CN109796584A - A kind of preparation system and preparation method of aromatic series thermotropic liquid crystal polymer - Google Patents
A kind of preparation system and preparation method of aromatic series thermotropic liquid crystal polymer Download PDFInfo
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Abstract
The invention discloses the preparation systems and preparation method of a kind of aromatic series thermotropic liquid crystal polymer; the preparation system includes: mixing arrangement; for being uniformly mixed aromatic hydroxyl in polymer monomer and/or amine compound monomer with surplus of acylation reagent, to obtain mixed material；First reactor for making the mixed material carry out acylation reaction, and carries out devolatilization, obtains acylate；Second reactor obtains aromatic liquid crystal polymer for making the aromatic carboxyl compounds monomer in received acylate and polymer monomer carry out polycondensation reaction and optional in-situ blending modification；Polymerization process of the invention carries out in the extruder of special designing, can reduce monomer homopolymerization ratio, improves properties of product, and reaction time is short, and product color is excellent, and production stability is high, high production efficiency.
Description
Technical field
The invention discloses a kind of preparation system of aromatic liquid crystal polymer and preparation method, especially application responses to squeeze
The technique that bulk polymerization prepares aromatic liquid crystal polymer out.
Background technique
Aromatic liquid crystal polymer (LCP) is a kind of high-performance polymer, has excellent thermal stability, mechanically performance
And machine-shaping property.Aromatic series LCP includes aromatic polyester and polyester-amides thermotropic liquid crystal polymer.Most common preparation
The method of aromatic series LCP is the aromatic hydroxyl or amine by removing by-product acetic acid after aromatic carboxyl compounds and acetylation
What the polymerization reaction between based compound was realized.
The acetic acid esters of typical aromatic hydroxyl or amine compound is by acetic anhydride and aromatic hydroxyl or aminated
It closes object and occurs what acetylization reaction and removing obtained after by-product acetic acid.Usually fusible aromatic series LCP is with the shape of copolymer
Formula exists, and the purpose for introducing copolymerization units is to reduce the melting temperature of product.
Patent document US4067852, which is proposed, prepares fusible full virtue using slurry polymerization in inert heat transfer medium
Polyester.The disadvantages of the method are as follows needing just obtain pure polymeric articles, preparation side by subsequent filter, washing step
Method is not economical enough.
Patent document US4868278 is described in the item using inert organic solvents, inorganic particulate and dispersion stabilizer
Aromatic copolyester is prepared using the technique of dispersin polymerization under part.The technique is equally not economical enough, needs subsequent filter, purge step
Suddenly, and in product it is mixed with inorganic particulate impurity.
Preparing the most-often used technique of aromatic copolyester is bulk technique, patent document US4181792,
It is mentioned in US4355132, US4375530, US4522974, US5798432 etc..A kind of polymerization methods are to directly heat aromatic series
The esterification derivative (such as acetic acid esters) of hydroxycarboxylic acid, aromatic diol (and/or aromatic hydroxyl amine) and aromatic diacid is just
It can trigger polycondensation reaction.Another polymerization methods are first by aromatic hydroxy-carboxylic, aromatic diol (and/or aromatic series hydroxyl
Base amine) and aromatic diacid and acetic anhydride, catalyst heat together in a kettle, acetylization reaction occurs and removes acetic acid simultaneously；
After the completion of acetylization reaction, reactant is further heated to higher temperature and carries out polycondensation reaction.It is whole in latter polymerization methods
A process carries out in single reaction kettle, and the production cycle is up to 8-24 hours.Patent document US5616680 proposes acetylation and contracting
The technique that poly- reaction step mutually separates reduces reactant by the way of controlling gas phase reflux ratio and loses and be conducive to maintain reaction
The stoichiometric ratio of each reactant in the process.The technique drops to a certain extent using two kettle series systems, compared to one-pot
The low production cycle, but due to the accumulation of high viscous material, need often to carry out washing kettle, production efficiency is not still high.
The polyester such as the chemical structure of aromatic series LCP and PET and PBT are different.In the production process of PET and PBT, list is used
Body diacid (terephthalic acid (TPA)) or two acid esters (dimethyl terephthalate (DMT)) and aliphatic diol (ethylene glycol or 1,4- butanediol)
Reaction.Usually pass through excessive glycol (30-150% is excessive) Lai Tigao direct esterification/ester exchange reaction rate and diacid/diacid
Ester conversion rate.The polycondensation reaction of substantially PET and PBT is self-balancing, and excessive glycol can phase removing after the reaction.Also
It is to say that the loss of monomer (diacid or glycol) or oligomer during the reaction will not influence the Nomenclature Composition and Structure of Complexes of final products.But
It is that in the production of aromatic series LCP, the constant of monomer stoichiometry ratio seems extremely important.It not only influences kinetics
And the chain growth of polymer, and will affect final products composition.In addition, the various monomers for participating in aromatic series LCP polymerization are anti-
Answer activity also different.Thus, the loss of reactant also results in the unbalance of stoichiometric ratio in temperature-rise period.Certain is excessively added
The mode of reactant is also unable to improve the unbalance of stoichiometric ratio, because this mode may inherently aggravate stoichiometric ratio
It is unbalance.Such as excessive hydroquinone diaeetate has just been used in patent document US4370466, chemistry be unable to completely control
Metering ratio.A variety of competitive reactions known to having in aromatic series LCP synthesis process occur, and for the reactant of those generations
The case where capable of influencing reaction condition in turn again, is then increasingly complex.The variation of reaction condition not only can be in acetylation/deacetylated
Stoichiometric ratio is influenced in reaction, it is also possible to lead to product degradation, and excessive catabolite can cause final products performance
Adverse effect.
Simultaneously as the fusing point of LCP polymerized monomer aromatic diacid is up to 300 DEG C, it is substantially carried out when being lower than 300 DEG C
It is the homopolymerization of aromatic hydroxy-carboxylic.The considerations of material stirring viscous for height, polymerize in tank reactor and is often used without
The internals such as inner coil pipe, diabatic process rely primarily on the heat transfer of kettle wall.In process units, polymerization reaction kettle specific surface area is smaller, heating
Rate is slow, can aggravate the autohemagglutination of aromatic hydroxy-carboxylic monomer, causes the deterioration and mechanical performance of Polymer Processing performance
Reduction.
Compare tank reactor, in an extruder by reactive extrursion prepare polymer have feed it is easy to control, dispersion with
Distributed rendering is excellent, and quick heating, the residence time is short, and residence time destribution is narrow, is easy to be carried out continuously, and is easy to switch, flexibility
Height, unreacted monomer and by-product can efficient removal, the advantages that viscous melt discharge of height is easy.However differential responses process is to extrusion
The requirement difference of machine is very big, it is difficult to directly cover existing extruder and be used in other chemical reactions, therefore design and develop and is suitable
Answer the extruder of specific reaction most important.
For polyester, reported in patent document it is mostly be the chain extending reaction of polyester oligomer in an extruder, directly from list
Body sets out the case for preparing polymer there is not yet report.Application response is squeezed out carries out the poly- of polycondensation reaction preparation by monomer
It closes in object, reports that more is polyetherimide.Such as polyethers is prepared using double screw extruder in patent document US4073773
Acid imide, but the extruder in the patent is difficult to use in the reactive extrursion of LCP.This is because extruder leading portion in that patent
Polymerized monomer melting is slow, will cause a large amount of homopolymerizations of aromatic hydroxy-carboxylic, while easily distillation monomer and oligomer also can be from regions 2
Exhaust outlet largely lose, seriously affect monomer mole ratio.Patent document WO2007/038373 proposes that the reaction of LCP a kind of is squeezed
Continuous polymerization technique out starts to polymerize using the acetic acid esters of monomer as reactant.Devolatilization of this technique in the first mixing section
The loss that will cause easily distillation monomer and oligomer, results in the relatively low problem of melting point polymer in embodiment, seriously affects it
Performance.In conclusion that there are production efficiencys in the existing technique for preparing aromatic polymer is low, the problem of poor product quality.Cause
This, the preparation method for developing a kind of aromatic liquid crystal polymer of new adaptation LCP polymerization is still of great significance.
Summary of the invention
It is an object of the present invention to prior art there are aiming at the problem that, a kind of system of aromatic liquid crystal polymer is provided
Standby system and preparation method, to guarantee aromatic series LCP product quality obtained.
One aspect to achieve the goals above, the preparation method system of aromatic liquid crystal polymer provided by the invention
It adopts the following technical scheme that
A kind of preparation system of aromatic liquid crystal polymer, wherein the preparation system includes:
Mixing arrangement, for making aromatic hydroxyl in polymer monomer and/or amine compound monomer and surplus of acylation
Reagent is uniformly mixed, to obtain mixed material；
First reactor for making the mixed material carry out acylation reaction, and carries out devolatilization, obtains acylate；
Second reactor, for make the aromatic carboxyl compounds monomer in received acylate and polymer monomer into
Row polycondensation reaction and optional in-situ blending are modified, obtain aromatic liquid crystal polymer；The second reactor is extruder, institute
Extruder is stated to be successively arranged along its length:
Pre-polymerization section mixes for acidylating product with aromatic carboxyl compounds monomer and carries out prepolymerization reaction；
Polymeric segment, for making the prepolymer product further progress polycondensation reaction from the pre-polymerization section and devolatilization；
Vacuum zone, for making the reaction product from the polymeric segment further react devolatilization；With
Extruding zone, for melt to be discharged；
Optionally, the extruder is additionally provided with blending section, for making fluoropolymer resin and addition from the vacuum zone
Filler blending and modifying.
In the present invention, " length direction " refers to direction of the extruder from pre-polymerization section to extruding zone；It is " optional " that indicate can be with
With and without.In the present invention, polymer obtained or blended modified polymer-modified it is referred to as aromatic liquid-crystal
Polymer.
It will be appreciated by those skilled in the art that being equipped with screw unit in extruder to realize the push of materials inside, extruder
It is the piston flow reactor for having the characteristics that multistage is easy to control, preferably double screw extruder, relatively single screw extrusion machine, twin-screw squeezes
Machine has stronger mixed, extruding machine with two screw rods engaging more preferably in the same direction, this is because it is with self-cleaning spy out
Point can effectively improve production efficiency.
Preparation system according to the present invention, it is preferable that the pre-polymerization section is equipped with spout and protection gas import, and does not set
There is exhaust outlet, screw unit (screw unit i.e. in corresponding segment) is made of screwing element and kneading block along its length；
Wherein, protection gas can be nitrogen or other inert gases；The polymeric segment is equipped with the exhaust outlet that can connect negative pressure, screw unit
It is made of screwing element, to be preferably vented, the Opening length of the exhaust outlet for connecing negative pressure of polymeric segment can account for this section of overall length
The 50%-100% of degree, preferably 60%-80%, such as 70%；The vacuum zone is equipped with the exhaust outlet that can connect negative pressure, screw rod list
Member is made of left-hand thread element, screwing element and left-hand thread element along its length, and the left-hand thread element of both ends of them is used for
Melt sealant is realized, preferably to form negative pressure；The section that is blended is equipped with spout and can connect the exhaust outlet of negative pressure, spiral shell
Bar unit is made of screwing element and kneading block along its length；The extruding zone is equipped with the exhaust outlet that can connect negative pressure, spiral shell
Bar unit is made of screwing element；It will be appreciated by those skilled in the art that in the present invention, " exhaust outlet that can connect negative pressure " refers to work
When the exhaust outlet can connect to the device of such as air-extractor to form negative pressure；Each section of " spout " being equipped with can be one
A or multiple, each section of " exhaust outlet that can connect negative pressure " being equipped with can be one or more.
In the present invention, the length of the extruder is calculated as the spiro rod length being arranged inside, and is pre-polymerization section, polymeric segment, true
The sum of dead band, extruding zone and optional length (being calculated as the spiro rod length in respective section respectively) of blending section, it is preferable that described to squeeze
The screw slenderness ratio of machine is 25-60, preferably 30-50 out, for example ratio is 35,40 or 45；The lead of the screwing element is
The lead of 0.5-2 times of screw diameter, such as 1 or 1.5 times, the kneading block and left-hand thread element is 0.5-1 times of screw diameter,
Such as 0.8 times.
Preparation system according to the present invention, it is preferable that when the extruder is equipped with, and section is blended, the pre-polymerization section accounts for extrusion
The 10-20% of machine total length, such as 15%；Polymeric segment accounts for the 20-30% of extruder total length, such as 25%；Vacuum zone accounts for crowded
The 10-20% of machine total length out, such as 15%；The 20-30% that section accounts for extruder total length, such as 25% is blended；Extruding zone accounts for
The 5-10% of extruder total length, such as 8%；It is remaining pre-polymerization section, polymeric segment, true when the extruder is not set, and section is blended
Length ratio between dead band and extruding zone is constant, namely compared with the above-mentioned extruder being equipped with when section is blended, except not setting blending
Section is outer, and other each section of mutual length relations are constant.
Preparation system according to the present invention, it is preferable that the first reactor is selected from tank reactor, and is furnished with and is condensed back to
Device is flowed with devolatilization while stablizing reaction temperature；Preferably, the tank reactor is that more kettles are arranged in parallel,
It is continuously prepared to match extruder (being respectively connected to extruder pre-polymerization section).
Other side for achieving the above object, preparation method of the invention adopt the following technical scheme that
A kind of preparation method of aromatic liquid crystal polymer uses preparation system as described above to carry out aromatic liquid-crystal
The preparation of polymer, comprising the following steps:
(1) by polymer monomer and surplus of acylation reagent mixing arrangement after mixing, and be sent into first reactor；
(2) make mixed material after first reactor carries out acylation reaction and devolatilization, be sent into second reactor；
(3) make material after second reactor carries out polycondensation and optional blending and modifying, obtain polymer melt or modification
The melt of polymer.
Polymerization reaction obtain aromatic liquid crystal polymer polymerized monomer raw material be it is known in the art, in a kind of embodiment party
In formula, the aromatic hydroxyl and/or amine compound monomer are aromatic hydroxy-carboxylic, aromatic diol, aromatic diamine
With one of aromatic hydroxyl aminate or a variety of；The aromatic carboxyl compounds monomer is aromatic diacid；The acyl
Change reagent is aliphatic carboxylic acid acid anhydride, preferably acetic anhydride；
Preferably, in the polymer monomer each monomer dosage accounting are as follows:
Aromatic hydroxy-carboxylic is 30mol%-80mol%, such as 40mol%, 50mol%, 60mol% or 70mol%；
Aromatic diacid is 10mol%-35mol%, such as 15mol%, 20mol%, 25mol% or 30mol%；
Aromatic diol is 10mol%-35mol%, such as 15mol%, 20mol%, 25mol% or 30mol%；
Aromatic diamine is 0mol%-15mol%, such as 5mol%, 8mol%, 10mol% or 12mol%；
Aromatic hydroxyl aminate is 0mol%-15mol%, such as 5mol%, 8mol%, 10mol% or 12mol%；
Wherein, the total amount of each monomer is 100mol% in the polymer monomer, it will be appreciated by those skilled in the art that working as certain list
When body accounting is 0, that is, be free of the monomer.
In the present invention, the aromatic hydroxy-carboxylic can be one of compound shown in following 1~formula of formula 6 or more
Kind:
In formula 2, X is selected from alkyl, alcohol radical or halogen, such as the alkyl of C1-C10, the alcohol radical of C6-C10, chlorine or bromine；Formula 6
In, Y is selected from-O- ,-S- ,-SO2- ,-CO- ,-CH2- or-C (CH3) 2-.
In the present invention, the aromatic diacid can be one of compound shown in following 7~formula of formula 12 or a variety of:
In formula 8, X is selected from alkyl, alcohol radical or halogen, such as the alkyl of C1-C10, the alcohol radical of C6-C10, chlorine or bromine；Formula 12
In, Y is selected from-O- ,-S- ,-SO2- ,-CO- ,-CH2- or-C (CH3) 2-.
In the present invention, the aromatic diol can be one of compound shown in following 13~formula of formula 18 or more
Kind:
In formula 14, X is selected from alkyl, alcohol radical or halogen, such as the alkyl of C1-C10, the alcohol radical of C6-C10, chlorine or bromine；Formula 18
In, Y is selected from-O- ,-S- ,-SO2- ,-CO- ,-CH2- or-C (CH3) 2-.
In the present invention, the aromatic diamine can be one of compound shown in following 19~formula of formula 24 or more
Kind:
In formula 20, X is selected from alkyl, alcohol radical or halogen, such as the alkyl of C1-C10, the alcohol radical of C6-C10, chlorine or bromine；Formula 24
In, Y is selected from-O- ,-S- ,-SO2- ,-CO- ,-CH2- or-C (CH3) 2-.
In the present invention, the aromatic hydroxyl aminate can be one of compound shown in following 25~formula of formula 30
Or it is a variety of:
In formula 26, X is selected from alkyl, alcohol radical or halogen, such as the alkyl of C1-C10, the alcohol radical of C6-C10, chlorine or bromine；Formula 30
In, Y is selected from-O- ,-S- ,-SO2- ,-CO- ,-CH2- or-C (CH3) 2-.
The preparation of aromatic series LCP mainly includes two reactions: 1) hydroxyl/amido on phenyl ring and acylating reagent be (usually
Aliphatic carboxylic acid acid anhydride) acylation reaction of ester is formed, generate such as acetic acid esters；2) shape that acetic acid esters and aromatic carboxylic acid occur
At the polycondensation reaction (melting acidolysis) of polymer chain.
Preparation method according to the present invention, it is preferable that the hydroxyl and amido in polymer monomer being added in step (1)
Integral molar quantity and the acylating reagent molar ratio be 1:1.01-2, preferably 1:1.01-1.5, more preferably 1:1.01-
1.2。
The acylation reaction that acylating reagent occurs with the hydroxyl on aromatic ring/amido can be carried out without using catalyst.It is acylated
Reaction also can choose using catalyst, especially need the case where accelerating acylation reaction in process.Of the invention preferred
Acylation reaction catalyst is added in embodiment.It can choose and acylation reaction catalyst is added in step (1) or step (2)；It is suitable
The acylation reaction catalyst of conjunction is base catalyst and/or acid catalyst, is preferably selected from amine, 2- dimethylaminopropionitrile, tributyl
One of phosphine, p-methyl benzenesulfonic acid, zinc chloride and cupric perchlorate are a variety of；Preferably, the dosage of the acylation reaction catalyst
5-1000ppm by the polymer monomer quality being added in step (1), for example, 10ppm, 100ppm, 200ppm, 500ppm or
800ppm。
Acidolysis and polycondensation reaction usually carry out in the presence of polymerization catalyst.Preferably, step (1), step (2) or
Polymerization catalyst is added in step (3).Polymeric additive is if filler and antioxidant etc. also can choose in the course of the polymerization process
It is added.
The suitable polymerization catalyst can be oxidation dialkyl tin, oxidation diaryltin, titanium dioxide, alkyl silication
One of titanium, alcohol titanium, carboxylic acid alkali salt and lewis acid are a variety of, are preferably selected from sodium acetate, potassium acetate and magnesium acetate
One of or it is a variety of；Preferably, the dosage of the polymerization catalyst is the 5-500ppm of resulting polymers quality, such as
10ppm, 100ppm, 200ppm or 300ppm.
It will be appreciated by those skilled in the art that the hybrid manipulation of step (1) is because acylation reaction can occur at high temperature and acetic acid
Acid anhydride meeting evaporation loss, so temperature is unsuitable excessively high.In one embodiment, it is 1- that the process conditions of step (1), which include: pressure,
5atm, temperature are not higher than 140 DEG C, can be 20-120 DEG C；It is preferred that carrying out under inert gas protection, such as in nitrogen or dioxy
Change the lower progress of carbon protection.
In the present invention, the acylation reaction of step (2) is known in the art, and reaction condition can be with are as follows: reaction temperature
It is 140-230 DEG C, preferably 150 DEG C -180 DEG C, such as 160 DEG C or 170 DEG C；Reaction time is 10min-3h, preferably 30min-
2h, such as 1h or 1.5h；It carries out under inert gas shielding, is preferably carried out under nitrogen or carbon-dioxide protecting；Reaction pressure is
1-5atm, preferably 1-2atm；Meanwhile the part carboxylic acid that acylation reaction generates is removed, such as acetic acid, remaining carboxylic acid can be
Further removing, devolatilization rate are preferably not less than 85%, such as 85%-95% after the reaction was completed.
Preparation method according to the present invention, it is preferable that the feed rate of extruder is maintained at full of extruder in step (3)
The starvation of volume 1/3-1/2；Screw speed is 30-400rpm, such as 50rpm, 100rpm, 200rpm or 300rpm；It squeezes
150 DEG C -320 DEG C of built-in temperature pre-polymerization section out, such as 180 DEG C, 200 DEG C, 250 DEG C or 300 DEG C, 250 DEG C -380 DEG C of polymeric segment, than
Such as 280 DEG C, 300 DEG C, 350 DEG C or 370 DEG C, 300 DEG C -380 DEG C of vacuum zone, for example, 320 DEG C, 350 DEG C, 360 DEG C or 370 DEG C, altogether
Mixed 300 DEG C -380 DEG C of section, such as 320 DEG C, 350 DEG C, 360 DEG C or 370 DEG C and 300 DEG C -380 DEG C of extruding zone, such as 320 DEG C,
350 DEG C, 360 DEG C or 370 DEG C, wherein the temperature from pre-polymerization section to vacuum zone is stepped up；Preferably, material is in extruder
Residence time is in 1min-20min range, preferably 2min-12min, such as 3min, 5min, 8min or 10min.
In the present invention, the course of work of the extruder is as follows: acylate concentrated solution and virtue from first reactor
Fragrant race's diacid monomer is added separately to the spout of extruder pre-polymerization section, two strands of materials in the case where protecting gas (such as nitrogen) atmosphere
Pre-polymerization section carries out mixing pre-polymerization, and it is pre- that the Strong shear that kneading block provides makes monomer material be rapidly achieved melting (such as 300 DEG C) beginning
Combinate form generates carboxylic acid gas (such as acetic acid gas) at pre-polymer melt.Unlike the prior art, the present invention is straight to material
Tapping into row Strong shear makes acetylation monomer and aromatic dicarboxylic acid monomers melt copolymerization rapidly, it is suppressed that aromatic hydroxy-carboxylic
Autohemagglutination.Design without exhaust outlet avoids the loss of monomer and oligomer, maintains constant molar ratio.Nitrogen is passed through
Other than providing inert atmosphere, it can also prevent acetic acid gas backmixing to the pre-polymerization section spout generated from causing feeding difficult.Feeding
Rate is maintained at the starvation full of extruder volume 1/3-1/2, to obtain biggish specific surface area, is conducive to mixing devolatilization.
The reaction was continued in polymeric segment for pre-polymer melt, and acetic acid gas is de- from exhaust outlet under the low vacuum of normal pressure or 100-300mmHg
It removes, the exhaust outlet of the threaded elements of large pitch and big aperture ensure that effective removing of small molecule.In vacuum zone, polymer
Further it polymerize under the high vacuum of 2-10mmHg, acetic acid and remaining oligomer are removed by exhaust outlet.Vacuum zone upstream and downstream is logical
It crosses and carries out melt sealant using left-hand thread element, to reach condition of high vacuum degree, the use of steep-lead thread element can be mentioned effectively
High-specific surface area is conducive to devolatilization.After polymer enters blending section, blending and modifying is carried out with the filler that the addition of section spout is blended.
Modified filler can be selected from least one of glass fibre, whisker, carbon fiber, polytetrafluoroethylene (PTFE)；And/or wollastonite, talcum
At least one of powder, mica, titanium dioxide, carbon black, calcium carbonate, clay, barium sulfate, silica.Modified melt is by squeezing out
Section squeezes out.Entire extruder barrel temperature of each section can be adjusted by cooling water, prevent material from crossing thermal decomposition.
In the present invention, the step of preparation method can also include: that the polymer melt/polymer-modified is molten
The step of body is granulated, and obtains polymeric aggregate.Melt in extruder is after air-cooled or water cooling, and pelletizing obtains in pelleter
Polymeric aggregate.
In the present invention, the aromatic liquid crystal polymer has following general formula :-(- aromatic unit-connection unit A-)
m-；
Aromatic unit includes the structure as shown in following formula (I)-formula (VI):
Wherein, the X in formula (II) is selected from alkyl, alcohol radical or halogen, the Y in formula (VI) be selected from-O- ,-S- ,-SO2- ,-
CO- ,-CH2- or-C (CH3) 2-；Connection unit A is selected from-O-CO- ,-CO-O- ,-CO-NH- or-NH-CO-.
In connection unit A, the molar content of ester group is 60-100%, preferably 80-100%.Aromatic series LCP needs contain
The aromatic unit of proper proportion, so that its property for showing thermotropic liquid crystal during melt-processed.The liquid of aromatic series LCP
Crystal phase transition temperature or melting temperature are heavily dependent on the composition of aromatic unit and connection unit A.For fusible
Melt the resin of processing, the melting temperature of aromatic series LCP is typically designed to lower than 360 DEG C.Aromatic series LCP fusing point exists in the present invention
320 DEG C of -360 DEG C of ranges.
The LCP of the method for the present invention preparation is widely used in electric, industrial fibre as fiber, film and molded article
The fields such as dimension, communication, packaging, automobile, illumination, kitchen and bath and medical treatment.
The beneficial effect of technical solution of the present invention is:
The present invention is matched by tank reactor and extruder, enhances the control to aromatic series LCP polymerization reaction
System can be greatly shortened the reaction time under high temperature to reduce autohemagglutination, degradation and other side reactions, make color, the heat of product
Stability and fluidity of molten are improved, and can obtain the polymer of more high melt viscosity and molecular weight.
It is more superior compared with the extruder of patent literature report that the extruder used is designed in the process.Pre-polymerization section of the present invention
The application of Strong shear can effectively solve the problems, such as that monomer autohemagglutination and monomer mole ratio are unbalance.Polymeric segment big opening exhaust outlet
Design and the design of vacuum zone melt sealant can be effectively improved devolatilization, improve polymer molecular weight.The use of section is blended
It may be implemented in-situ modified, prevent polymer to be repeatedly heated and cause the decline of thermal stability and mechanical performance.
In the present invention, by tank reactor in parallel, which can very easily be used for the continuous metaplasia of LCP
It produces.The present invention can produce the aromatic series LCP of different compositions and molecular weight.
Detailed description of the invention
Fig. 1 is a kind of schematic diagram of embodiment of aromatic liquid crystal polymer preparation system of the invention；
Fig. 2 is a kind of schematic diagram of embodiment of extruder used in the present invention.
Specific embodiment
Below with reference to drawings and examples, invention is further explained, but the present invention is not limited to this.
As illustrated in fig. 1 and 2, the preparation system of aromatic liquid crystal polymer of the invention include mixing arrangement R0, it is first anti-
Answer device R1 and second reactor R2, wherein the mixing arrangement R0 is used to make the aromatic hydroxyl and/or amine in polymer monomer
Based compound monomer is uniformly mixed with surplus of acylation reagent, to obtain mixed material；The mixing arrangement R0 is stirred tank.
First reactor R1 carries out devolatilization for making the mixed material carry out acylation reaction, using acetic anhydride as acyl
For changing reagent, that is, acetic acid is removed, acylate is obtained；The first reactor R1 is tank reactor, is internally provided with and stirs
Part is mixed, and is furnished with condensation reflux unit；The condensation reflux unit includes reflux column C2, condenser C1 and surge tank T1, described
Condenser C1 is for condensing the acetic acid steam from reflux column C2, and the surge tank T1 is for storing the liquid for carrying out condenser C1
Acetic acid, and using part of acetic acid as reflux be sent into reflux column C2, in reflux column C2 with the acetic acid from first reactor
Steam counter-flow contact is then refluxed for first reactor R1.In one embodiment, the tank reactor is that more kettles are in parallel
Setting, such as 2,3 or 4 kettles are arranged in parallel, and are continuously prepared with matching extruder.
Second reactor R2 is extruder, for making the aromatic carboxyl in received acylate and polymer monomer
Monomer adduct carries out polycondensation reaction and optional in-situ blending is modified, obtains aromatic liquid crystal polymer.The first reactor
Dehvery pump P1 is additionally provided between R1 and second reactor R2, it is anti-for second will to be sent into from the acylate of first reactor R1
Answer device R2.
As shown in Fig. 2, the extruder by being disposed with pre-polymerization section J1, polymeric segment J2, vacuum zone along its length
J3, section J4 and extruding zone J5 is blended, wherein the pre-polymerization section J1 is mixed for acidylating product and aromatic carboxyl compounds monomer
Merge and carries out prepolymerization reaction；The polymeric segment J2 is for making the prepolymer product further progress polycondensation reaction from the pre-polymerization section
And devolatilization；The vacuum zone J3 is for making the reaction product from the polymeric segment further react devolatilization；The blending section J4
For making the filler blending and modifying of the fluoropolymer resin from the vacuum zone and addition；The extruding zone J5 is molten for being discharged
Body.1 diameter of screw rod of extruder is 26mm, and draw ratio is about 45；Pre-polymerization section J1 length is 175mm；Polymeric segment J2 length is
351mm；Vacuum zone J3 length is 175mm；Blending section J4 length is 351mm；Extruding zone J5 length is 117mm, melt is discharged
And residual monomer.
The pre-polymerization section J1 tool of the extruder there are two spout 7 and protection gas import, (do not show in figure by nitrogen inlet
Out), wherein the first pre-polymerization section spout is connected to first reactor R1 for acylate charging, the second pre-polymerization section spout is used
It is fed in aromatic diacid；Pre-polymerization section J1 is not provided with exhaust outlet, and screw unit is made of screwing element 3 and kneading block 2.Polymerization
Section J2 has the exhaust outlet 8 that can connect negative pressure, and exhaust outlet opening accounts for the 70% of this section of total length, and screw unit is by screwing element
3 compositions.Vacuum zone J3 has the exhaust outlet that can connect negative pressure, and the both ends of screw unit are left-hand thread element 4, and centre is screw thread member
Part 3 collectively forms the effect of melt sealant.Section J4, which is blended, to be had a spout 7 and can connect the exhaust outlet 8 of negative pressure, spiral shell
Bar unit is made of screwing element 3 and kneading block 2；Extruding zone J5 has the exhaust outlet 8 that can connect negative pressure, and screw unit is by screw thread member
Part 3 forms.3 lead of screwing element is in 0.5-2d (d is screw diameter) range, the lead of kneading block 2 and left-hand thread element 4
For 1d.
The course of work of the extruder is as follows: the acylate solution from first reactor R1 is added by delivery pump P1
Enter first pre-polymerization section spout to pre-polymerization section J1, aromatic diacid monomer is added to second of pre-polymerization section by weightless title
Pre-polymerization section spout, two strands of materials carry out mixing pre-polymerization in pre-polymerization section under nitrogen atmosphere.Pre-polymer melt is in polymeric segment J2
The reaction was continued, and acetic acid gas removes under the low vacuum of 250mmHg from the exhaust outlet that can connect negative pressure.In vacuum zone J3, polymer
Further it polymerize under the high vacuum of 5mmHg, acetic acid and remaining oligomer are removed by the exhaust outlet that can connect negative pressure.Polymer into
After entering to be blended section J4, blending and modifying is carried out with the filler that the addition of section spout is blended.Modified melt is squeezed out by extruding zone J5.It squeezes out
Section screwing element lead is gradually decreased to be pressurized from 6 discharge of head.Entire extruder barrel temperature is adjusted by cooling water
Section, prevents material from crossing thermal decomposition.The extruder is preferably extruding machine with two screw rods engaging in the same direction.
The present invention is further illustrated with reference to embodiments.
The source of the reaction raw materials of following embodiment is as follows:
Terephthalic acid (TPA), lark prestige；
M-phthalic acid, Aladdin；
P-hydroxybenzoic acid, Zhejiang sage effect；
6-Hydroxy-2-naphthoic acid, lark prestige；
Hydroquinone, Aladdin；
'-biphenyl diphenol, lark prestige；
P-phenylenediamine, Aladdin；
P-aminobenzoic acid, Aladdin；
Acetic anhydride, Aladdin；
Polymerisation catalysts, potassium acetate, Aladdin；
Acylation reaction catalyst, p-methyl benzenesulfonic acid, lark prestige；
Filler, glass fibre, megalith group.
Extruder used in following embodiment is extruding machine with two screw rods engaging in the same direction, specific as shown in Figure 2.
Embodiment 1
As shown in Figure 1, stirred tank R0 is added in stream stock A.Flowing stock A includes: P-hydroxybenzoic acid 732.5g, 6- hydroxyl -2- naphthalene
Formic acid 146.7g, hydroquinone 232.7g, '-biphenyl diphenol 285.8g, p-phenylenediamine 85.9g, p-aminobenzoic acid 78.6g, acetic acid
Acid anhydride 1872.5g, potassium acetate 8.9g (polymerisation catalysts) and p-methyl benzenesulfonic acid 12.0g (acylation reaction catalyst).
After reactant mixes in stirred tank R0, into the first reactor R1 with stirring in nitrogen atmosphere, 160 DEG C of reflux
Lower progress acetylization reaction 1.5h, byproduct of reaction acetic acid steam enter reflux column C2, are stored in after condenser C1 condensation slow
It rushes in tank T1.Between 1 and 3 back to reflux column C2 control reflux ratio, another part is defeated as stream stock B for acetic acid liquid a part
It send to by-product holding vessel and (is not marked in figure).After the reaction was completed, first reactor R1 is decompressed under 500mmHg under stiring
Remaining acetic acid is removed, it is desirable that acetic acid removing amount is greater than the 90% of theoretical value.
Concentrated solution in first reactor R1 is connected with the rate of 950g/h by the first pre-polymerization section spout through dehvery pump P1
It is continuous to be delivered to extruder R2.Meanwhile it flowing stock C and being continuously conveyed by the second pre-polymerization section spout to extruder with the rate of 450g/h
R2.Stream stock B is terephthalic acid powder.Two strands of materials pass sequentially through pre-polymerization section, polymeric segment and vacuum zone in an extruder and carry out
Polycondensation reaction, and section mixing is being blended with from the stream stock D for section spout is blended being added with 320g/h rate.Stream stock D is glass fibers
Dimension.Modified material is squeezed out by extruding zone.Screw speed is 80rpm.Barrel temperature is respectively 315 DEG C of pre-polymerization section, polymeric segment
350 DEG C, 350 DEG C of vacuum zone, 345 DEG C of section of blending and 340 DEG C of extruding zone；Residence time in extruder is 11min.
After the melt that extruder squeezes out is finally by sink cooling, polymeric aggregate is obtained by pelleter pelletizing.
Through detecting, product color is shallower, uniform quality, 339 DEG C of product fusing point (7.5 DEG C of half-peak breadth), 1000s at 350 DEG C-1
When capillary viscosity be 41.3Pas.
Whole flow process may be carried out batchwise, and can also be realized by a set of reaction kettle identical with first reactor R1 in parallel
Continuous production.
Embodiment 2
As shown in Figure 1, stirred tank R0 is added in stream stock A.Flowing stock 1 includes: P-hydroxybenzoic acid 852.3g, 6- hydroxyl -2- naphthalene
Formic acid 151.2g, '-biphenyl diphenol 362.5g, acetic anhydride 1872.5g, potassium acetate 6.7g (polymerisation catalysts) and to toluene sulphur
Sour 8.6g (acylation reaction catalyst).
After reactant mixes in stirred tank R0, into the first reactor R1 with stirring in nitrogen atmosphere, 160 DEG C of reflux
Lower progress acetylization reaction 1.5h, byproduct of reaction acetic acid steam enter reflux column C2, are stored in after condenser C1 condensation slow
It rushes in tank T1.Between 1 and 3 back to reflux column C2 control reflux ratio, another part is defeated as stream stock B for acetic acid liquid a part
It send to by-product holding vessel and (is not marked in figure).After the reaction was completed, first reactor R1 is decompressed under 500mmHg under stiring
Remaining acetic acid is removed, it is desirable that acetic acid removing amount is greater than the 90% of theoretical value.
Concentrated solution in first reactor R1 is connected with the rate of 870g/h by the first pre-polymerization section spout through dehvery pump P1
It is continuous to be delivered to extruder R2.Meanwhile it flowing stock C and being continuously conveyed by the second pre-polymerization section spout to extruder with the rate of 430g/h
R2.Flow stock C are as follows: the mixture that terephthalic acid (TPA) and M-phthalic acid mass ratio are 2.2:1.Two strands of materials are in an extruder successively
Polycondensation reaction is carried out by pre-polymerization section, polymeric segment and vacuum zone, and the reaction was continued section is blended.Material is squeezed out by extruding zone.
Screw speed is 95rpm.Barrel temperature is respectively that 360 DEG C of polymeric segment, 360 DEG C of vacuum zone, section 360 is blended in 320 DEG C of pre-polymerization section
DEG C and 360 DEG C of extruding zone；Residence time in extruder is 9.5min.
After the melt that extruder squeezes out is finally by sink cooling, polymeric aggregate is obtained by pelleter pelletizing.
Through detecting, product color is shallower, uniform quality, 352 DEG C of product fusing point (8.2 DEG C of half-peak breadth), 1000s at 360 DEG C-1
When capillary viscosity be 148.3Pas.Product viscosity meets extrusion grade requirement, can be used for the preparation of LCP film.
Claims (10)
1. a kind of preparation system of aromatic liquid crystal polymer, which is characterized in that the preparation system includes:
Mixing arrangement, for making aromatic hydroxyl in polymer monomer and/or amine compound monomer and surplus of acylation reagent
It is uniformly mixed, to obtain mixed material；
First reactor for making the mixed material carry out acylation reaction, and carries out devolatilization, obtains acylate；
Second reactor, for making received acylate contract with the aromatic carboxyl compounds monomer in polymer monomer
Poly- reaction and optional in-situ blending are modified, obtain aromatic liquid crystal polymer；The second reactor is extruder, described to squeeze
Machine is successively arranged along its length out:
Pre-polymerization section mixes for acidylating product with aromatic carboxyl compounds monomer and carries out prepolymerization reaction；
Polymeric segment, for making the prepolymer product further progress polycondensation reaction from the pre-polymerization section and devolatilization；
Vacuum zone, for making the reaction product from the polymeric segment further react devolatilization；With
Extruding zone, for melt and residual monomer to be discharged；
Optionally, the extruder is additionally provided with blending section, for filling out the fluoropolymer resin from the vacuum zone with what is added
Expect blending and modifying.
2. preparation system according to claim 1, which is characterized in that
The pre-polymerization section is equipped with spout and protection gas import, and is not provided with exhaust outlet, and screw unit is along its length
It is made of screwing element and kneading block；The polymeric segment is equipped with the exhaust outlet that can connect negative pressure, and screw unit is by screwing element group
At；The vacuum zone is equipped with the exhaust outlet that can connect negative pressure, and screw unit is along its length by left-hand thread element, screwing element
It is formed with left-hand thread element, the left-hand thread element of both ends of them is for realizing melt sealant；The blending section be equipped with spout with
And the exhaust outlet of negative pressure can be connect, screw unit is made of screwing element and kneading block along its length；The extruding zone is set
There is the exhaust outlet that can connect negative pressure, screw unit is made of screwing element；
Preferably, the screw slenderness ratio of the extruder is 25-60, preferably 30-50；The lead of the screwing element is screw rod
The lead of 0.5-2 times of diameter, the kneading block and left-hand thread element is 0.5-1 times of screw diameter；
And/or；The Opening length of the exhaust outlet for connecing negative pressure of polymeric segment accounts for the 50%-100% of this section of total length, preferably
60%-80%.
3. preparation system according to claim 2, which is characterized in that described pre- when the extruder is equipped with, and section is blended
Poly- section accounts for the 10-20% of extruder total length；Polymeric segment accounts for the 20-30% of extruder total length；Vacuum zone accounts for extruder overall length
The 10-20% of degree；The 20-30% that section accounts for extruder total length is blended；Extruding zone accounts for the 5-10% of extruder total length；When described
When extruder does not set blending section, the length ratio between remaining pre-polymerization section, polymeric segment, vacuum zone and extruding zone is constant.
4. preparation system according to any one of claim 1-3, which is characterized in that the first reactor is selected from autoclave
Reactor, and it is furnished with condensation reflux unit；Preferably, the tank reactor is that more kettles are arranged in parallel, to match extruder
Continuously prepared.
5. a kind of preparation method of aromatic liquid crystal polymer, which is characterized in that using as described in any one of claim 1-4
Preparation system carry out aromatic liquid crystal polymer preparation, the preparation method comprises the following steps:
(1) by polymer monomer and surplus of acylation reagent mixing arrangement after mixing, and be sent into first reactor；
(2) make mixed material after first reactor carries out acylation reaction and devolatilization, be sent into second reactor；With
(3) make material after second reactor carries out polycondensation and optional blending and modifying, obtain polymer melt or modified poly
The melt of object.
6. preparation method according to claim 5, which is characterized in that the aromatic hydroxyl and/or amine compound list
Body is one of aromatic hydroxy-carboxylic, aromatic diol, aromatic diamine and aromatic hydroxyl aminate or a variety of；It is described
Aromatic carboxyl compounds monomer is aromatic diacid；The acylating reagent is aliphatic carboxylic acid acid anhydride, preferably acetic anhydride；
Preferably, in the polymer monomer each monomer dosage accounting are as follows:
Wherein, the total amount of each monomer is 100mol% in the polymer monomer.
7. preparation method according to claim 5 or 6, which is characterized in that in the polymer monomer being added in step (1)
Hydroxyl and amido integral molar quantity and the acylating reagent molar ratio be 1:1.01-2, preferably 1:1.01-1.5, it is more excellent
It is selected as 1:1.01-1.2.
8. the preparation method according to any one of claim 5-7, which is characterized in that be added in step (1) or step (2)
Acylation reaction catalyst；Preferably, the dosage of the acylation reaction catalyst is by the polymer monomer matter that is added in step (1)
The 5-1000ppm of amount；
Polymerization catalyst is added in step (1), step (2) or step (3)；Preferably, the dosage of the polymerization catalyst is institute
Obtain the 5-500ppm of polymer quality.
9. the preparation method according to any one of claim 5-8, which is characterized in that the acylation of preparation method step (2)
Reaction condition are as follows: reaction temperature is 140-230 DEG C, preferably 150 DEG C -180 DEG C；Reaction time is 10min-3h, preferably
30min-2h；It carries out under inert gas shielding, is preferably carried out under nitrogen or carbon-dioxide protecting；Reaction pressure is 1-5atm,
Preferably 1-2atm；Devolatilization rate is not less than 85%.
10. the preparation method according to any one of claim 5-9, which is characterized in that extruder feeds in step (3)
Material rate is maintained at the state full of extruder volume 1/3-1/2；Screw speed is in 30-400rpm range；Squeeze out built-in temperature
150 DEG C -320 DEG C of pre-polymerization section, 300 DEG C -380 DEG C of vacuum zone, is blended 300 DEG C -380 DEG C of section and squeezes 250 DEG C -380 DEG C of polymeric segment
300 DEG C -380 DEG C of section out, wherein the temperature from pre-polymerization section to vacuum zone is stepped up；Preferably, material stops in extruder
Stay the time in 1min-20min range, preferably 2min-12min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225884A (en) * | 2020-09-08 | 2021-01-15 | 惠生(泰州)新材料科技有限公司 | Method and system for continuously preparing liquid crystal polymer with adjustable molecular structure |
| CN117844349A (en) * | 2024-01-12 | 2024-04-09 | 研彩新材料科技南通有限公司 | Wear-resistant weather-resistant titanium-containing powder coating capable of increasing hardness of coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353417A (en) * | 2007-07-25 | 2009-01-28 | 四川琢新生物材料研究有限公司 | Multistage reaction continuous polymerization unit for synthesizing polylactic acid material with lactides monomer |
| CN102816308A (en) * | 2012-08-09 | 2012-12-12 | 东华大学 | Preparation method of thermotropic liquid crystal polyarylate |
| CN103819658A (en) * | 2012-11-19 | 2014-05-28 | 中国石油化工股份有限公司 | Method for producing polylactic acid with low lactide monomer content |
-
2018
- 2018-12-26 CN CN201811603245.8A patent/CN109796584B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353417A (en) * | 2007-07-25 | 2009-01-28 | 四川琢新生物材料研究有限公司 | Multistage reaction continuous polymerization unit for synthesizing polylactic acid material with lactides monomer |
| CN102816308A (en) * | 2012-08-09 | 2012-12-12 | 东华大学 | Preparation method of thermotropic liquid crystal polyarylate |
| CN103819658A (en) * | 2012-11-19 | 2014-05-28 | 中国石油化工股份有限公司 | Method for producing polylactic acid with low lactide monomer content |
Non-Patent Citations (5)
| Title |
|---|
| 李伯耿，潘祖仁: "聚合反应工程进展", 《合成橡胶工业》 * |
| 杨鸣波，黄锐: "《塑料成型工艺学》", 31 December 2014 * |
| 温变英，陈雅君: "《高分子材料加工》", 31 December 2016 * |
| 耿孝正: "《塑料混合及连续混合设备》", 31 December 2008 * |
| 贾润礼，李宁: "《塑料成型加工新技术》", 31 December 2006 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225884A (en) * | 2020-09-08 | 2021-01-15 | 惠生(泰州)新材料科技有限公司 | Method and system for continuously preparing liquid crystal polymer with adjustable molecular structure |
| CN112225884B (en) * | 2020-09-08 | 2023-02-07 | 惠生(中国)投资有限公司 | Method and system for continuously preparing liquid crystal polymer with adjustable molecular structure |
| CN117844349A (en) * | 2024-01-12 | 2024-04-09 | 研彩新材料科技南通有限公司 | Wear-resistant weather-resistant titanium-containing powder coating capable of increasing hardness of coating and preparation method thereof |
| CN117844349B (en) * | 2024-01-12 | 2024-06-11 | 研彩新材料科技南通有限公司 | Wear-resistant weather-resistant titanium-containing powder coating capable of increasing hardness of coating and preparation method thereof |
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