Solve that traditional handicraft molecular weight product is not high, the low problem of physics, chemical property makes it possible to and is preferably applied to the fields such as fiber, film, plate, electronic component, greatly expands the application field and use scope of PPS.
Description
Technical field
The present invention relates to polymeric material field, more particularly to a kind of preparation method of film-grade PPS resin.
Background technique
Film-grade PPS resin have excellent thermal stability, chemical stability, corrosion resistance and electrical property, and with it is various
Inorganic filler has good compatibility, can be compound with various inorganic fillers and other high molecular materials, and various have excellent performance is made
Engineering plastics and blend alloy, be to promote Hi-tech Industry Development in China and traditional industry upgrading indispensable a kind of new
Type high molecular material.
Film-grade polyphenylene sulfide is the raw material for preparing PPS films.The research of PPS films started from for 20th century
The mid-1970s are begun one's study by pioneer's U.S. Philips oil company that PPS resin is studied first.Soon toray industry
Company also entered this field in 1977.It hereafter is that Japanese Wu Yu chemical industry, Tohpren company, Bayer company of Germany etc. are successive
Into the ranks of PPS thin film study.Wherein the research of U.S. Philips Corporation and toray company is leading, realizes work
Industry metaplasia produces.Dong Lilina is that the beautiful first item in east realizes industrialized PPS film product in the world.Due to having brilliance
Electrical characteristic and dimensional stability, and by UL certification permanent heat resistance, Dong Lilina product with reveal Miller for original
The product of material, which is compared, can be subjected to higher temperature.Dong Lilina film itself also just has certain anti-flammability.
China's PPS thin film study is started late, but with the emergence of some large size PPS manufacturers domestic in recent years,
They are dedicated to the production, modification and the exploitation of PPS subsequent product of PPS.There are also domestic scientific research institutions also to have carried out many PPS
The paper in terms of many PPS film formings, application and test analysis has been delivered in the research work of film.Present PPS film industry
Just as a kind of emerging industry, mushroom development is got up at home.
Film-grade polyphenylene sulfide has the thermal stability under excellent chemical resistance and high temperature, and has fire-retardant, exhausted
Edge, radiation hardness and good mechanical performance.The thin film application prepared using polyphenylene sulfide as raw material is very extensive: PPS film tool
There are high-fire resistance, high-insulativity, high dielectric property and excellent anti-flammability, mechanicalness, there is wide application in electronic field.This
Outside, because its flame retardancy can be used as wall material (including aviation inner decoration material), wire covering materials, shutter etc..Yin Qinai
Corrosion can make vaporizer diaphragm and other purposes related with automobile.Masking splicing tape can be done using its heat resistance, sensible heat is multiple
Print, printing, acoustic diaphragm and hot-fill food packaging bag and container etc..Magnetic recording material can be done using its humidity stability
Deng.
It is the seeking of being continually striving to always of researchers of various countries for the synthetic method for exploring film-grade polyphenylene sulfide.
It is described in United States Patent (USP) NO:4761468 and NO:4820801 chemical using sulfydryl and sulfydryl metal salt and reducing agent etc.
Substance poly-p-phenylene sulfide ether resin after polyphenylene sulfide synthesis is handled, to obtain film-grade PPS.But in fact this
For the PPS resin that kind method obtains in addition to the content of chlorine element is substantially reduced, the performance change of resin is smaller.Due to both
Technology is to be handled by the way of sealing end the polyphenylene sulfide of low molecular weight, used sulfydryl and sulfydryl gold
It is relatively high to belong to salt compound and reducing agent price, to increase the cost of polyphenylene sulfide.
From the point of view of existing polyphenylene sulfide synthetic technology, generally use at present vulcanized sodium and Isosorbide-5-Nitrae-paracide (P-DCB) for
Raw material add the mode of chain extender to improve PPS molecular weight, and then obtain film polyphenylene sulfide resin, but existing chain extension
There are the problems such as unstable, harsh to technique requirement for agent, it is difficult to be applied to industrial production, therefore, current thin film grade PPS's
Production technology is also immature, and product requirement is not achieved after properties of product can be made to reduce or form in jejune production technology.
Although the film-grade polyphenylene sulfide of the polyphenylene sulfide of Phillips company of the U.S. and Japan production company production
Resin substantially do not change on raw material how much, to realize film-grade by the technology controlling and process means that auxiliary material is added
The synthesis of polyphenylene sulfide, but specific technique is not disclosed, technically also to China's current thin film grade polyphenylene sulfide
There is compacting in the development of resin.
Summary of the invention
The present invention provides a kind of preparation method of film-grade PPS resin, to solve the production of prior art film-grade PPS
Technique is immature so that the technical issues of properties of product reduce or product requirement is not achieved after forming.
To solve the above technical problem, the invention adopts the following technical scheme:
A kind of preparation method of film-grade PPS resin, using aqueous vulcanized sodium, Isosorbide-5-Nitrae-paracide as raw material, with inorganic salts
It, using sodium hydroxide as auxiliary agent, is carried out in batch condensation polymerization reactor for catalyst using NMP as solvent, by solvent, catalyst, hydroxide
After sodium and aqueous vulcanized sodium are dehydrated under nitrogen protection, pre-polymerization is carried out respectively again after Isosorbide-5-Nitrae-paracide solution is added dropwise
Conjunction, polymerization, separation, washing, drying process obtain PPS resin, also added in Isosorbide-5-Nitrae-paracide solution as chain extension
The 1,2,4- trichloro-benzenes of agent.
Preferably, Isosorbide-5-Nitrae-paracide and 1, the process for preparation of 2,4- trichlorobenzene solutions are as follows: injected to being added dropwise in kettle
Then NMP opens the solid feeding port that kettle is added dropwise, put into Isosorbide-5-Nitrae-paracide and 1 to being added dropwise in kettle, 2,4- trichloro-benzenes feed intake
After, seal feed opening；It is heated up with high temperature heat conductive oil to kettle is added dropwise, when temperature in the kettle reaches 10~25 DEG C, is opened
The blender of kettle is added dropwise, is sufficiently stirred to get Isosorbide-5-Nitrae-paracide and 1, the nmp solution of 2,4- trichloro-benzenes is arrived.
Preferably, dehydration procedure specifically: solvent, sodium hydroxide, aqueous vulcanized sodium, catalyst are sequentially added into contracting
In poly- reaction kettle, under nitrogen protection, according to the heating rate of 6.5 DEG C/10min or so, 204 DEG C are to slowly warm up to by room temperature,
To material dewatering in batch condensation polymerization reactor, after dehydration, opens recirculated cooling water and cool down to batch condensation polymerization reactor, when warm in kettle
When degree is down to 150~170 DEG C, recirculated cooling water is closed.
Preferably, prepolymerization process specifically: Isosorbide-5-Nitrae-paracide solution of 1,2,4- trichloro-benzenes will be contained, slowly
And be uniformly added dropwise in batch condensation polymerization reactor, time for adding is controlled in 25~35min, after being added dropwise, with nitrogen displacement polycondensation
Air in reaction kettle is replaced rear closed batch condensation polymerization reactor；Lead to high temperature heat conductive oil into batch condensation polymerization reactor collet, makes object in kettle
Material temperature degree is gradually warming up to assigned temperature by the heating rate of average 1 DEG C/min or so, and constant temperature polymerize 1~3h, obtains low molecule
The prepolymer of amount.
Preferably, polymerization process specifically: lead to high temperature heat conductive oil into batch condensation polymerization reactor collet, make material temperature in kettle
Degree is gradually warming up to assigned temperature by the heating rate of average 1 DEG C/min or so, and constant temperature polymerize 2~4h, obtains macromolecule
Polymer；After polymerization reaction, first cooled down with low temperature conduction oil to batch condensation polymerization reactor, when temperature in the kettle is down to 180~200 DEG C
When, 0.5~1h of constant temperature, then continue to cool down with recirculated cooling water, when temperature in the kettle is down to room temperature, stop cooling.
Preferably, the molar ratio for participating in each component of reaction is respectively as follows: vulcanized sodium: paracide=1.0~1.04:
1；1,2,4- trichloro-benzenes: paracide=0.025~0.2:1, inorganic salts: vulcanized sodium=0.5~0.8:1；Sodium hydroxide: to two
Chlorobenzene=0.06~0.17:1.
Preferably, the inorganic salts are one of sodium acetate, sodium phosphate, lithium chloride, sodium carbonate.
Compared with prior art, the beneficial effects of the present invention are:
(1) chain extender that the present invention uses, property is stablized, of less demanding to technique, in traditional equipment and production technology item
The PPS resin that film-grade can be produced under part reduces the production difficulty and production cost of film-grade PPS；To original PPS tree
Rouge processing line hardly makes an amendment, and can be achieved with product up-gradation (the common upgrading for arriving film-grade), technological transformation is at low cost；
(2) present invention use new synthesis technology, obtained film-grade PPS resin, have particle is uniform, molecular weight is high,
The advantages that narrow molecular weight distribution, high income, while the mechanical property of resin and viscosity have and are significantly promoted；Solves traditional work
Skill molecular weight product is not high, the low problem of physics, chemical property, make it possible to preferably be applied to fiber, film, plate,
The fields such as electronic component；
(3) present invention can synthesize branched chain type PPS resin, overcome traditional processing technology PPS products molecule chain regularity
By force, crystallinity is high, it is not easy to which the problem of being processed to film greatly expands the application field and use scope of PPS.
Specific embodiment
It is right combined with specific embodiments below in order to make those skilled in the art more fully understand technical solution of the present invention
The present invention is described in further detail.
Embodiment 1
The technological process of production of PPS resin are as follows:
(1) preparation of the nmp solution of 1,4- paracide
To the NMP for injecting 440g in kettle is added dropwise, the solid feeding port that kettle is added dropwise then is opened, puts into 817g to being added dropwise in kettle
Isosorbide-5-Nitrae-paracide, after feeding intake, seal feed opening.It is heated up with high temperature heat conductive oil to kettle is added dropwise, works as temperature in the kettle
When reaching 20 DEG C, the blender that kettle is added dropwise is opened, is sufficiently stirred, obtains Isosorbide-5-Nitrae-paracide nmp solution.
(2) vulcanized sodium is dehydrated
3600g NMP, 15g sodium hydroxide, the aqueous vulcanized sodium of 970g, 260g sodium acetate etc. are sequentially added into batch condensation polymerization reactor
In, under nitrogen protection, according to the heating rate of 6.5 DEG C/10min or so, 204 DEG C are to slowly warm up to by room temperature, it is anti-to polycondensation
Material dewatering in kettle is answered, after material dewatering to specified requirement in kettle, dehydration terminates.Recirculated cooling water is opened to batch condensation polymerization reactor
Cool down, when temperature in the kettle is down to 160 DEG C, closes recirculated cooling water.
(3) it is added dropwise
1. Isosorbide-5-Nitrae-paracide nmp solution that step is obtained, slowly and is uniformly added dropwise in batch condensation polymerization reactor, drop
Control is in 25~35min between added-time.After being added dropwise, with air in nitrogen displacement batch condensation polymerization reactor, it is replaced rear closed contracting
Poly- reaction kettle.
(4) prepolymerization
Lead to high temperature heat conductive oil into batch condensation polymerization reactor collet, make material temperature in kettle, by the heating of average 1 DEG C/min or so
Rate is gradually warming up to assigned temperature, and constant temperature polymerize 120min, obtains the prepolymer of low molecular weight.
(5) it polymerize
Continue to lead to high temperature heat conductive oil into batch condensation polymerization reactor collet, make material temperature in kettle, by average 1 DEG C/min's or so
Heating rate is gradually warming up to assigned temperature, and constant temperature polymerize 240min, obtains the polymer of macromolecule.
(6) cool down
After polymerization reaction, first cooled down with low temperature conduction oil to batch condensation polymerization reactor, when temperature in the kettle is down to 180~200
DEG C when, constant temperature 30min, then continue to cool down with recirculated cooling water stops drop when temperature in the kettle is down to room temperature (30~50 DEG C)
Temperature, sampling, observes the synthetic effect of resin.
(7) it separates
Synthetic slurry that step (6) obtains is delivered to screening plant by synthetic slurry pump, obtained resin granular material into
Enter in washing kettle.
(8) it washs
Distilled water is added into washing kettle for the ratio of 7:1 according to the mass ratio of resin granular material, PPS resin is washed
It washs, wash temperature is controlled at 50~80 DEG C, and each wash time control is in 30~50min, as conductivity≤500 μ S/ of wash water
When cm, it can stop washing.
(9) dry
It is dried being delivered in double cone dryer through the qualified PPS resin of step (8) washing by screw conveyor,
Drying temperature controls between 100~130 DEG C, and drying pressure is tiny structure, and every 60min takes a resin-like to send in drying process
The moisture content into analysis detection Spot detection resin is dry qualified when moisture content≤0.5%.
It is tested according to above-mentioned steps, and measures melt flow rate (MFR), fusing point, density, the mechanical property of PPS resin,
It the results are shown in Table 1.
1 embodiment of table, 1 polyphenylene sulfide product testing result
Embodiment 2
The technological process of production of film-grade PPS resin are as follows:
(1) preparation of the nmp solution of 1,4- paracide and 1,2,4- trichloro-benzenes
To the NMP for injecting 440g in kettle is added dropwise, the solid feeding port that kettle is added dropwise then is opened, puts into 817g to being added dropwise in kettle
Isosorbide-5-Nitrae-paracide and 1.0g 1,2,4- trichloro-benzenes, after feeding intake, seal feed opening.With high temperature heat conductive oil to dropwise addition
Kettle heats up, and when temperature in the kettle reaches 10~25 DEG C, opens the blender that kettle is added dropwise, is sufficiently stirred, obtains Isosorbide-5-Nitrae-to two
The nmp solution of chlorobenzene and 1,2,4- trichloro-benzenes.
(2) vulcanized sodium is dehydrated
3600g NMP, 15g sodium hydroxide, the aqueous vulcanized sodium of 970g, 150g sodium phosphate etc. are sequentially added into batch condensation polymerization reactor
In, under nitrogen protection, according to the heating rate of 6.5 DEG C/10min or so, 204 DEG C are to slowly warm up to by room temperature, it is anti-to polycondensation
Material dewatering in kettle is answered, after material dewatering to specified requirement in kettle, dehydration terminates.Recirculated cooling water is opened to batch condensation polymerization reactor
Cool down, when temperature in the kettle is down to 160 DEG C, closes recirculated cooling water.
(3) it is added dropwise
1. Isosorbide-5-Nitrae-paracide and 1 that step is obtained, the nmp solution of 2,4- trichloro-benzenes slowly and are uniformly added dropwise to
In batch condensation polymerization reactor, time for adding is controlled in 25~35min.After being added dropwise, with air in nitrogen displacement batch condensation polymerization reactor, set
Closed batch condensation polymerization reactor after changing.
(4) prepolymerization
Lead to high temperature heat conductive oil into batch condensation polymerization reactor collet, make material temperature in kettle, by the heating of average 1 DEG C/min or so
Rate is gradually warming up to assigned temperature, and constant temperature polymerize 120min, obtains the prepolymer of low molecular weight.
(5) it polymerize
Continue to lead to high temperature heat conductive oil into batch condensation polymerization reactor collet, make material temperature in kettle, by average 1 DEG C/min's or so
Heating rate is gradually warming up to assigned temperature, and constant temperature polymerize 240min, obtains the polymer of macromolecule.
(6) cool down
After polymerization reaction, first cooled down with low temperature conduction oil to batch condensation polymerization reactor, when temperature in the kettle is down to 180~200
DEG C when, constant temperature 40min, then continue to cool down with recirculated cooling water stops drop when temperature in the kettle is down to room temperature (30~50 DEG C)
Temperature, sampling, observes the synthetic effect of resin.
(7) it separates
Synthetic slurry that step (6) obtains is delivered to screening plant by synthetic slurry pump, obtained resin granular material into
Enter in washing kettle.
(8) it washs
Distilled water is added into washing kettle for the ratio of 7:1 according to the mass ratio of resin granular material, PPS resin is washed
It washs, wash temperature is controlled at 50~80 DEG C, and each wash time control is in 30~50min, as conductivity≤500 μ S/ of wash water
When cm, it can stop washing.
(9) dry
It is dried being delivered in double cone dryer through the qualified PPS resin of step (8) washing by screw conveyor,
Drying temperature controls between 100~130 DEG C, and drying pressure is tiny structure, and every 60min takes a resin-like to send in drying process
The moisture content into analysis detection Spot detection resin is dry qualified when moisture content≤0.5%.
It is tested according to above-mentioned steps, and measures melt flow rate (MFR), fusing point, the density, mechanics of film-grade PPS resin
Performance the results are shown in Table 2.
2 embodiment of table, 2 polyphenylene sulfide product testing result
Embodiment 3
The technological process of production of film-grade PPS resin are as follows:
(1) preparation of the nmp solution of 1,4- paracide and 1,2,4- trichloro-benzenes
To the NMP for injecting 440g in kettle is added dropwise, the solid feeding port that kettle is added dropwise then is opened, puts into 817g to being added dropwise in kettle
Isosorbide-5-Nitrae-paracide and 1.3g 1,2,4- trichloro-benzenes, after feeding intake, seal feed opening.With high temperature heat conductive oil to dropwise addition
Kettle heats up, and when temperature in the kettle reaches 10~25 DEG C, opens the blender that kettle is added dropwise, is sufficiently stirred, obtains Isosorbide-5-Nitrae-to two
The nmp solution of chlorobenzene and 1,2,4- trichloro-benzenes.
(2) vulcanized sodium is dehydrated
3600g NMP, 15g sodium hydroxide, the aqueous vulcanized sodium of 970g, 124g lithium chloride etc. are sequentially added into batch condensation polymerization reactor
In, under nitrogen protection, according to the heating rate of 6.5 DEG C/10min or so, 204 DEG C are to slowly warm up to by room temperature, it is anti-to polycondensation
Material dewatering in kettle is answered, after material dewatering to specified requirement in kettle, dehydration terminates.Recirculated cooling water is opened to batch condensation polymerization reactor
Cool down, when temperature in the kettle is down to 160 DEG C, closes recirculated cooling water.
(3) it is added dropwise
1. Isosorbide-5-Nitrae-paracide and 1 that step is obtained, the nmp solution of 2,4- trichloro-benzenes slowly and are uniformly added dropwise to
In batch condensation polymerization reactor, time for adding is controlled in 25~35min.After being added dropwise, with air in nitrogen displacement batch condensation polymerization reactor, set
Closed batch condensation polymerization reactor after changing.
(4) prepolymerization
Lead to high temperature heat conductive oil into batch condensation polymerization reactor collet, make material temperature in kettle, by the heating of average 1 DEG C/min or so
Rate is gradually warming up to assigned temperature, and constant temperature polymerize 120min, obtains the prepolymer of low molecular weight.
(5) it polymerize
Continue to lead to high temperature heat conductive oil into batch condensation polymerization reactor collet, make material temperature in kettle, by average 1 DEG C/min's or so
Heating rate is gradually warming up to assigned temperature, and constant temperature polymerize 240min, obtains the polymer of macromolecule.
(6) cool down
After polymerization reaction, first cooled down with low temperature conduction oil to batch condensation polymerization reactor, when temperature in the kettle is down to 180~200
DEG C when, constant temperature 60min, then continue to cool down with recirculated cooling water stops drop when temperature in the kettle is down to room temperature (30~50 DEG C)
Temperature, sampling, observes the synthetic effect of resin.
(7) it separates
Synthetic slurry that step (6) obtains is delivered to screening plant by synthetic slurry pump, obtained resin granular material into
Enter in washing kettle.
(8) it washs
Distilled water is added into washing kettle for the ratio of 7:1 according to the mass ratio of resin granular material, PPS resin is washed
It washs, wash temperature is controlled at 50~80 DEG C, and each wash time control is in 30~50min, as conductivity≤500 μ S/ of wash water
When cm, it can stop washing.
(9) dry
It is dried being delivered in double cone dryer through the qualified PPS resin of step (8) washing by screw conveyor,
Drying temperature controls between 100~130 DEG C, and drying pressure is tiny structure, and every 60min takes a resin-like to send in drying process
The moisture content into analysis detection Spot detection resin is dry qualified when moisture content≤0.5%.
It is tested according to above-mentioned steps, and measures melt flow rate (MFR), fusing point, the density, mechanics of film-grade PPS resin
Performance the results are shown in Table 3.
3 embodiment of table, 3 polyphenylene sulfide product testing result
As can be seen from the above embodiments, a kind of preparation method of film-grade PPS resin described in technical scheme, system
Standby obtained film-grade PPS mechanical property is good and relatively stable, and repeatability is high.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (7)
1. a kind of preparation method of film-grade PPS resin is with inorganic salts using aqueous vulcanized sodium, Isosorbide-5-Nitrae-paracide as raw material
Catalyst, using sodium hydroxide as auxiliary agent, is carried out using NMP as solvent in batch condensation polymerization reactor, by solvent, catalyst, sodium hydroxide
And after aqueous vulcanized sodium is dehydrated under nitrogen protection, be added dropwise Isosorbide-5-Nitrae-paracide solution after again respectively carry out prepolymerization,
Polymerization, separation, washing, drying process obtain PPS resin, it is characterised in that: also added in Isosorbide-5-Nitrae-paracide solution
1,2,4- trichloro-benzenes as chain extender.
2. a kind of preparation method of film-grade PPS resin as described in claim 1, it is characterised in that: Isosorbide-5-Nitrae-paracide and
The process for preparation of 1,2,4- trichlorobenzene solution are as follows: NMP is injected to being added dropwise in kettle, then opens the solid feeding port that kettle is added dropwise, to
It is added dropwise in kettle and puts into Isosorbide-5-Nitrae-paracide and 1,2,4- trichloro-benzenes after feeding intake, seal feed opening；With high temperature heat conductive oil to drop
Add kettle to heat up, when temperature in the kettle reaches 10~25 DEG C, open the blender that kettle is added dropwise, is sufficiently stirred to get Isosorbide-5-Nitrae-is arrived
The nmp solution of paracide and 1,2,4- trichloro-benzenes.
3. a kind of preparation method of film-grade PPS resin as described in claim 1, it is characterised in that: dehydration procedure specifically:
Solvent, sodium hydroxide, aqueous vulcanized sodium, catalyst are sequentially added in batch condensation polymerization reactor, under nitrogen protection, according to 6.5 DEG C/
The heating rate of 10min or so is to slowly warm up to 204 DEG C by room temperature, to material dewatering in batch condensation polymerization reactor, after dehydration,
It opens recirculated cooling water to cool down to batch condensation polymerization reactor, when temperature in the kettle is down to 150~170 DEG C, closes recirculated cooling water.
4. a kind of preparation method of film-grade PPS resin as described in claim 1, it is characterised in that: prepolymerization process is specific
Are as follows: the Isosorbide-5-Nitrae-paracide solution that will contain 1,2,4- trichloro-benzenes slowly and is uniformly added dropwise in batch condensation polymerization reactor, when dropwise addition
Between control in 25~35min, after being added dropwise, with air in nitrogen displacement batch condensation polymerization reactor, it is anti-to be replaced rear closed polycondensation
Answer kettle；Lead to high temperature heat conductive oil into batch condensation polymerization reactor collet, make material temperature in kettle, by the heating speed of average 1 DEG C/min or so
Rate is gradually warming up to assigned temperature, and constant temperature polymerize 1~3h, obtains the prepolymer of low molecular weight.
5. a kind of preparation method of film-grade PPS resin as described in claim 1, it is characterised in that: polymerization process specifically:
Lead to high temperature heat conductive oil into batch condensation polymerization reactor collet, make material temperature in kettle, gradually by the averagely heating rate of 1 DEG C/min or so
It is warming up to assigned temperature, constant temperature polymerize 2~4h, obtains the polymer of macromolecule；It is first thermally conductive with low temperature after polymerization reaction
Oil cools down to batch condensation polymerization reactor, when temperature in the kettle is down to 180~200 DEG C, 0.5~1h of constant temperature, then continued with recirculated cooling water
Cooling stops cooling when temperature in the kettle is down to room temperature.
6. a kind of preparation method of film-grade PPS resin as described in claim 1, it is characterised in that: participate in each group of reaction
The molar ratio divided is respectively as follows: vulcanized sodium: paracide=1.0~1.04:1；1,2,4- trichloro-benzenes: paracide=0.025~
0.2:1, inorganic salts: vulcanized sodium=0.5~0.8:1；Sodium hydroxide: paracide=0.06~0.17:1.
7. a kind of preparation method of film-grade PPS resin as described in claim 1, it is characterised in that: the inorganic salts are vinegar
One of sour sodium, sodium phosphate, lithium chloride, sodium carbonate.
Priority Applications (1)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115139556A (en) * | 2022-08-18 | 2022-10-04 | 四川中科兴业高新材料有限公司 | Preparation method of PPS or PASS high-performance film based on intelligent learning |
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