CN107383365A - A kind of Semi-aromatic polyamide resin and preparation method thereof - Google Patents
A kind of Semi-aromatic polyamide resin and preparation method thereof Download PDFInfo
- Publication number
- CN107383365A CN107383365A CN201710674996.8A CN201710674996A CN107383365A CN 107383365 A CN107383365 A CN 107383365A CN 201710674996 A CN201710674996 A CN 201710674996A CN 107383365 A CN107383365 A CN 107383365A
- Authority
- CN
- China
- Prior art keywords
- acid
- diamines
- raw material
- semi
- polyamide resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- 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
Abstract
The present invention relates to a kind of Semi-aromatic polyamide resin and preparation method thereof, belong to technical field of organic synthesis.It is more than 18 fatty acid units comprising p dimethylamine's construction unit, two acid units of the straight-chain aliphatic diacid of carbon atom 10 18 and carbon number, and by straight-chain aliphatic dicarboxylic acids and raw material diamines, the catalytic reaction under the conditions of polymerization catalyst is made.The polyamide excellent flowability of the present invention, heat resistance is good, water absorption rate is low, satisfactory mechanical property, particularly suitable for high-fire resistance, various electronic units, the surface mounting assembly of low water absorbable, it is required that highly crystallineization speed, high final crystallization degree, the small-sized thin molded article of low water absorbable, it is desirable to the automobile component such as heat resistance, rigid car headlamp reflecting plate, engine circumferential component.
Description
Technical field
The present invention relates to a kind of Semi-aromatic polyamide resin and preparation method thereof, more particularly to a kind of excellent flowability,
Heat resistance is good, and water absorption rate is low, the Semi-aromatic polyamide resin of satisfactory mechanical property and its preparation, belongs to organic synthesis technology
Field.
Background technology
Using nylon 6, nylon66 fiber as the crystallinity aliphatic polyamide resin of representative, there are excellent toughness, chemically-resistant medicine
Moral character, electrical characteristic and be easy to melt molding processing, be widely used in chemical industry, electrical equipment, automobile and other mechanical manufacturing fields.
However, require higher field to heat resistance at some, as automobile engine, blast pipe and semiconductor surface encapsulate, due to
Nylon 6, the fusing point of nylon66 fiber are relatively low, and heat resistance is insufficient and hygroscopic, cause the dimension stability of shaping bad, mechanical
Intensity decreases.Particularly in recent years, automotive light weight technology requires that more metal parts are replaced with plastic components on automobile, and
The development of semiconductor surface encapsulation technology (SMT), the more excellent polyamide of increasing manufacturer's required performance.
Therefore, it is quite necessary to develop the polyamide of a kind of heat resistance, dimensional stability and good mechanical performance.
Obtained semiaromatic polyamide composition (such as PA9T) is wherein synthesized by terephthalic acid (TPA) and Long carbon chain aliphatic diamine, with
Existing aliphatic polyamide resin is compared, and has the advantages of excellent heat resistance, high intensity, low water absorbable, be used to substitute gold
Category, the automobile component and electrical and electronic parts of light weight miniaturization.
For PA9T fusing points more than 300 DEG C, mobility is poor, conventional polymerizing polyamide technique can not be used to prepare.Noting simultaneously
When penetrating shaping, shaping thin wall, the easy warpage of product of shaping are not easy.
The content of the invention
It is an object of the present invention to overcome the above deficiencies, there is provided a kind of excellent flowability, heat resistance is good, water absorption rate
It is low, the polyamide of satisfactory mechanical property.
According to technical scheme provided by the invention, a kind of Semi-aromatic polyamide resin, it includes terephthaldehyde's amine structure
Unit, carbon atom 10-18 straight-chain aliphatic diacid two acid units and carbon number be more than 18 fatty acid units；Its
315 DEG C, the melt index under 2.16kg is 2-8.
Straight-chain aliphatic dicarboxylic acids, Long carbon chain aliphatic acid and polymerization catalyst are added in a kettle, then pass to inertia
Gas, maintenance reaction kettle pressure, and heat and reacted；Then the raw material diamines of melting, temperature reaction are slowly added to thereto；
Maintenance reaction temperature is kept stirring for after stopping charging, system is pressurizeed finally by nitrogen, polymer, tie rod are extruded from end of extruded band
Cooling and dicing obtains Semi-aromatic polyamide resin particle.
Comprise the following steps that：Straight-chain aliphatic dicarboxylic acids, Long carbon chain aliphatic acid and polymerization catalyst are added in a kettle；
Inert gas is passed through, excludes the air in reactor, and the pressure of maintenance reaction kettle is in 0.2-0.4MPa；Heating response kettle makes instead
Answer kettle temperature degree to be raised to 220-240 DEG C, open stirring, mixing speed 10-100r/min；Then to being slowly added to original in reactor
Expect diamines, while temperature of reaction kettle is slowly raised to 290-310 DEG C, 120 minutes process used times are added dropwise；
The diacid and the mol ratio of diamines wherein added is 0.95-1.05, Long carbon chain aliphatic acid integral molar quantity be diamines and
The 0.1%-10% of dicarboxylic acids integral molar quantity；The addition of catalyst is straight-chain aliphatic dicarboxylic acids and the total matter of Long carbon chain aliphatic acid
The 0.01%-0.05% of amount；
The diacid and the mol ratio of diamines wherein added is 0.95-1.05, Long carbon chain aliphatic acid integral molar quantity be diamines and
The 0.1%-10% of dicarboxylic acids integral molar quantity；Maintenance reaction kettle pressure is 0.2-0.4MPa during dropwise addition；The water of generation leads to
Cross outside segregator and cooler discharge reaction system, the temperature control of segregator is at 140-150 DEG C；Add the raw material with ormal weight
After diamines, stop charging；The pressure of reactor is slowly down to normal pressure within 1 hour, is kept stirring for, maintenance reaction kettle temperature degree
290-310℃；The electric current of stirring is monitored, after 30-50 minutes, system is pressurizeed with nitrogen, polymer, tie rod are extruded from end of extruded band
Cooling and dicing obtains Semi-aromatic polyamide resin particle.
The polyamide of the present invention, come from 70 moles of more than % of the construction unit of diamine component, preferably 80 rub
Your more than the % of more than %, more preferably 90 moles come from p dimethylamine.The concentration of p dimethylamine in diamine component is higher,
Obtained polyamide more shows high-melting-point, high crystalline, because heat resistance, resistance to chemical reagents etc. are excellent, therefore, is suitable as
The purposes of the object of the invention.When the concentration of p dimethylamine in diamine component is less than 70 moles of %, due to heat resistance, drug-resistant
Property reduce, therefore, be not preferred.
Described polyamide, come from 70 moles of more than % of the construction unit of dicarboxylic acid component, preferably 80 rub
Your more than the % of more than %, more preferably 90 moles come from the aliphatic dicarboxylic acid that carbon number is 10-18.By being rubbed containing 70
Your more than % carbon number 10-18 straight-chain aliphatic dicarboxylic acids, the polyamide of acquisition have excellent mobility, height
Crystallinity, low water absorption and heat resistance, chemical proofing, molding processibility, excellent in dimensional stability.Raw material dicarboxylic acid component
In carbon number 10-18 straight-chain aliphatic dicarboxyl acid concentration when being less than 70 moles of %, mobility, heat resistance, processing and forming
Property decline.
Described polyamide, the aliphatic acid using carbon number more than 18 is as molecular weight regulator, relative to two
Amine component and the total amount of dicarboxylic acid component, 0.1-10 moles of % or so, preferably 0.1-5 moles of % or so, more preferably 0.1-1 rubs
Your % or so.Research finds that polyamide can be improved in the case where not damaging the precursor of mechanical performance using Long carbon chain aliphatic acid
Mobility.
As the raw material diamine component beyond p dimethylamine, Putriscine, 1,6- hexamethylene diamines, 1,8- can be exemplified
Octamethylenediamine, 1,10- decamethylene diamines, 1,12- dodecamethylene diamines, 2- methyl isophthalic acids, 5- pentanediamines, 2,2,4- trimethyl -1,6- hexamethylene diamines,
2,4,4- trimethyl -1,6- hexamethylene diamines, 2- methyl isophthalic acids, 8- octamethylenediamines, the aliphatic diamine such as 5- methyl isophthalic acids, 9- nonane diamines, 1,
Double (aminomethyl) hexamethylenes of 3-, 1,4- double (aminomethyl) hexamethylene, cyclohexanediamine, methyl cyclohexane diamines, IPDs etc.
The aromatic diamines such as ester ring type diamines, m-xylene diamine or their mixture, but it is not limited to this.
As carbon number 10-18 straight-chain aliphatic dicarboxylic acids, decanedioic acid, heneicosanedioic acid, 12 can be exemplified
Docosandioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid) etc..Wherein, decanedioic acid, 12 are preferably selected from
At least one kind of, particularly preferred decanedioic acid and/or dodecanedioic acid in the group of docosandioic acid and tetracosandioic acid composition.It is former using carbon
Subnumber is less than 10 aliphatic dicarboxylic acid, and resulting polyamide mobile performance and machine-shaping property are poor.
As the raw material dicarboxylic acids beyond carbon number 10-18 straight-chain aliphatic dicarboxylic acids, can exemplify adipic acid,
Pimelic acid, suberic acid, azelaic acid malonic acid, butanedioic acid, 2- methyl adipic acid, trimethyladipic acid, 2,2- dimethylated pentanedioic acids,
2,4- dimethylated pentanedioic acids, 3,3- dimethylated pentanedioic acids, 3,3- diethyl butanedioic acid, 1,3- cyclopentane dicarboxylic acids, 1,3- hexamethylenes
Alkane dicarboxylic acids, 1,4- cyclohexane dicarboxylic acids, M-phthalic acid, terephthalic acid (TPA), 2,6 naphthalene dicarboxylic acid, 15- naphthalene dicarboxylic acids, 1,4-
Naphthalene dicarboxylic acids, 2,7- naphthalene dicarboxylic acids or their mixture, but it is not limited to this.
In addition to foregoing diamine component and dicarboxylic acid component, can also be used in the range of effect of the present invention is not damaged ε-
The aliphatic amines such as the lactams such as caprolactam, lauric lactam, aminocaproic acid, amino undecanoic acid carboxylic acids is as composition
The copolymer composition of polyamide.
The polyamide of the present invention is prepared without using solvent by the polycondensation of diamine component and dicarboxylic acid component.
First diacid is melted in stirred autoclave, then continuously or intermittently adds diamines under elevated pressure to carry out polycondensation.Control is anti-
Answer the temperature of system in the scope of 20 DEG C of fusing point-fusing point with the molten condition of maintenance reaction system.Reaction temperature compares reaction mass
When fusing point is low, the material in reactor is possible to solidify, and in more than+20 DEG C of fusing point, the material in reactor is possible to degrade,
Cause hydraulic performance decline.After diamines addition terminates, the molten condition of maintenance reaction mixture, while the temperature of reactant mixture is existed
It is more than the fusing point of target polyamide.
For maintenance reaction system molten condition, it is necessary to control the speed of addition diamines.Condenser can be used to react
The diamines of the water and steam entrainment of discharge, diacid separation, keep reaction system material ratio.
According to the difference of the diamines beyond the dicarboxylic acid component and p dimethylamine used, necessary reaction pressure is not yet
Together, preferably 0.1-0.6MPa, more preferably 0.2-0.5MPa.Pressurization can be carried out using inert gas, can also utilize reaction
The steam of middle generation condensation water is carried out.
After diamine component addition terminates, the pressure of reaction system is finally depressured to below 0.08MPa.The speed of decompression is not
Can be too fast, prevent unreacted material to be entrained with reactor by vapor.Can not be too slow, it is so that material stops in reactor
Stay the time oversize, cause heat drop valency, reduce performance.
It after dropping to normal pressure, can at ambient pressure continue to react, lower further reaction can also be depressurized.Reaction time can root
Judge according to stir current.Reaction system molecular weight is bigger, and viscosity is higher, and stir current is also higher.Reached when reaching stir current
To after predetermined electric current, can discharge.
The melt polycondensation is carried out in the presence of polymerization catalyst.It can be included as polymerization catalyst：Phosphoric acid, Asia
The phosphorus compound of phosphoric acid, hypophosphorous acid etc., or their salt or ester compounds.Example as salt can be enumerated：Potassium, sodium, magnesium,
The metal salt of calcium, zinc, cobalt, manganese, tin, tungsten, vanadium, germanium, titanium, antimony etc.；Ammonium salt.Example as ester compounds can include：Second
Ester, isopropyl esters, butyl ester, hexyl ester, stearyl, 18 phosphinylidyne base esters, phenylester etc..Urged to suppress above-mentioned polymerization
Cohesion or abnormal response in polyamide caused by agent heat deterioration, can be used together alkali metal compound, alkali earths
Metallic compound.It can include but be not limited only to as its specific example：Sodium hydroxide, calcium hydroxide, potassium hydroxide, hydrogen
The alkali metal hydroxides such as magnesia and alkaline-earth metal hydroxide, and it is carbonic acid, boric acid, acetic acid, propionic acid, butyric acid, different
Butyric acid, butenoic acid, valeric acid, caproic acid, isocaproic acid, enanthic acid, octanoic acid, n-nonanoic acid, octadecanoid acid, cyclopentane-carboxylic acid, cyclohexane-carboxylic acid, hydrogen
Change cinnamic acid, γ-phenylbutyric acid, to phenoxy benzoic acid, o-hydroxy cinnamic acid, o- β-chlorophenyl propionic acid, a chlorophenyl
The alkali metal salt and alkali earth metal salt of propionic acid.
In the range of effect of the present invention is not damaged, polyamide of the invention can also contain other resins, with
And pigment, dyestuff, lubricant, delustering agent, heat-resisting stabilizing agent, weathering stabilizers, ultra-violet absorber, plasticizer, fire retardant, band
Additives such as electric preventing agent, releasing agent etc..During containing other resins, the amount of the resin is usually 0-20% by weight.
In addition, when containing additive, the amount of the additive is usually 0-5 weight %.
The present invention polyamide can by injection moulding, blow molding, extrusion molding, compression forming, extension, very
The method of forming shaping such as sky shaping.Engineering plastics formed body can be not only shaped to, and is shaped to film, thin slice, hollow appearance
The forms such as device, fiber, pipe, go for the preparation of industry goods, materials and equipments, industrial materials, household supplies etc..
Beneficial effects of the present invention：The polyamide excellent flowability of the present invention, heat resistance is good, and water absorption rate is low, machine
Tool is functional, particularly suitable for high-fire resistance, various electronic units, the surface mounting assembly of low water absorbable, it is desirable to Gao Jie
Crystallization rate, high final crystallization degree, the small-sized thin molded article of low water absorbable, it is desirable to heat resistance, rigid vehicle front lighting
The automobile components such as lamp reflecting plate, engine circumferential component.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, comparative example, but the present invention is not limited in following realities
Apply example.The evaluation method used in embodiment and comparative example is as follows：
(1) relative viscosity：Accurate weighing 1g polyamides, are added in 100mL 96% sulfuric acid, are stirred at 20-30 DEG C
Mix dissolving.After being completely dissolved, solution is taken to be placed in Ubbelohde viscometer, after 25 DEG C of thermostats are placed 10 minutes, measure declines
Speed (t).In addition, decrease speed (the t of the same sulfuric acid of measure 96%0).According to the following formula by t and t0Calculate relative viscosity.
Relative viscosity=t/t0
(2) melt index：Test device uses fusion index instrument.315 DEG C of test temperature, counterweight weight 2.16kg.Measure
The 10 minutes weight being extruded of fused materials.
(3) mechanical performance：Melted in injection (mo(u)lding) machine, at a temperature of 20 DEG C of the fusing point higher than polyamide,
Injection pressure 600kgf/cm2, injection time 1.0sec, obtain being injected into matrix under conditions of 80 DEG C of mold temperature.Obtained note
After penetrating the annealing that matrix band implements 24 hours at 25 DEG C, tests below has been carried out in the state of adiabatic drying.Draw
Stretch intensity, elongation at break is determined by ISO527-2 methods.Bending strength, bending modulus are determined by ISO178 methods.Cantilever beam
Notch impact strength is determined by ISO180 methods.
Embodiment 1
It is provided with the anti-with chuck of agitator, segregator, cooler, thermometer, dropwise adding tank and nitrogen ingress pipe
Answer and 2.02kg decanedioic acid, 20g stearic acid, 5g phosphoric acid are put into kettle.Inert gas is passed through to reactor, excludes the sky in reactor
Gas, and the pressure of maintenance reaction kettle is in 0.2Mpa.Heating response kettle makes temperature of reaction kettle be raised to 240 DEG C, opens stirring, and stirring turns
Fast 60rpm.Then the p dimethylamine of melting is slowly added into reactor, while temperature of reaction kettle is slowly raised to 290 DEG C.Drop
Add the process used time 120 minutes.The maintenance reaction kettle pressure 0.2MPa during dropwise addition, the water of generation pass through segregator and cooler
Discharge outside reaction system.Scope of the temperature control of segregator at 140-150 DEG C.After adding 1.36kg p dimethylamine, stop
Only feed.The pressure of reactor is slowly down to normal pressure within 1 hour, is kept stirring for, 290 DEG C of maintenance reaction kettle temperature degree.Prison
The electric current of stirring is controlled, after 30 minutes, system is pressurizeed with nitrogen, extrudes polymer from end of extruded band, tie rod cooling and dicing is gathered
Polymer particle.
Embodiment 2
It is provided with the anti-with chuck of agitator, segregator, cooler, thermometer, dropwise adding tank and nitrogen ingress pipe
Answer and 2.30kg dodecanedioic acids, 20g stearic acid, 5g phosphorous acid are put into kettle.Inert gas is passed through to reactor, excludes reactor
Interior air, and the pressure of maintenance reaction kettle is in 0.3MPa.Heating response kettle makes temperature of reaction kettle be raised to 230 DEG C, opens stirring,
Speed of agitator 60rpm.Then the p dimethylamine of melting is slowly added into reactor, while is slowly raised to temperature of reaction kettle
290℃.120 minutes dropwise addition process used times.The maintenance reaction kettle pressure 0.3MPa during dropwise addition, the water of generation pass through segregator
Outside cooler discharge reaction system.Scope of the temperature control of segregator at 140-150 DEG C.Add 1.36kg terephthaldehyde
After amine, stop charging.The pressure of reactor is slowly down to normal pressure within 1 hour, is kept stirring for, maintenance reaction kettle temperature degree
290℃.The electric current of stirring is monitored, after 50 minutes, system is pressurizeed with nitrogen, extrudes polymer from end of extruded band, tie rod cooling is cut
Grain obtains polymer particle.
Embodiment 3
It is provided with the anti-with chuck of agitator, segregator, cooler, thermometer, dropwise adding tank and nitrogen ingress pipe
Answer and 2.58kg tetracosandioic acids, 20g stearic acid, 5g sodium hypophosphites are put into kettle.Inert gas is passed through to reactor, is excluded anti-
The air in kettle is answered, and the pressure of maintenance reaction kettle is in 0.4MPa.Heating response kettle makes temperature of reaction kettle be raised to 220 DEG C, opens
Stirring, speed of agitator 60rpm.Then the p dimethylamine of melting is slowly added into reactor, while slowly by temperature of reaction kettle
It is raised to 290 DEG C.120 minutes dropwise addition process used times.The maintenance reaction kettle pressure 0.4MPa during dropwise addition, the water of generation is by dividing
Outside condenser and cooler discharge reaction system.Scope of the temperature control of segregator at 140-150 DEG C.Add 1.36kg to benzene
After dimethylamine, stop charging.The pressure of reactor is slowly down to normal pressure within 1 hour, is kept stirring for, maintenance reaction kettle temperature
290 DEG C of degree.The electric current of stirring is monitored, after 50 minutes, system is pressurizeed with nitrogen, polymer, tie rod cooling are extruded from end of extruded band
Pelletizing obtains polymer particle.
Comparative example
It is provided with the anti-with chuck of agitator, segregator, cooler, thermometer, dropwise adding tank and nitrogen ingress pipe
Answer and 1.46kg adipic acids, 20g stearic acid, 5g phosphorous acid are put into kettle.Inert gas is passed through to reactor, is excluded in reactor
Air, and the pressure of maintenance reaction kettle is in 0.3Mpa.Heating response kettle makes temperature of reaction kettle be raised to 220 DEG C, opens stirring, stirring
Rotating speed 50rpm.Then the p dimethylamine of melting is slowly added into reactor, while temperature of reaction kettle is slowly raised to 310 DEG C.
120 minutes dropwise addition process used times.The maintenance reaction kettle pressure 0.3Mpa during dropwise addition, the water of generation pass through segregator and cooling
Outside device discharge reaction system.Scope of the temperature control of segregator at 140-150 DEG C.After adding 1.36kg p dimethylamine,
Stop charging.The pressure of reactor is slowly down to normal pressure within 1 hour, is kept stirring for, 310 DEG C of maintenance reaction kettle temperature degree.
The electric current of stirring is monitored, electric current rises quickly, and system is pressurizeed with nitrogen, can not extrude polymer from end of extruded band.
Table 1
According to upper table, it can be seen that, Semi-aromatic polyamide resin is while higher mechanical strength is kept, mobility
Preferably, particularly suitable for high-fire resistance, various electronic units, the surface mounting assembly of low water absorbable, it is desirable to highly crystallineization speed
Degree, high final crystallization degree, the small-sized thin molded article of low water absorbable, it is desirable to heat resistance, the reflection of rigid car headlamp
The automobile components such as plate, engine circumferential component.
The above-mentioned description to embodiment is that this hair is understood that and used for ease of those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment,
Those skilled in the art do not depart from improvement that scope made and modification all should be in this hairs according to the announcement of the present invention
Within bright protection domain.
Claims (9)
1. a kind of Semi-aromatic polyamide resin, it is characterized in that：It includes p dimethylamine's construction unit, carbon atom 10-18
Two acid units and carbon number of straight-chain aliphatic diacid are more than 18 fatty acid units.
2. Semi-aromatic polyamide resin as claimed in claim 1, it is characterized in that：Its melting under 315 DEG C, 2.16 kg refers to
Number is 2-8.
3. the preparation method of the Semi-aromatic polyamide resin of claim 1 or 2, it is characterized in that step is as follows：In reactor
Middle addition raw material dicarboxylic acids, Long carbon chain aliphatic acid and polymerization catalyst, then pass to inert gas, maintenance reaction kettle pressure, and
Heating is reacted；Then the raw material diamines of melting, temperature reaction are slowly added to thereto；It is kept stirring for maintaining after stopping charging
Reaction temperature, system is pressurizeed finally by nitrogen, extrudes polymer from end of extruded band, tie rod cooling and dicing obtains semiaromatic adoption
Amide resin particle.
4. the preparation method of Semi-aromatic polyamide resin as claimed in claim 3, it is characterized in that comprising the following steps that：Reacting
Raw material dicarboxylic acids, Long carbon chain aliphatic acid and polymerization catalyst are added in kettle；Inert gas is passed through, excludes the air in reactor,
And the pressure of maintenance reaction kettle is in 0.2-0.4MPa；Heating response kettle makes temperature of reaction kettle be raised to 220-240 DEG C, opens stirring,
Mixing speed is 10-100r/min；Then to being slowly added to raw material diamines in reactor, while slowly temperature of reaction kettle is raised to
290-310 DEG C, 120 minutes process used times are added dropwise；
The raw material dicarboxylic acids and the mol ratio of raw material diamines wherein added is 0.95-1.05, Long carbon chain aliphatic acid integral molar quantity
For diamines and the 0.1%-10% of dicarboxylic acids integral molar quantity；The addition of catalyst is straight-chain aliphatic dicarboxylic acids and Long carbon chain fat
The 0.01%-0.05% of sour gross mass；
Maintenance reaction kettle pressure is 0.2-0.4MPa during dropwise addition；The water of generation passes through segregator and cooler discharge reaction
Outside system, the temperature control of segregator is at 140-150 DEG C；After adding the raw material diamines with ormal weight, stop charging；It is small at 1
When it is interior the pressure of reactor is slowly down to normal pressure, be kept stirring for, 290-310 DEG C of maintenance reaction kettle temperature degree；Monitor the electricity of stirring
Stream, after 30-50 minutes, system is pressurizeed with nitrogen, extrudes polymer from end of extruded band, tie rod cooling and dicing obtains semiaromatic adoption
Amide resin particle.
5. the preparation method of Semi-aromatic polyamide resin as claimed in claim 4, it is characterized in that in the raw material dicarboxylic acids
Long carbon chain aliphatic dicarboxylic acid accounts for its molar percentage more than 70%.
6. the preparation method of Semi-aromatic polyamide resin as claimed in claim 5, it is characterized in that other described raw material dicarboxylic acids
For in decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid or hexadecandioic acid (hexadecane diacid)
One or more.
7. the preparation method of Semi-aromatic polyamide resin as claimed in claim 4, it is characterized in that pair in the raw material diamines
Benzene dimethylamine construction unit accounts for raw material diamines molar percentage more than 70%.
8. the preparation method of Semi-aromatic polyamide resin as claimed in claim 7, the raw material diamines is Putriscine, 1,
6- hexamethylene diamines, 1,8- octamethylenediamines, 1,10- decamethylene diamines, 1,12- dodecamethylene diamines, 2- methyl isophthalic acids, 5- pentanediamines, 2,2,4- front threes
Base -1,6- hexamethylene diamines, 2,4,4- trimethyl -1,6- hexamethylene diamines, 2- methyl isophthalic acids, 8- octamethylenediamines, 5- methyl isophthalic acids, 9- nonane diamines
Deng aliphatic diamine, 1,3- double (aminomethyl) hexamethylenes, Isosorbide-5-Nitrae-bis- (aminomethyl) hexamethylene, cyclohexanediamine, methyl cyclohexane diamines,
One kind or its mixture in the aromatic diamine such as the ester ring type such as IPD diamines or m-xylene diamine.
9. the preparation method of Semi-aromatic polyamide resin as claimed in claim 4, it is characterized in that：The polymerization catalyst is phosphorus
One or more in compound, salt or ester compounds；Can also and with alkali metal compound or alkali earth metallic compound；
Wherein, phosphorus compound is specially phosphoric acid, phosphorous acid or hypophosphorous acid；
Salt is the metal salt or ammonium salt of potassium, sodium, magnesium, calcium, zinc, cobalt, manganese, tin, tungsten, vanadium, germanium, titanium or antimony；
Ester compounds are ethyl ester, isopropyl esters, butyl ester, hexyl ester, stearyl, 18 phosphinylidyne base esters or phenylester；
Alkali metal compound is sodium hydroxide, calcium hydroxide, potassium hydroxide or magnesium hydroxide；
Alkali earth metallic compound is carbonic acid, boric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, butenoic acid, valeric acid, caproic acid, dissident
It is acid, enanthic acid, octanoic acid, n-nonanoic acid, octadecanoid acid, cyclopentane-carboxylic acid, cyclohexane-carboxylic acid, hydrocinnamic acid, γ-phenylbutyric acid, right
Phenoxy benzoic acid, o-hydroxy cinnamic acid, o- β-chlorophenyl propionic acid, the alkali metal salt and alkaline earth of a chloro phenylpropionic acid
Metalloid salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710674996.8A CN107383365A (en) | 2017-08-09 | 2017-08-09 | A kind of Semi-aromatic polyamide resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710674996.8A CN107383365A (en) | 2017-08-09 | 2017-08-09 | A kind of Semi-aromatic polyamide resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107383365A true CN107383365A (en) | 2017-11-24 |
Family
ID=60354346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710674996.8A Pending CN107383365A (en) | 2017-08-09 | 2017-08-09 | A kind of Semi-aromatic polyamide resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107383365A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054775A (en) * | 2019-04-26 | 2019-07-26 | 东莞市江南现代远程信息研究院 | A kind of polyesteramide continuous production technology |
| CN110903477A (en) * | 2019-12-20 | 2020-03-24 | 山东安岩新材料科技有限公司 | Mixed diamine modified long carbon chain nylon and preparation method thereof |
| CN112029090A (en) * | 2019-06-03 | 2020-12-04 | 上海凯赛生物技术股份有限公司 | High-temperature-resistant low-water-absorption polyamide copolymer 5XT and preparation method thereof |
| CN112888339A (en) * | 2018-10-22 | 2021-06-01 | 可乐丽粘贴扣带株式会社 | Male molded hook and loop fastener having excellent heat resistance, method for producing same, and method for fixing automobile interior material using same |
| CN114058009A (en) * | 2021-12-13 | 2022-02-18 | 山东广垠新材料有限公司 | Process for preparing semi-aromatic polyamides with reduced loss of diamine monomer, semi-aromatic polyamides and molding compositions |
| US11905370B2 (en) | 2020-11-10 | 2024-02-20 | Zhengzhou University | Method for synthesizing long carbon chain semi-aromatic nylon |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102159621A (en) * | 2008-09-18 | 2011-08-17 | 三菱瓦斯化学株式会社 | Method for producing polyamide |
| CN102449068A (en) * | 2009-05-28 | 2012-05-09 | 三菱瓦斯化学株式会社 | Polyamide resin composition and molded article |
| CN102575099A (en) * | 2009-09-14 | 2012-07-11 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
| CN102575100A (en) * | 2009-09-14 | 2012-07-11 | 三菱瓦斯化学株式会社 | Flame-retardant polyamide resin composition |
| CN103987782A (en) * | 2011-12-16 | 2014-08-13 | 三菱瓦斯化学株式会社 | Molded article |
| CN105339435A (en) * | 2013-07-09 | 2016-02-17 | 三菱工程塑料株式会社 | Resin composition, resin molded product, manufacturing method of resin molded product, laser direct structuring additive |
-
2017
- 2017-08-09 CN CN201710674996.8A patent/CN107383365A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102159621A (en) * | 2008-09-18 | 2011-08-17 | 三菱瓦斯化学株式会社 | Method for producing polyamide |
| CN102449068A (en) * | 2009-05-28 | 2012-05-09 | 三菱瓦斯化学株式会社 | Polyamide resin composition and molded article |
| CN102575099A (en) * | 2009-09-14 | 2012-07-11 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
| CN102575100A (en) * | 2009-09-14 | 2012-07-11 | 三菱瓦斯化学株式会社 | Flame-retardant polyamide resin composition |
| CN103987782A (en) * | 2011-12-16 | 2014-08-13 | 三菱瓦斯化学株式会社 | Molded article |
| CN105339435A (en) * | 2013-07-09 | 2016-02-17 | 三菱工程塑料株式会社 | Resin composition, resin molded product, manufacturing method of resin molded product, laser direct structuring additive |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112888339A (en) * | 2018-10-22 | 2021-06-01 | 可乐丽粘贴扣带株式会社 | Male molded hook and loop fastener having excellent heat resistance, method for producing same, and method for fixing automobile interior material using same |
| CN110054775A (en) * | 2019-04-26 | 2019-07-26 | 东莞市江南现代远程信息研究院 | A kind of polyesteramide continuous production technology |
| CN110054775B (en) * | 2019-04-26 | 2021-05-18 | 东莞市江南现代远程信息研究院 | Continuous production process of polyesteramide |
| CN112029090A (en) * | 2019-06-03 | 2020-12-04 | 上海凯赛生物技术股份有限公司 | High-temperature-resistant low-water-absorption polyamide copolymer 5XT and preparation method thereof |
| CN110903477A (en) * | 2019-12-20 | 2020-03-24 | 山东安岩新材料科技有限公司 | Mixed diamine modified long carbon chain nylon and preparation method thereof |
| US11905370B2 (en) | 2020-11-10 | 2024-02-20 | Zhengzhou University | Method for synthesizing long carbon chain semi-aromatic nylon |
| CN114058009A (en) * | 2021-12-13 | 2022-02-18 | 山东广垠新材料有限公司 | Process for preparing semi-aromatic polyamides with reduced loss of diamine monomer, semi-aromatic polyamides and molding compositions |
| CN114058009B (en) * | 2021-12-13 | 2023-11-10 | 山东广垠新材料有限公司 | Process for the preparation of semi-aromatic polyamides with reduced diamine monomer loss, semi-aromatic polyamides and molding compositions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107383365A (en) | A kind of Semi-aromatic polyamide resin and preparation method thereof | |
| JP5664243B2 (en) | Polyamide resin | |
| US6156869A (en) | Method for producing polyamides | |
| US9611356B2 (en) | Copolymer polyamide | |
| JP6416756B2 (en) | Thermoplastic melt blend composition containing amino acid heat stabilizer | |
| KR102234828B1 (en) | Process for the continuous preparation of an aliphatic or partially aromatic polyamide | |
| US9228057B2 (en) | Polyamide, polyamide composition, and molded article | |
| TW201130886A (en) | Copolymerized polyamide | |
| TWI649348B (en) | Polyamide manufacturing method | |
| JP2003055549A (en) | Polyamide composition | |
| JPH08502548A (en) | Polyamide having improved color and processability and method for producing the same | |
| JP2016521795A (en) | Process for the preparation of aliphatic or partially aromatic polyamides including solid phase polymerization | |
| PT3008106T (en) | Partially aromatic copolyamides with a high glass transition temperature and high degree of crystallinity | |
| JP2013525559A (en) | Semi-aromatic polyamide | |
| JP6097189B2 (en) | Polyamide resin composition | |
| EP3008108B1 (en) | Method for producing partially aromatic copolyamides with high diamine excess | |
| CA2914102C (en) | Method for the continuous production of an aliphatic or semi-aromatic polyamide oligomer | |
| JP2000186142A (en) | Production of polyamide | |
| KR102203359B1 (en) | Xylylene diamine composition, and method for producing polyamide resin | |
| KR101563250B1 (en) | Xylylenediamine composition, and method for producing polyamide resin | |
| EP3896113A1 (en) | Semi-aromatic polyamide resin and method for manufacturing same | |
| KR101358226B1 (en) | Method for Synthesizing Semi-crystalline and Semi-aromatic copolyamide with Ultra High Molecular Weight Using Solid-state Polymerization | |
| TW201942192A (en) | Semi-aromatic polyamide resin and method for manufacturing same | |
| JP6042114B2 (en) | Copolymerized polyamide and copolymerized polyamide composition | |
| EP3064528B1 (en) | Xylylenediamine composition and method for producing polyamide resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171124 |