CN107189060B - A kind of semiaromatic polyamide composition and preparation method thereof - Google Patents
A kind of semiaromatic polyamide composition and preparation method thereof Download PDFInfo
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- CN107189060B CN107189060B CN201610144957.2A CN201610144957A CN107189060B CN 107189060 B CN107189060 B CN 107189060B CN 201610144957 A CN201610144957 A CN 201610144957A CN 107189060 B CN107189060 B CN 107189060B
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
- C08G69/30—Solid state polycondensation
Abstract
The invention discloses a kind of semiaromatic polyamide composition and preparation method thereof, the preparation method is the following steps are included: (a) dicarboxylic acids and diamine take water as a solvent carry out neutralization reaction, formation semiaromatic polyamide composition salting liquid；(b) the semiaromatic polyamide composition salting liquid that step (a) obtains is further heated up, by constantly draining promotion polycondensation, obtains semiaromatic polyamide composition performed polymer by prepolymerization；(c) obtained performed polymer carries out thickening reaction and obtains semiaromatic polyamide composition in step (b).The present invention uses the diamine and binary acid of polymer grade, simplify operating process, diamine is separated and recovered using diamine online separating and reclaiming device in pre-polymerization process, diamine is effectively reduced to be lost with the volatilization of water vapour, it avoids generating pollution, the molar ratio of diamine and dicarboxylic acids, improves yield, obtains the stable product of quality during holding prepolymerization reaction.
Description
Technical field
The present invention relates to polyamide material fields, and in particular to the preparation method of semiaromatic polyamide composition.
Background technique
Polyamide is since realizing industrialization, and since it is with excellent mechanical performance and preferable electrical property, and its is resistance to
Hot, wear-resisting, chemical-resistant resistance and self-lubricating property are excellent, and have good processing performance, are widely used in clothing fibers
It is also widely used in automobile, electronic and electrical field with industrial materials field and as general engineering plastic.But due to
The general polyamide, which is easy water suction, causes size unstable, and heat resistance is inadequate.With the development of science and technology, electric
Requirement of the fields such as industry to material is higher and higher.To the polyamide for being applied to these fields, high heat resistance and size are needed
Stability.However, as traditional polyamide material such as nylon 6, nylon66 fiber is no longer satisfied, hyundai electronics are electrical and garage
The requirement of industry.Therefore, there is an urgent need to develop new polyamide materials, improve the mechanical performance and heat resistance of material.
Semiaromatic polyamide composition in main chain due to importing aromatic ring, to improve heat resistance and mechanical performance, drops
Low water imbibition, can satisfy the requirement of electric industry and automobile industry.With the development of science and technology, semiaromatic polyamide composition
Application have new breakthrough and progress, the field of application is more and more extensive, the market demand in rise trend.
Semiaromatic polyamide composition product mainly has 4T copolymer, 6T copolymer, 9T, 10T and MXD6 etc. at present.6T series half
Aromatic polyamide product is had excellent performance as earliest semiaromatic polyamide composition is invented, and raw material output is big and channel source is wide
It is general, it is low in cost, it is produced and is widely applied on a large scale.
In existing technology, there are mainly four types of the preparation methods of high-temperature nylon: high temperature and pressure solution polycondensation, cryogenic fluid
Condensation methods, polycondensation of polyester method, direct melt polycondensation method.
Currently, since high temperature and pressure solution polycondensation technique is relatively stable, process is relatively simple, products pure, process route
Diversification has industrially been widely used.
Patent CN101456949 describes the technique road that a kind of high temperature and pressure solution polycondensation prepares semiaromatic polyamide composition
The diamine of aromatic dicarboxylic acid and 4-14 carbon atom is first dissolved in organic solvent and carries out neutralization reaction by line, then carries out
Separating, washing obtains semiaromatic polyamide composition salt, then takes water as a solvent and polymerize semiaromatic polyamide composition salt to obtain semiaromatic
Polyamide performed polymer, then performed polymer is subjected to thickening reaction and obtains semiaromatic polyamide composition.Although being purified using the method
Reaction raw materials improve the accuracy of raw material proportioning, but be easy to cause pollution using organic solvent at salt recrystallization process,
The salt of generation needs to wash purification, needs to be recycled at solvent used in salt, increases energy consumption and cost, extends reaction week
Phase.
Patent CN101200542 describe first by dicarboxylic acids and diamines it is soluble in water after carry out mixing to be again neutralized into salt anti-
It answers, obtained salting liquid carries out recrystallizing isolated polyamide salt again, then is polymerize obtained salt to obtain polyamide
Primary polymer, primary polymer, which reacts after crushing using thickening, obtains semiaromatic polyamide composition.This method is molten using water
Agent purifies raw material, guarantees the proportion of raw material, and salt soluble in water can not be kept completely separate, and reduces yield, and at salt worker
Sequence is more complex, increases operating process.
A kind of preparation method of semiaromatic polyamide composition is disclosed in patent US6133406: first being taken water as a solvent, lower
At a temperature of the lower semiaromatic polyamide composition primary polymer of composite character viscosity, it is viscous then to obtain characteristic by solid phase
Higher polymer is spent, obtains highly viscous polymer end product using double screw extruder melting thickening.This preparation method
It is related to prepolymerization, solid phase, melt polymerization three-step reaction, production process is complicated, and device therefor is more, and the reaction time is long, increases
The unstability of product.
It is described in the patents such as the U.S. US5981692, US5516882 and rises to 300 DEG C after mixing dicarboxylic acids and diamine
More than, the method for polyamide 6 T copolymer is prepared by high-temperature fusion polymerization.The preparation method material stops at high operating temperatures
It stays of long duration, be easy to cause product degradation, cause amido bond to shift and the side reactions such as gelation, the hue difference of polymerizate.
Patent US5663284 discloses a kind of method for preparing polyamide 6 T/66 copolymer, is having item existing for water first
Discharge then prepolymerization maintains pressure using high-pressure steam in the case that in melting point polymer temperature below under part,
Then polyamide finished product is obtained using twin-screw melt polymerization.But meet the prepolymer of melt polymerization requirement in order to obtain, in advance
The temperature of polymerization reaction close to polymer fusing point, to obtain the high polymer of inherent viscosity.
For direct melt polycondensation method, patent JP57200420, JP58111829, EP1074585A1, CN1624021A are public
A kind of preparation method of the semiaromatic polyamide compositions such as MXD6 polyamide, CN1365989, JP57-200420, JP58- are opened
A kind of method that direct melt polycondensation hair prepares polyamide is described in 111829.In the disclosed methods, by diamines in normal pressure
Or be added drop-wise under low pressure in the dicarboxylic acids of melting, it raises simultaneously system temperature and removes the water that polymerization reaction generates to promote polymerization anti-
It answers.This method can realize polymerization close under condition of normal pressure solvent-free, but connect dicarboxylic acids sufficiently with diamine
Touching reacts, and prevents diamine from escaping, and keeps reaction system uniform and proportion speed is stablized, raw material is residual in reduction product
It stays, product is made to keep true qualities, be the main problem for limiting direct melt polycondensation method industrial applications.
Patent US6355769 describes a kind of low-temperature solution polycondensation, and typical process flow is that equimolar is compared binary
Amine and dicarboxylic acids and a certain amount of stabilizer are dissolved in the mixed organic solvents (mixing of such as N-Methyl pyrrolidone and pyridine
Liquid) in system, a small amount of CaCl is added2, LiCl etc., one section of constant temperature under the conditions of lower temperature (100 DEG C or so) and nitrogen protection
Time uses methanol washes clean after cooling, obtains the performed polymer with certain molecular weight.It uses organic solution system, stabilization
Agent, catalyst realize that low-temperature atmosphere-pressure prepares semi-aromatic nylon, and process route is complicated, needs the moisture in strict control system, separately
The outer organic solution used is generally all more expensive, and reaction system contains chloride ion, and production is easily corroded in reaction process
Equipment, and organic solvent and additive are easy to pollute product and environment, it is more difficult to it realizes and is not suitable for industrialized production.
Patent CN101469070B describes that a kind of low-temperature solution polycondensation prepares semi-aromatic and fatty polyamide is embedding
The process route of section copolymer, first to being added to a certain amount of hydrotropy salt (CaCl2, the alkali halides, alkaline-earth metal such as LiCl
Halide or combinations thereof) solvent in put into two acid halide reagents and corresponding diamines, then at a certain temperature, polymerization one timing
Between.Acyl chlorides or amino-terminated low molecular weight prepolymer solution are obtained by controlling feed ratio.Thereafter by gained acyl chloride terminated
Low molecule pre-polymer solution instills in amino-terminated pre-polymer solution, reacts certain time at a certain temperature.Finally will
Resulting polymers are precipitated out and wash, are dried in vacuo, and obtain high-temperature nylon block polymer.The process route is complicated, preparation
Need to use a variety of organic solvents and auxiliary agent, long preparation period in the process, product needs to purify, it is more difficult to realize industrialized production.
Patent US5837803, US6l07438, US6355769, CN 1168898A, EP 0801090B1, US
7244792B2, DE69700819D1 etc. describe the polycondensation of polyester method for belonging to macromolecular reaction scope, and this method is mainly with big
Molecule polyester and diamine are raw material, are that reaction medium carries out instead with organic solvent (hydro carbons, halogenated hydrocarbon, ethers and acetals)
It answers, prepares the lower performed polymer of molecular weight, then obtain the product of high molecular weight by viscosifying reaction.Polycondensation of polyester method is with big
Molecule polyester resin is raw material, cause the molecular weight of target product semi-aromatic polyamide is uncontrollable, later period molecule chain growth is difficult,
Molecular weight distribution is wider, molecule segment irregular distribution, product single variety and impure, it is more difficult to meet industrialized production and want
It asks.
In conclusion to lack a kind of process simple, efficiently for this field at present, product is stable, high-quality semiaromatic adoption
The preparation method of amide, the preparation method can effectively simplify the production procedure of semiaromatic polyamide composition, be easier to production process
Control, while production cost can be reduced, it improves efficiency, the semiaromatic polyamide composition molecular weight distribution obtained by the preparation method
Uniformly, hot property is stablized.
Summary of the invention
The problem of present invention exists in view of the prior art provides a kind of preparation method of semiaromatic polyamide composition, the party
Method simple process, with short production cycle, high-efficient, adaptable, production process is easily controllable, while the performance of product is stable, matter
It measures excellent.
The present invention realizes that the technical solution of above-mentioned purpose is as follows:
A kind of preparation method of semiaromatic polyamide composition, comprising the following steps:
(a) binary acid and diamine, which take water as a solvent, carries out neutralization salt-forming reaction, obtains semiaromatic polyamide composition salting liquid；
(b) semiaromatic polyamide composition salting liquid made from step (a) is further heated up into carry out prepolymerization, obtains half
Aromatic polyamide performed polymer；
(c) step (b) obtains semiaromatic polyamide composition performed polymer by thickening reaction further polymerization obtain it is described
Semiaromatic polyamide composition；
Defoaming agent is added in step (a) or step (b), the defoaming agent is rolydimethylsiloxane defoamer, polyethers-
One of dimethylsiloxane copolymer defoaming agent or two kinds of mixture, the quality for adding defoaming agent is as raw material
The 0.05-5% of the gross mass of binary acid.
During prepolymerization, with the progress of reaction, the product of generation is constantly precipitated from solvent, and system is viscous
Degree gradually increases, and with the discharge of small molecule volatile matter, can generate a large amount of bubble in phase interface, improve small molecule volatile matter
The difficulty evaporated from system, causing small molecule volatile matter to be trapped in system can not volatilize in time, reduce reaction speed
Rate extends reaction time, it is not necessary to which strategic point consumes power more.In addition excessive foam can also reduce batch charging coefficient, make to produce
Ability is restricted.In the present invention, after specific defoaming agent is added, the characteristic on the one hand effectively improving product is viscous
Number, on the other hand makes molecular weight distribution narrower, improves the performance of product.
The defoaming agent of addition needs in right amount, and otherwise excessive defoaming agent residual influences the quality of product, defoaming in the product
The optimum efficiency of defoaming is not achieved in agent very little.
In step (a), binary acid be one or more of aromatic acid mixture or aromatic acid with
The mixture of aliphatic dibasic acid.Aromatic acid be terephthalic acid (TPA), M-phthalic acid, 2- methylterephthalic acid, 2,
5- dimethyl terephthalic acid, oreinol dioctyl phthalate, aliphatic dibasic acid are 1, 4- succinic acid, 1,5- glutaric acid, 1,6-
Adipic acid, 1,7- pimelic acid, 1,8- suberic acid, 1,9- azelaic acid, 1,10- decanedioic acid, 1,11- ten one carbon diacid, 1,12- ten two
Carbon diacid.In the mixture of aromatic acid and aliphatic dibasic acid, mole of aromatic acid and aliphatic dibasic acid
Than being between 35/65-99/1, in preferably 40/60~95/5 range.
In step (a), diamines is the mixture of one or more of aliphatic diamine.Diamine is 1,4- fourth two
Amine, 1,5- pentanediamine, 2- methyl-1,5- pentanediamine, 1,6- hexamethylene diamine, 2,2,4- trimethyl -1,6- hexamethylene diamines, 2,4,4- front threes
Base -1,6- hexamethylene diamine, 1,7- heptamethylene diamine, 1,8- octamethylenediamine, 1,9- nonamethylene diamine, 1,10- certain herbaceous plants with big flowers diamines, 1,11- ten one carbon amine, 1,
12 carbon amine of 12-.
In step (a), the quality of water is the 10%-50% of dicarboxylic acids and diamine gross mass, and the water of addition is very little, can lead
Material when polymerization reaction is caused to solidify, reaction can not continue；If the water being added is too many, the rate of polymerization reaction can be reduced, is reduced
The intrinsic viscosity of prepolymer causes subsequent increasing stick reaction difficult, and too low heating and reaction rate will lead to and polymerize
It generates and mutually separates in the process, cause reaction that can not continue, in addition, since a large amount of water to be discharged in pre-polymerization process, not only
It will lead to the serious loss of diamines, and a large amount of heat can be taken away, cause polymerization heating rate slack-off, increase energy consumption.
In step (a), the molar ratio of diamines and dicarboxylic acids is between 1-1.1, preferably 1.01-1.08, due to diamines
Boiling point is lower, is easy the discharge with dampening in reaction and is lost, therefore in prepolymerization reaction, diamine is often excessive, with more
Mend the loss of diamine.The temperature of salt-forming reaction is 100-200 DEG C, preferably 120-160 DEG C.
In step (b), using the online separating and reclaiming device of diamine to vapor when draining during prepolymerization
The diamine of entrainment is separated and recovered, and the loss of diamine is effectively prevent, and is kept reaction raw materials proportion, is reduced material loss,
Guarantee product quality, reduces the processing difficulty of the water of discharge.
In step (b), the temperature of prepolymerization is 220-280 DEG C, pressure 0-4.0Mpa, and the time is 1-6 hours, instead
The later period is answered to pass through the water in exclusion system to promote prepolymerization.Temperature of the prepolymer obtained by prepolymerization at 30 DEG C
Intrinsic viscosity under degree in phenol tetrachloroethane (mass ratio 3:2) solvent is 0.1-0.5dL/g.
System reaction environment is set for anaerobic and without carbon dioxide environment by nitrogen or helium in step (a) or step (b)
The steam in system is changed or is expelled directly out to remove the oxygen and carbon dioxide in reaction system.The diamine of raw material be easy with
It is rotten to lead to it for carbon dioxide reaction, and amido bond is easy to happen under the conditions of high temperature is aerobic existing in the course of the polymerization process
The side reactions such as oxidation dehydration, seriously affect the performance of product, change the color of product.In addition, a small amount of in the course of the polymerization process decompose
Free amido out is oxidized easily, and is also resulted in product flavescence, is influenced the appearance and performance of product.
Addition phosphorus-containing catalyst and molecular weight regulator, the phosphorous catalysis in step (a) or step (b) or step (c)
Agent is one of phosphate, phosphite, hypophosphites or several compositions, and the amount of the substance of catalyst is as former
The 0.01-2% of the amount of the dicarboxylic acids total material of material.The molecular weight regulator is C2-C18Representative examples of saturated aliphatic monocarboxylic acid, benzene
The mixture of one or more of formic acid or phenylacetic acid, the amount of the substance of molecular weight regulator be as raw material dicarboxylic acids it is total
The 0.01-10% of the amount of substance, preferably 0.1-5%, if molecular weight regulator is excessive, it is relatively low to will lead to polymer molecular weight,
Molecular weight regulator will lead to that polymer molecular weight is bigger than normal or active terminal content is more very little, cause in subsequent use process
Middle processing difficulties, properties of product change.
When the binary acid is the combination of terephthalic acid (TPA) and adipic acid, as most preferably, the defoaming agent is
Dimethyl silicone polymer, the molecular weight regulator are acetic acid, and the phosphorus-containing catalyst is sodium hypophosphite, at this point, obtaining
Semiaromatic polyamide composition performance it is best.
The reaction of thickening described in step (c) is solid-phase polymerization or melt polymerization, preferred molten polymerization reaction.
The solid-phase polymerization temperature is 200-300 DEG C, reaction time 2-20h, preferably 4-10 hour.To prevent
Polymer oxidation, and the small molecule that polymerization generates is taken away in time, promote the progress of reaction, solid phase is protected in nitrogen, helium
Or carried out under vacuum condition, it is carried out preferably in nitrogen.Due to solid phase be polymer the following amorphous area of fusing point into
Capable, polymerization reaction is slow, the time is long, and the polymeric long time keeps flavescence easy to oxidize under the high temperature conditions, due to solid polycondensation
During conjunction, it can not be reacted between prepolyer granule, it is uneven so as to cause molecular weight distribution.
There are two types of implementations for melt polymerization: melt polymerization in situ or the performed polymer for obtaining prepolymerization turn
It moves to and carries out melt polymerization in melting extrusion equipment, the performed polymer for preferably obtaining prepolymerization is transferred to melting extrusion equipment
Upper carry out melt polymerization.
The original position melt polymerization refers to be continued to heat up after step (b) is completed by reaction system, when temperature rises to
System pressure is reduced into normal pressure at 280-320 DEG C, then vacuumizes or be passed through nitrogen or helium 5-30min, in removing system
Volatile matter, promote polymerization reaction, while system temperature risen to 300-350 DEG C and obtains semiaromatic polyamide composition finished product.This is poly-
It is simple to close method and process process, semiaromatic polyamide composition finished product can be directly obtained, but reaction temperature is high, material is in the condition of high temperature
The lower residence time is longer, easily causes the side reactions such as decomposition oxidation, leads to that product property is unstable, hue difference.It is molten to react the later period
It is very sticky to melt state polyamide, is not easy discharging, and the common more difficult polyamide for making generation of mixing plant keeps uniform state, shadow
Ring product quality.
The another kind melt polymerization mode is carried out in melting extrusion equipment, and the melting extrusion equipment has
Exhaust and nitrogen or helium protective device, preferably nitrogen are as protective gas, in melting point polymer with enterprising when melt polymerization
Capable, reaction temperature is 280-350 DEG C, reaction time 1-10min, preferably 2-8min.When the advantages of melt polymerization is polymerization
Between it is short, reaction rate is fast, and the extent of reaction is thorough, and side reaction is relatively fewer, and the molecular weight of product can be controlled relatively narrow
In range, the hot property and stable mechanical property of product can be with continuous productions, and to be able to maintain comparison natural for product colour
State.
The present invention also provides a kind of semiaromatic polyamide composition obtained by the preparation method, the semi-aromatic polyamides
For amine under conditions of 30 DEG C, the intrinsic viscosity in phenol tetrachloroethane (mass ratio 3:2) is 0.6-2.0dL/g, preferably 0.8-
1.5dL/g, intrinsic viscosity is too low, and requirement is not achieved in performance, and intrinsic viscosity is too high, and mobility dies down, not easy to be processed；Fusing point
It is 280-350 DEG C, preferably 290-340 DEG C.Fusing point is too low, and requirement of the invention is not achieved in product, and fusing point is excessively high, in following process
Using when can decompose, processing difficulties.
Compared with prior art, the invention has the following advantages:
(1) production procedure is relatively easy, and production cost is low, and the reaction time is short, easy to operate, and reaction is easy to control；
(2) present invention utilizes the online separating and reclaiming device of diamine to the binary of entrainment with steam in pre-polymerization production procedure
Amine is separated and recovered, and the loss of diamine is effectively reduced, and can accurately control the molar ratio of dicarboxylic acids and diamine, secondary anti-
Answer less, obtained semiaromatic polyamide composition inherent viscosity height, even molecular weight distribution, hot property is stable, mechanical property is good；
(3) present invention uses water as solvent, can be applied in process of production with direct circulation, in addition, in pre-polymerization system
The diamine of entrainment with steam is separated and recovered using diamine online separating and reclaiming device during standby, is effectively reduced useless
Binary amine content in water, increases the recycling number of aqueous solvent, and production technology is relatively more environmentally protective.
Specific embodiment
Below with reference to specific embodiment, present invention is described, and the characteristic of the product in embodiment is according to lower section
Method test.
1, intrinsic viscosity
The in the mixed solvent for dissolving a sample in phenol tetrachloroethane (mass ratio 3:2), obtain concentration be 0.1,0.5,
The solution of 1.0g/dL, in 30 DEG C of water bath with thermostatic control environment, with the dense logarithm viscosity number of the ratio of Ubbelohde viscometer sample solution
ηln。
ηln=[ln (t/t0)]/C (dL/g)
Wherein t0For the flow time (second) of solvent, t is the flow time (second) of solution, and C is the concentration (g/ of sample solution
dL)。
By ηlnData Extrapolation to concentration be 0 range, the intrinsic viscosity of sample can be obtained.
2、DSC
DSC test is carried out on model TA Q20 differential scanning calorimeter.It is demarcated with pure indium and pure zinc, temperature
Spending measuring accuracy is 0.01 DEG C, using nitrogen atmosphere, nitrogen flow rate 50mL/min.Test sample quality is 10 ± 0.5mg.It surveys
When examination, sample is warming up to 350 DEG C, constant temperature 1min from -50 DEG C of rates with 20 DEG C/min, eliminates after thermal history again with 20 DEG C/min
Rate be down to -50 DEG C, then rise to 350 DEG C again with the rate of 20 DEG C/min, obtain DSC map, DSC spectrogram is carried out corresponding
Analysis obtain glass transition temperature (Tg) and fusing point (Tm).Using the vertex of melting peak as fusing point, the area at peak is melting enthalpy.
The hot property of polymer is characterized by Tg and Tm.
3、TGA
TGA test is using carrying out on the thermogravimetric analyzer of model TA Q500.Take the sample of 10~15mg in platinum
In pallet, 600 DEG C, nitrogen flow rate 50mL/min are warming up to from 20 DEG C in nitrogen environment with the heating rate of 20 DEG C/min,
Obtain the curve graph of temperature with corresponding percent weight loss.In TGA curve graph, the straight line and baseline of weightless 20% and 50% two o'clock
The intersection point of extended line be defined as decomposition temperature.The thermal stability of polymer is evaluated with decomposition temperature.
4、GPC
Molecular weight distribution is tested on the gel permeation chromatograph of model Waters 1515.It is with nylon 6
Standard specimen, the methylene chloride that volume ratio is 3:1-hexafluoroisopropanol solution is solvent.The molecular weight of polymer is characterized by GPC
Distribution.
Embodiment 1
It is poly- that stirring is added to after solid hexamethylene diamine of the 30Kg content greater than 99.7% is dissolved completely in 65 DEG C of water-bath
Close in reaction kettle, be then turned on stirring, 15Kg deionized water is added into reaction kettle, the interior addition 24.50Kg of backward reaction kettle
Terephthalic acid (TPA), the adipic acid of 14.38Kg, the acetic acid of 590.7g, the sodium hypophosphite of 130.3g, 194.4g polydimethylsiloxanes
Then the deionized water of 2.5Kg is added in alkane into reaction kettle again, start to warm up after being replaced 3 times with nitrogen, when temperature rises to
After 130 DEG C, the exhaust valve exhaust 2min on reaction kettle is opened, then proceedes to heat up.Temperature is risen to 220 within 1.5 hours
DEG C, in 220 DEG C of constant temperature 10min, then proceed to that reaction temperature is made to rise to 240 DEG C.In temperature-rise period, when reaction pressure reaches
When 2.0MPa, exhaust valve is opened, steam is discharged and keeps pressure constant in 2.0MPa, the steam of discharge is condensed by condenser
Liquid water.Reaction continues 30min under conditions of 240 DEG C and 2.0MPa.It discharges after the reaction was completed, obtains prepolymer.In advance
Polymers is dried in vacuo 24 hours under conditions of 100 DEG C, and the intrinsic viscosity of sample is 0.18dL/g.Then it is protected in 320 DEG C of nitrogen
Melt polymerization is carried out in shield atmosphere in an extruder, the residence time of sample in an extruder is 5min.Sample is in an extruder
By being once vacuum-evacuated and being vented naturally twice after melting, then passes through pelletizing, drying, obtain flaxen semiaromatic adoption
Amide products.The intrinsic viscosity of product is 1.01dL/g, and glass transition temperature is 97.59 DEG C, and fusing point is 318.61 DEG C, melting
Enthalpy is 58.75J/g, and decomposition temperature is 429 DEG C, molecular weight distribution 1.8.
Comparative example 1
The preparation step of embodiment 1 is repeated, the difference is that it is not added with dimethyl silicone polymer, other ingredient proportions and implementation
Example 1 is identical.The intrinsic viscosity of gained prepolymer is 0.10dL/g after the completion of prepolymerization reaction, then is obtained after melting extrusion faint yellow
Semiaromatic polyamide composition product, but its intrinsic viscosity is 0.55dL/g, and molecular weight distribution reaches 4.2.
Embodiment 2
The preparation step of embodiment 1 is repeated, the difference is that the thickening mode of prepolymer is changed to solid phase.In nitrogen atmosphere
Under conditions of enclosing with 250 DEG C, solid phase polymerization time 8 hours, lurid Semi-aromatic polyamide resin is obtained.Its characteristic
Viscosity number is 0.89dL/g, and glass transition temperature is 94.76 DEG C, and fusing point is 316.07 DEG C, melting enthalpy 52.53J/g, decomposes temperature
Degree is 424 DEG C, molecular weight distribution 3.7.
Embodiment 3
It is poly- that stirring is added to after solid hexamethylene diamine of the 30Kg content greater than 99.7% is dissolved completely in 65 DEG C of water-bath
Close in reaction kettle, be then turned on stirring, 15Kg deionized water is added into reaction kettle, the interior addition 24.75Kg of backward reaction kettle
Terephthalic acid (TPA), the M-phthalic acid of 16.50Kg, the benzoic acid of 606.5g, 157.9g the poly- diformazan of sodium hypophosphite, 195.1g
Then the deionized water of 2.81Kg is added in radical siloxane into reaction kettle again, start to warm up after being replaced 3 times with nitrogen, work as temperature
After degree rises to 130 DEG C, the exhaust valve exhaust 2min on reaction kettle is opened, then proceedes to heat up.By temperature liter within 1.5 hours
To 230 DEG C, in 230 DEG C of constant temperature 10min, then proceed to that reaction temperature is made to rise to 250 DEG C.In temperature-rise period, work as reaction pressure
When reaching 2.50MPa, exhaust valve is opened, steam is discharged and keeps pressure constant in 2.50MPa, the steam of discharge passes through condenser
It is condensed into liquid water.Reaction continues 20min under conditions of 250 DEG C and 2.50MPa.It discharges, obtains pre- after the reaction was completed
Polymers.Prepolymer is dried in vacuo 24 hours under conditions of 120 DEG C, and the intrinsic viscosity of sample is 0.17dL/g.Then 330
Melt polymerization is carried out in DEG C nitrogen protection atmosphere in an extruder, the residence time of sample in an extruder is 7min.Sample exists
By being once vacuum-evacuated and being vented naturally twice after being melted in extruder, then passes through pelletizing, drying, obtain flaxen half
Aromatic polyamide product.The intrinsic viscosity of product is 1.09dL/g, and glass transition temperature is 129.87 DEG C, and fusing point is
325.12 DEG C, melting enthalpy 27.97J/g, decomposition temperature is 441 DEG C, molecular weight distribution 2.1.
Embodiment 4
It is poly- that stirring is added to after solid hexamethylene diamine of the 30Kg content greater than 99.7% is dissolved completely in 65 DEG C of water-bath
Close reaction kettle in, be then turned on stirring, into reaction kettle addition 15Kg deionized water, backward reaction kettle in 28.87Kg is added
Terephthalic acid (TPA), 8.25Kg M-phthalic acid, 3.63Kg adipic acid, 758g phenylacetic acid, 176.2g sodium phosphite, 203.8g are poly-
Then ether-dimethylsiloxane copolymer is added 5Kg deionized water into reaction kettle again, then starts to warm up, when temperature rises to
At 140 DEG C, the exhaust valve exhaust 5min on reaction kettle is opened, then proceedes to heat up.Temperature is risen to 230 within 1.5 hours
DEG C, in 230 DEG C of constant temperature 10min, then proceed to be warming up to 250 DEG C.In temperature-rise period, when reaction pressure reaches 2.40MPa,
Exhaust valve is opened, steam is discharged and keeps pressure constant in 2.40MPa, the steam of discharge is condensed into liquid water by condenser.
Reaction continues 30min under conditions of 250 DEG C and 2.40MPa.It discharges after the reaction was completed, obtains prepolymer.Prepolymer exists
It under conditions of 120 DEG C, is dried in vacuo 24 hours, the intrinsic viscosity of sample is 0.19dL/g.Then in 330 DEG C of nitrogen protection atmosphere
In carry out melt polymerization in an extruder, the residence time of sample in an extruder is 6min.After sample melts in an extruder
By being once vacuum-evacuated and being vented naturally twice, then passes through pelletizing, drying, obtain flaxen semiaromatic polyamide composition and produce
Product.The intrinsic viscosity of product is 1.03dL/g, and glass transition temperature is 123.29 DEG C, and fusing point is 321.57 DEG C, and melting enthalpy is
29.56J/g, decomposition temperature are 435 DEG C, molecular weight distribution 2.0.
Embodiment 5
1, the 9- nonamethylene diamine that 35Kg content is greater than 99.7% is added into stirring polymerization reaction kettle, is then turned on stirring, to
20Kg deionized water is added in reaction kettle, backward reaction kettle in the terephthalic acid (TPA) of addition 36.55Kg, 268.7g benzene first
Then the deionized water of 3.85Kg is added in acid, the sodium phosphate of 108.22g, 146.2g dimethyl silicone polymer into reaction kettle again,
It is started to warm up after being replaced 3 times with nitrogen.Temperature is risen to 250 DEG C within 2 hours.In temperature-rise period, work as reaction pressure
When reaching 2.30MPa, exhaust valve is opened, steam is discharged and keeps pressure constant in 2.30MPa, the steam of discharge passes through condenser
It is condensed into liquid water.Reaction continues 1 hour under conditions of 250 DEG C and 2.30MPa.It discharges, obtains after the reaction was completed
Prepolymer.Prepolymer is dried in vacuo 12 hours under conditions of 100 DEG C, and the intrinsic viscosity of sample is 0.21dL/g.Then exist
Melt polymerization is carried out in 320 DEG C of nitrogen protection atmosphere in an extruder, the residence time of sample in an extruder is 5min.Sample
By being once vacuum-evacuated and being vented naturally twice after melting in an extruder, then passes through pelletizing, drying, obtain flaxen
Semiaromatic polyamide composition product.The intrinsic viscosity of product is 1.05dL/g, and glass transition temperature is 124.61 DEG C, and fusing point is
306.81 DEG C, melting enthalpy 67.75J/g, decomposition temperature is 424 DEG C, molecular weight distribution 1.8.
Embodiment 6
Dehydration condensate liquid 10kg obtained in Example 5 carries out test amine content titration test, measures hexamethylene diamine content
For 0.3mol/kg, i.e., contain 0.35kg hexamethylene diamine and 9.65kg water in 10L condensate liquid.Being added into stirring polymerization reaction kettle should
10kg condensate liquid, 34.65Kg content are greater than 99.7% 1,9- nonamethylene diamine, are then turned on stirring, are added into reaction kettle
10.35Kg deionized water, backward reaction kettle in be added the terephthalic acid (TPA) of 36.55Kg, the benzoic acid of 268.7g, 108.22g
Sodium phosphate, 146.2g dimethyl silicone polymer, then again into reaction kettle be added 3.85Kg deionized water, replaced with nitrogen
It is started to warm up after 3 times.Prepolymerization, extruder melt polymerization and finished product reprocessing method are same as Example 5.It finally obtains
The glutinous number of product characteristic be 0.98dL/g, glass transition temperature is 124.33 DEG C, and fusing point is 306.64 DEG C, and melting enthalpy is
66.97J/g, decomposition temperature are 423 DEG C, molecular weight distribution 1.9.
Claims (10)
1. a kind of preparation method of semiaromatic polyamide composition, comprising the following steps:
(a) binary acid and diamine, which take water as a solvent, carries out neutralization salt-forming reaction, obtains semiaromatic polyamide composition salting liquid；
(b) semiaromatic polyamide composition salting liquid made from step (a) is further heated up into carry out prepolymerization, obtains semiaromatic
Polyamide performed polymer；
(c) by thickening reaction, further polymerization obtains half virtue to the semiaromatic polyamide composition performed polymer that step (b) obtains
Fragrant polyamide；It is characterized by:
In step (a), the temperature of the salt-forming reaction is 120-160 DEG C；In step (b), the temperature of the prepolymerization
It is 220-280 DEG C；
Defoaming agent is added in step (a) or step (b), the defoaming agent is rolydimethylsiloxane defoamer, polyethers-diformazan
One of radical siloxane copolymer defoaming agent or two kinds of mixture, the quality for adding defoaming agent is the total of raw material binary acid
The 0.05-5% of quality.
2. the preparation method of semiaromatic polyamide composition according to claim 1, which is characterized in that described in step (a)
Binary acid is the mixing of the mixture or aromatic acid and aliphatic dibasic acid of one or more of aromatic acid
Object；
The diamine is the mixture of one or more of aliphatic diamine.
3. the preparation method of semiaromatic polyamide composition according to claim 1, which is characterized in that in step (a), aqueous solvent
Quality be dicarboxylic acids and diamine gross mass 10%-50%, the molar ratio of diamine and dicarboxylic acids is 1~1.1:1.
4. the preparation method of semiaromatic polyamide composition according to claim 1, which is characterized in that in step (b), prepolymerization
The pressure of reaction is 0-4.0MPa, and the time is 1-6 hours, promotes pre-polymerization by the water vapour in exclusion system in reaction process
Close reaction.
5. the preparation method of semiaromatic polyamide composition according to claim 1, which is characterized in that in prepolymerization steam discharge
The diamine of entrainment with steam is separated and recovered using diamine online separating and reclaiming device in the process.
6. the preparation method of semiaromatic polyamide composition according to claim 1, which is characterized in that step (a) or step (b)
Or step (c) in add phosphorus-containing catalyst, the phosphorus-containing catalyst be one of phosphate, phosphite, hypophosphites or
Several composition of person, the amount of the substance of added catalyst are the 0.01- of the amount of the total material of the dicarboxylic acids as raw material
2%.
7. the preparation method of semiaromatic polyamide composition according to claim 1, which is characterized in that step (a) or step (b)
Or molecular weight regulator is added in step (c), the molecular weight regulator is monocarboxylic acid, and the monoacid is C2-C18It is full
With the mixture of one or more of aliphatic monocarboxylic acid, benzoic acid or phenylacetic acid, the molecular weight regulator being added
The amount of substance is the 0.01-10% of the amount of the dicarboxylic acids total material as raw material.
8. the preparation method of semiaromatic polyamide composition according to claim 1, which is characterized in that described in step (c)
Thickening reaction is solid-phase polymerization or melt polymerization.
9. the preparation method of semiaromatic polyamide composition according to claim 8, which is characterized in that
The solid-phase polymerization carries out under nitrogen, helium or vacuum condition, and reaction temperature is 200-300 DEG C, reaction
Time is 2-20h；
The melt polymerization is that melt polymerization in situ or performed polymer is transferred in melting extrusion equipment melts
Polymerization；
The melt polymerization in situ is to continue to heat up by reaction system after step (b) is completed, when temperature rises to
System pressure is reduced into normal pressure at 280-320 DEG C, then vacuumizes or be passed through nitrogen or helium 5-30min, while by system
Temperature rises to 300-350 DEG C and obtains semiaromatic polyamide composition finished product；
It is described that performed polymer is transferred in melting extrusion equipment to carry out melt polymerization squeezed with the melting of exhaust apparatus
It is carried out in equipment out, reaction temperature is 280-350 DEG C, reaction time 1-10min.
10. a kind of semiaromatic polyamide composition being prepared by any one of claim 1~9 preparation method.
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| CN108178831B (en) * | 2017-12-28 | 2020-06-02 | 湖南文理学院 | Preparation method of PA (66-co-6T) copolymer |
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| CN112480396B (en) * | 2020-10-31 | 2022-07-05 | 山东广垠新材料有限公司 | Process and apparatus for producing semi-aromatic polyamide |
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