CN109824897A - A kind of polyamidoimide and preparation method thereof - Google Patents
A kind of polyamidoimide and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of polyamidoimide, the following steps are included: aromatic diamine, maleimide carboxylic acid and organic bases catalyst are added in non-proton nitrogenous polar organic solvent, heating carries out back flow reaction after stirring, it is dried after the reaction was completed, obtains the powder of amino acids monomer with imide group；Powder of amino acids monomer, ortho phosphorous acid salt catalyst and deionized water are added in high pressure polymerisation reaction kettle and carry out self-condensation reaction, the suspension of polyamidoimide prepolymer is obtained after the reaction was completed, after drying, vacuum solid-phase tack producing is carried out again, and the polyamidoimide of different molecular weight can be obtained.This method process route is simple, can effectively recycle organic solvent, at low cost and without considering that monomer equivalent compares control problem, it is easy to accomplish industrialization.The present invention also provides polyamidoimides obtained by this method to have the characteristics such as high-intensitive, high-modulus and excellent heat resistance with good processing and forming characteristic.
Description
Technical field
The invention belongs to polymeric material fields more particularly to a kind of polyamidoimide and preparation method thereof.
Background technique
Polyamide-imides (abbreviation PAI) is a kind of high-temperature-resistant thermoplastic engineering plastics of performance brilliance.Due to molecule master
On chain simultaneously contain heat-resisting imide group and amide group flexible, PAI product not only have polyimides heat resistance,
The characteristics such as low creep, high intensity, high-modulus, solvent resistant, while the mechanical property and moulding processability for having polyamide excellent,
The techniques such as conventional injection molding, extrusion, molding can be used and carry out processing and forming, therefore set in aerospace, military equipment, chemical industry
The fields such as standby, electronic equipments are widely used, and have vast potential for future development.
Moulding compound generallys use chloride method with PAI at present, i.e., using inclined three acyl chlorides of benzene (TMAc) and aromatic diamine as raw material,
PAI is prepared by polycondensation in nitrogenous polar organic solvent.Chloride method production PAI has realized industrialization, and technology is more mature, but
Have the following problems: (1) critical materials Trimellitic Anhydride Chloride is expensive, storage stability is poor, and the inclined benzene of its upstream raw material
Three acid anhydrides (TMA) because of it there is breathing sensitization to be determined as paying high attention to substance at present by European Union；(2) acid chloride route is related to
The processing steps such as prepolymerization, Cheng Fen, the hot imidization of polyamic acid, route is longer, and the difficulty of properties of product stability control increases
Add；(3) the HCl gas that chloride method releases in process of production pollutes the environment, and corrodes equipment, increases production cost.These
Defect largely becomes the limiting factor of PAI development.
Chinese patent application CN102718969A discloses the conjunction of half fatty polyamide of abietyl-acid imide PA6I a kind of
At method.First maleopimaric acid acyl chlorides is prepared by raw material of gum rosin in this method, then poly- by melting with 1,6- hexamethylene diamine
Close preparation PAI；But the chemical equivalent ratio of acyl chlorides and diamines is generally difficult to accurate control, and melt polymerization temperature is higher, unfavorable
In the synthesis of high molecular weight PAI.Document One-pot synthesis of linear and branched poly (amide
Aspartimide) s with good solubility in organic solvents is described with 4,4'- diamino hexichol
Methane and 4- maleimide yl benzoic acid are the method that raw material prepares PAI, this method simple process but entire reaction process is having
It is carried out in solvent, solvent-oil ratio is big and solvent recovery is more difficult, and the molecular chain conformation of product is not easy to adjust.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind polyamidoimide, while the high pressure aqueous phase synthesis method of the polyamidoimide being also provided.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of preparation method of polyamidoimide, comprising the following steps:
(1) the non-proton nitrogenous polarity of aromatic diamine, maleimide carboxylic acid and organic bases catalyst addition is organic
In solvent, heating carries out back flow reaction after stirring, is dried after the reaction was completed, obtains the amino acid powder with imide group
Last monomer；
(2) high pressure is added in powder of amino acids monomer, ortho phosphorous acid salt catalyst and the deionized water after step (1) to gather
It closes in reaction kettle and carries out self-condensation reaction, obtain the suspension of polyamidoimide prepolymer after the reaction was completed, after drying, then
Vacuum solid-phase tack producing is carried out, the polyamidoimide of different molecular weight can be obtained.
Above-mentioned preparation method, it is preferred that in the step (1), the general structure of aromatic diamine is NH2—Z—NH2,
Wherein Z isX be-O-,-S-,-CO-,-
CH2- or-SO2—；
The general structure of maleimide carboxylic acid isWherein Y is —(CH2)n- or-(CH2CH2O)n CH2CH2—；
Organic bases catalyst be sodium ethoxide, triethylamine, hexahydropyridine, n-butyl alcohol potassium, Sodamide, in level Four amine base extremely
Few one kind；
Preparation method of the invention contains benzene ring structure in selected aromatic diamine, is introduced into products molecule structure
The heat resistance and mechanical property of product can effectively be promoted；The maleimide carboxylic acid chemical structural formula of selection is simple, at present
Industrialized production is realized, cost is relatively low, and commercial product purity is higher, is conducive to later period polyamidoimide product mechanics
The promotion of performance；The organic bases catalyst of selection can not only be such that the electron density on carbon-to-carbon double bond subtracts after activated group
It is small, outside acceptant nucleophilic attack, and anion bring charge can also be made more to disperse, enable Michacel addition reaction
With the progress of reasonable speed.
Above-mentioned preparation method, it is preferred that in the step (1), non-proton nitrogenous polar organic solvent is dimethyl second
Amide (DMAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP), methyl ethyl ketone
(MEK), at least one of hexamethyl phosphoramide (HMPA).
Since amine monomers are oxidized easily, the present invention use micro- excessive mode with ensure react can be normally carried out,
Excessive diamine monomer can be removed by way of washing after the completion of reaction；In view of organic bases catalyst itself is easy
Water suction leads to partial inactivation, if the amount for the catalyst being added is very few, reaction speed slows down, and the reaction time extends；If plus
The amount of the catalyst entered is excessive, then will increase unnecessary cost, causes to waste；Therefore, the present invention by by aromatic diamine,
The molar ratio control of maleimide carboxylic acid, organic bases catalyst three is in aromatic diamine: maleimide carboxylic acid: organic
Alkali catalyst=(1~1.03): 1:(0.2~0.5), to guarantee that Michacel addition reaction is gone on smoothly.
Preparation method of the invention carries out the self-condensation reaction of step (2), reaction process peace using deionized water as solvent
Entirely, environmentally friendly.It was found that on the one hand the additional amount of deionized water will affect reacting kettle inner pressure, body on the other hand also will affect
The mass-and heat-transfer efficiency of system, such as when the additional amount of deionized water is less, it is poor to will lead to system heat transfer efficiency, causes local appearance
Easily overheat, influences properties of product.In view of the pressure-resistant upper limit of autoclave (5~50L) wirking pressure table is 2.5MPa or so,
Temperature be lower than 250 DEG C under the conditions of, it is 2~4 times of powder of amino acids quality that the additive amount of deionized water, which is controlled, gained go from
Sub- aqueous systems pressure is no more than 2.4MPa, meets polymerization reaction and its safety requirements.It is additionally contemplates that catalytic efficiency simultaneously, is produced into
The comprehensive performance of this and product, the present invention is by the quality of powder of amino acids monomer, ortho phosphorous acid salt catalyst and deionized water
It is powder of amino acids monomer: ortho phosphorous acid salt catalyst: deionized water=100:(2~5 than control): (200~400)；It is described
Ortho phosphorous acid salt catalyst is at least one of sodium hypophosphite, ortho phosphorous acid potassium, Lime Hypophosphate, ortho phosphorous acid magnesium.
Above-mentioned preparation method, it is preferred that in the step (2), self-condensation reaction carries out under an inert atmosphere, from polycondensation
The heating rate of reaction is 1~5 DEG C/min, and reaction temperature is 170~220 DEG C, and the isothermal reaction time is 3~6h, pressure 1.5
~2.2MPa, stirring is aided in reaction process, and mixing speed is 50~400r/min.It is furthermore preferred that in the step (2), from
It is carried out under high-purity argon gas in polycondensation process.Preparation method of the invention controls self-condensation reaction temperature in the present invention
In the range of, it can be ensured that system pressure is kept within the scope of the invention, while again by reaction time and mixing speed control
System is within the scope of the invention, it can be ensured that reaction sufficiently carries out, it is ensured that reaction system mass-and heat-transfer efficiency with higher.
Above-mentioned preparation method, it is preferred that in the step (2), carry out self-condensation reaction before, by vacuumize repeatedly-
The mode of logical inert gas displaces the air in reaction kettle, and 5-10 time repeatedly, after the completion of displacement reserved 0.1 in reaction kettle~
0.3MPa pressure.Preparation method of the invention reserves 0.1~0.3MPa pressure in kettle, is on the one hand to ensure amine list
Body is also in always under the protection of inert atmosphere during being warming up to predetermined reaction temperature；On the other hand, pre-reservation pressure also has
Conducive in temperature-rise period self-condensation reaction it is mobile towards positive direction.
Above-mentioned preparation method, it is preferred that in the step (1), be warming up to 100~120 DEG C, the time of back flow reaction is
8~10 hours.Preparation method of the invention within the scope of the invention by the temperature and time control reacted in step (1) can
To guarantee the yield of powder of amino acids for 95%~97%；If temperature is relatively low or the time is insufficient, reacts insufficient, cause
Product yield reduces；If temperature drift or overlong time, reacts and be easy to generate by-product.
Above-mentioned preparation method, it is preferred that in the step (2), the temperature of control vacuum solid-phase tack producing is 200~250
DEG C, vacuum degree is -0.06~-0.04MPa, the thickening time is 12~for 24 hours, the number-average molecular weight of gained polyamidoimide is 3
×104~1.2 × 105.Although what the suspension of polyamidoimide prepolymer obtained after being separated by solid-liquid separation, being dried is also polyamides
Amine acid imide, but its molecular weight is relatively low (number-average molecular weight is between 17000~25000), can not effective processing and forming, Huo Zhejia
The mechanical property of product is insufficient after work, is unable to satisfy industrial application requirement.The present invention passes through to the polyamidoimide after drying
Carrying out vacuum solid-phase tack producing within the scope of the invention by the state modulator of solid-phase tack producing makes active end group under solid conditions
The reaction was continued to promote increasing for strand, to promote the comprehensive performance of product.If being lower than the scope of the present invention, viscosify
Effect is limited, is unable to satisfy the related request of industrial application；If beyond the scope of this invention, product may turn yellow, and influence
Product appearance and comprehensive performance.
Above-mentioned preparation method, it is preferred that in the step (1), be dried using vacuum spray dehydrator, in order to protect
Drying effect is demonstrate,proved, while improving solvent recovery efficiency, the intake air temperature for controlling vacuum spray dehydrator is 200~220 DEG C, very
Reciprocal of duty cycle is -0.06~-0.04MPa.
Above-mentioned preparation method, it is preferred that in the step (2), be dried, controlled using vacuum spray drying granulator
The intake air temperature of vacuum spray drying granulator processed is 120~150 DEG C, and vacuum degree is -0.08~-0.04MPa, is granulated partial size
It is 100~1000 μm.
Preparation method of the invention, by the state modulator being dried using spray-drying pelleting machine at this in step (2)
In the range of invention, the fast eliminating of solvent not only may be implemented, but also powder and granulation can be implemented as after solvent removal
Integration operation；When taking water as a solvent, vacuum degree reaches the removing that solvent can be realized in -0.08~-0.04MPa；Pass through control
Being granulated partial size can prevent from powder from being taken away during the vacuum solid-phase tack producing in later period by negative pressure causing to be lost；Intake air temperature is such as
Fruit is lower than the scope of the present invention, then drying effect is bad, and powder is easy adhesion, and pelletization partial size is not easy to control；Air inlet temperature
If degree is higher than the scope of the present invention, desciccate is also unfavorable for the regulation of granulation partial size in filiform.
Above-mentioned preparation method, it is preferred that in the step (1), the general structure of powder of amino acids monomer is
In the step (2), the general structure of polyimides imide prepolymer is
N is 50~100；
Wherein, Y is—(CH2)n- or-(CH2CH2O)n CH2CH2-, Z
ForX is-O-,-S-,-CO-,-CH2—
Or-SO2—。
The inventive concept total as one, the present invention also provides a kind of polyamides being prepared according to above-mentioned preparation method
Amine acid imide.
Technical solution of the present invention is based primarily upon following principle:
The invention firstly uses the Michael addition reactions between amino and dimaleoyl imino to be prepared with acyl Asia
PAI pre-polymerization is prepared using the self-condensation reaction of amino acid monomer then using water as solvent in the amino acid monomer of amine groups
Object, and then by the molecular chain conformation of vacuum Solid State Tackifing Technique regulation PAI, obtain the PAI of different performance.
In the present invention, shown in the chemical equation such as formula (1) that aromatic diamine and maleimide carboxylic acid react:
Amino acid monomer with imide group occurs self-condensation reaction and obtains the chemical equation such as formula of PAI prepolymer
(2) shown in:
Wherein, Y is—(CH2)n- or-(CH2CH2O)nCH2CH2-, Z
ForX is-O-,-S-,-CO-,-CH2—
Or-SO2—。
Compared with the prior art, the advantages of the present invention are as follows:
(1) preparation method of the invention, polyamidoimide is prepared using two-step method, and organic solvent is having acid imide
Can be directly by spray drying recycling after the completion of the amino acid monomer preparation of group, step is simple and recovery efficiency is high, avoids
The problems such as organic solvent is largely consumed with difficulty is separated in chloride method.
(2) preparation method of the invention is prepared poly- by the self-condensation reaction of the amino acid monomer with imide group
Amide imide, process route is simple, and polymerization process is participated in without trimellitic anhydride and its derivative species monomer, at low cost and nothing
It need to consider that monomer equivalent compares control problem；From polycondensation process using water as solvent, polymerization temperature is lower, easy-to-operate and
It is environmentally friendly.
(3) preparation method of the invention, by the way of " viscosifying after first pre-polymerization ", first it is sub- that polyamide acyl is prepared in polymerization
The suspension of amine prepolymer, discharging is convenient, and the later period can facilitate realization polyamide by changing the technological parameter of vacuum solid-phase tack producing
The regulation of the physico-chemical property of acid imide product, modification scope is wide and controllability is good, it is easy to accomplish industrialization.
(4) polyamidoimide that the present invention is prepared, appearance are creamy white, and conventional injection molding, extrusion, mould can be used
The techniques such as pressure carry out processing and forming, have good processing and forming characteristic, have high-intensitive, high-modulus and excellent heat resistance
Etc. characteristics, have the potential using value in fields such as aerospace, military equipment, chemical industry equipment, electronic equipments.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with preferred embodiment and more comprehensively, is meticulously retouched
It states, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Comparative example 1:
A kind of preparation method of polyamidoimide, comprising the following steps:
(1) 1045.44gN, N'- dimethyl is added in four mouthfuls of reaction flasks equipped with mechanical stirring, condenser pipe and thermometer
Then acetamide adds 200.24g 4,4'- diaminodiphenyl ether, 217.18g 4- maleimidobenzoyl, 20.42g
Sodium ethoxide (molar ratio of three is 1:1:0.3), opens stirring, and control mixing speed is 200r/min, is gradually warming up to 120
DEG C, back flow reaction 8 hours, it is cooled to room temperature after reaction；Solution is delivered in vacuum spray dehydrator by peristaltic pump,
Wriggling revolution speed is 75r/min, and the intake air temperature of vacuum spray dehydrator is 200 DEG C, and vacuum degree is -0.04MPa, spraying dry
The powder of amino acids monomer with imide group is obtained after dry, powder diameter is 20~100 μm；
(2) the powder of amino acids monomer being prepared in 300g step (1), 12g sodium hypophosphite and 1200g is weighed to go
Ionized water is added in 5L polymerization autoclave, and the sky in reaction kettle is displaced by way of vacuumizing-leading to high-purity argon gas repeatedly
Gas 6 times repeatedly, reserves 0.2MPa pressure in kettle after the completion of displacement；Under the protection of high-purity argon gas, with the heating speed of 2 DEG C/min
Temperature in the kettle is increased to 180 DEG C by rate, and mechanical stirring speed control is maintained at 1.6MPa, constant temperature in 200r/min, kettle internal pressure power
Self-condensation reaction 3 hours；After the reaction was completed, temperature in the kettle is gradually down to room temperature, then empties residual pressure in kettle, will obtains
Polyamidoimide prepolymer suspension from reactor bottom be discharged；
(3) suspension of polyamidoimide prepolymer is delivered in vacuum spray drying granulator by peristaltic pump,
Wriggling revolution speed is 75r/min, and the intake air temperature of vacuum spray drying granulator is 120 DEG C, and vacuum degree is -0.06MPa, spray
The polyamidoimide of low molecular weight is obtained after mist drying and granulation, grain diameter is at 200~1000 μm.
Embodiment 1:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1), (2), (3) are identical as (1) of comparative example 1, (2), (3) respectively；
(4) polyamidoimide of low molecular weight is delivered to progress vacuum solid-phase tack producing, vacuum solid phase in vacuum drum
Viscosifying temperature is 220 DEG C, and the thickening time is 12h, obtains polyamidoimide of the invention.
Embodiment 2:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1), (2), (3) are identical as (1) of comparative example 1, (2), (3) respectively；
(4) polyamidoimide of low molecular weight is delivered to progress vacuum solid-phase tack producing, vacuum solid phase in vacuum drum
Viscosifying temperature is 240 DEG C, and the thickening time is 12h, obtains polyamidoimide of the invention.
Embodiment 3:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1), (2), (3) are identical as (1) of comparative example 1, (2), (3) respectively；
(4) polyamidoimide of low molecular weight is delivered to progress vacuum solid-phase tack producing, vacuum solid phase in vacuum drum
Viscosifying temperature is 220 DEG C, and vacuum degree is -0.04MPa, and the thickening time is 18h, obtains polyamidoimide of the invention.
Embodiment 4:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1), (2), (3) are identical as (1) of comparative example 1, (2), (3) respectively；
(4) polyamidoimide of low molecular weight is delivered to progress vacuum solid-phase tack producing, vacuum solid phase in vacuum drum
Viscosifying temperature is 240 DEG C, and vacuum degree is -0.04MPa, and the thickening time is 18h, obtains polyamidoimide of the invention.
Embodiment 5:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1) 1045.44gN, N'- dimethyl is added in four mouthfuls of reaction flasks equipped with mechanical stirring, condenser pipe and thermometer
Then acetamide adds 200.24g 4,4'- diaminodiphenyl ether, 217.18g 4- maleimidobenzoyl, 20.42g
Sodium ethoxide (molar ratio of three is 1:1:0.3), opens stirring, and control mixing speed is 200r/min, is gradually warming up to 120
DEG C, back flow reaction 8 hours, it is cooled to room temperature after reaction；Solution is delivered in vacuum spray dehydrator by peristaltic pump,
Wriggling revolution speed is 75r/min, and the intake air temperature of vacuum spray dehydrator is 200 DEG C, and vacuum degree is -0.04MPa, spraying dry
The powder of amino acids monomer with imide group is obtained after dry, powder diameter is 20~100 μm；
(2) the powder of amino acids monomer being prepared in 300g step (1), 12g sodium hypophosphite and 1200g is weighed to go
Ionized water is added in 5L polymerization autoclave, and the sky in reaction kettle is displaced by way of vacuumizing-leading to high-purity argon gas repeatedly
Gas 6 times repeatedly, reserves 0.2MPa pressure in kettle after the completion of displacement；Under the protection of high-purity argon gas, with the heating speed of 2 DEG C/min
Temperature in the kettle is increased to 180 DEG C by rate, and mechanical stirring speed control is maintained at 1.6MPa, constant temperature in 200r/min, kettle internal pressure power
Self-condensation reaction 5 hours；After the reaction was completed, temperature in the kettle is gradually down to room temperature, then empties residual pressure in kettle, will obtains
Polyamidoimide prepolymer suspension from reactor bottom be discharged；
(3) suspension of polyamidoimide prepolymer is delivered in vacuum spray drying granulator by peristaltic pump,
Wriggling revolution speed is 75r/min, and the intake air temperature of vacuum spray drying granulator is 120 DEG C, and vacuum degree is -0.06MPa, spray
The polyamidoimide of low molecular weight is obtained after mist drying and granulation, grain diameter is at 200~1000 μm；
(4) polyamidoimide of low molecular weight is delivered to progress vacuum solid-phase tack producing, vacuum solid phase in vacuum drum
Viscosifying temperature is 220 DEG C, and vacuum degree is -0.04MPa, and the thickening time is 18h, obtains polyamidoimide of the invention.
Embodiment 6:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1), (2), (3) are identical as (1) of embodiment 5, (2), (3) respectively；
(4) polyamidoimide of low molecular weight is delivered to progress vacuum solid-phase tack producing, vacuum solid phase in vacuum drum
Viscosifying temperature is 240 DEG C, and vacuum degree is -0.04MPa, and the thickening time is 12h, obtains polyamidoimide of the invention.
Comparative example 2:
A kind of preparation method of polyamidoimide, comprising the following steps:
(1) 1045.44gN, N'- dimethyl is added in four mouthfuls of reaction flasks equipped with mechanical stirring, condenser pipe and thermometer
Then acetamide adds 200.24g 4,4'- diaminodiphenyl ether, 217.18g 4- maleimidobenzoyl, 20.42g
Sodium ethoxide (molar ratio of three is 1:1:0.3), opens stirring, and control mixing speed is 200r/min, is gradually warming up to 120
DEG C, back flow reaction 8 hours, it is cooled to room temperature after reaction；Solution is delivered in vacuum spray dehydrator by peristaltic pump,
Wriggling revolution speed is 75r/min, and the intake air temperature of vacuum spray dehydrator is 200 DEG C, and vacuum degree is -0.04MPa, spraying dry
The powder of amino acids monomer with imide group is obtained after dry, powder diameter is 20~100 μm；
(2) the powder of amino acids monomer being prepared in 300g step (1), 12g sodium hypophosphite and 1200g is weighed to go
Ionized water is added in 5L polymerization autoclave, and the sky in reaction kettle is displaced by way of vacuumizing-leading to high-purity argon gas repeatedly
Gas 6 times repeatedly, reserves 0.2MPa pressure in kettle after the completion of displacement；Under the protection of high-purity argon gas, with the heating speed of 2 DEG C/min
Temperature in the kettle is increased to 210 DEG C by rate, and mechanical stirring speed control is maintained at 1.9MPa, constant temperature in 200r/min, kettle internal pressure power
Self-condensation reaction 3 hours；After the reaction was completed, temperature in the kettle is gradually down to room temperature, then empties residual pressure in kettle, will obtains
Polyamidoimide prepolymer suspension from reactor bottom be discharged；
(3) suspension of polyamidoimide prepolymer is delivered in vacuum spray drying granulator by peristaltic pump,
Wriggling revolution speed is 75r/min, and the intake air temperature of vacuum spray drying granulator is 120 DEG C, and vacuum degree is -0.06MPa, spray
The polyamidoimide of low molecular weight is obtained after mist drying and granulation, grain diameter is at 200~1000 μm.
Embodiment 7:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1), (2), (3) are identical as (1) of comparative example 2, (2), (3) respectively；
(4) polyamidoimide of low molecular weight is delivered to progress vacuum solid-phase tack producing, vacuum solid phase in vacuum drum
Viscosifying temperature is 220 DEG C, and vacuum degree is -0.04MPa, and the thickening time is 18h, obtains polyamidoimide of the invention.
Embodiment 8:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1), (2), (3) are identical as (1) of comparative example 2, (2), (3)；
(4) polyamidoimide of low molecular weight is delivered to progress vacuum solid-phase tack producing, vacuum solid phase in vacuum drum
Viscosifying temperature is 240 DEG C, and vacuum degree is -0.04MPa, and the thickening time is 12h, obtains polyamidoimide of the invention.
Embodiment 9:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1) 1045.44gN, N'- dimethyl is added in four mouthfuls of reaction flasks equipped with mechanical stirring, condenser pipe and thermometer
Then acetamide adds 200.24g 4,4'- diaminodiphenyl ether, 217.18g 4- maleimidobenzoyl, 20.42g
Sodium ethoxide (molar ratio of three is 1:1:0.3), opens stirring, and control mixing speed is 200r/min, is gradually warming up to 120
DEG C, back flow reaction 8 hours, it is cooled to room temperature after reaction；Solution is delivered in vacuum spray dehydrator by peristaltic pump,
Wriggling revolution speed is 75r/min, and the intake air temperature of vacuum spray dehydrator is 200 DEG C, and vacuum degree is -0.04MPa, spraying dry
The powder of amino acids monomer with imide group is obtained after dry, powder diameter is 20~100 μm；
(2) the powder of amino acids monomer being prepared in 300g step (1), 12g sodium hypophosphite and 1200g is weighed to go
Ionized water is added in 5L polymerization autoclave, and the sky in reaction kettle is displaced by way of vacuumizing-leading to high-purity argon gas repeatedly
Gas 6 times repeatedly, reserves 0.2MPa pressure in kettle after the completion of displacement；Under the protection of high-purity argon gas, with the heating speed of 2 DEG C/min
Temperature in the kettle is increased to 210 DEG C by rate, and mechanical stirring speed control is maintained at 1.9MPa, constant temperature in 200r/min, kettle internal pressure power
Self-condensation reaction 5 hours；After the reaction was completed, temperature in the kettle is gradually down to room temperature, then empties residual pressure in kettle, will obtains
Polyamidoimide prepolymer suspension from reactor bottom be discharged；
(3) suspension of polyamidoimide prepolymer is delivered in vacuum spray drying granulator by peristaltic pump,
Wriggling revolution speed is 75r/min, and the intake air temperature of vacuum spray drying granulator is 120 DEG C, and vacuum degree is -0.06MPa, spray
The polyamidoimide of low molecular weight is obtained after mist drying and granulation, grain diameter is at 200~1000 μm.
(4) polyamidoimide of low molecular weight is delivered to progress vacuum solid-phase tack producing, vacuum solid phase in vacuum drum
Viscosifying temperature is 220 DEG C, and vacuum degree is -0.04MPa, and the thickening time is 18h, obtains polyamidoimide of the invention.
Embodiment 10:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1), (2), (3) are identical as (1) of embodiment 9, (2), (3) respectively；
(4) polyamidoimide of low molecular weight is delivered to progress vacuum solid-phase tack producing, vacuum solid phase in vacuum drum
Viscosifying temperature is 240 DEG C, and vacuum degree is -0.04MPa, and the thickening time is 12h, obtains polyamidoimide of the invention.
Embodiment 11:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1) 1045.44gN, N'- dimethyl is added in four mouthfuls of reaction flasks equipped with mechanical stirring, condenser pipe and thermometer
Then acetamide adds 200.24g 4,4'- diaminodiphenyl ether, 211.21g 6- maleimidohexanoic acid, 20.42g second
Sodium alkoxide (molar ratio of three is 1:1:0.3), opens stirring, and control mixing speed is 200r/min, is gradually warming up to 120 DEG C,
Back flow reaction 8 hours, it is cooled to room temperature after reaction；Solution is delivered in vacuum spray dehydrator by peristaltic pump, it is compacted
Dynamic revolution speed is 75r/min, and the intake air temperature of vacuum spray dehydrator is 200 DEG C, and vacuum degree is -0.04MPa, spray drying
The powder of amino acids monomer with imide group is obtained afterwards, and powder diameter is 20~100 μm；
(2), (3), (4) are identical as (2) of embodiment 9, (3), (4) respectively.
Embodiment 12:
A kind of preparation method of polyamidoimide of the invention, comprising the following steps:
(1) 1045.44gN, N'- dimethyl is added in four mouthfuls of reaction flasks equipped with mechanical stirring, condenser pipe and thermometer
Acetamide, then add 108.14g m-phenylene diamine (MPD), 211.21g 6- maleimidohexanoic acid, 20.42g sodium ethoxide (three's
Molar ratio is 1:1:0.3), stirring is opened, control mixing speed is 200r/min, is gradually warming up to 120 DEG C, back flow reaction 8 is small
When, it is cooled to room temperature after reaction；Solution is delivered in vacuum spray dehydrator by peristaltic pump, wriggling revolution speed is
75r/min, the intake air temperature of vacuum spray dehydrator are 200 DEG C, and vacuum degree is -0.04MPa, is had after spray drying
The powder of amino acids monomer of imide group, powder diameter are 20~100 μm；
(2), (3), (4) are identical as (2) of embodiment 9, (3), (4) respectively.
Following performance survey is carried out to the polyamidoimide that above-described embodiment 1~12 and comparative example 1~2 are prepared
Examination, test result are as shown in table 1:
1, number-average molecular weight: with N, N'- dimethylformamide is measured as solvent and leacheate by gel permeation chromatography
The number-average molecular weight of PAI resin；
2, it glass transition temperature: is tested by standard ASTM-D3418；
3, mechanical property: preparation PAI is molded test bars, tensile strength is tested according to standard GB/T1040.2, according to GB/
T9341-2008 tests bending strength and bending modulus, simple beam impact strength is tested according to standard GB/T10431, according to standard
ASTM-D648 tests heat distortion temperature；
The correlated performance of polyamidoimide obtained in 1 embodiment of the present invention 1~12 of table and comparative example 1~2
As can be seen from Table 1, self-condensation reaction, vacuum solid-phase tack producing conditional parameter pair are formulated and regulated and controled by changing
The performance of PAI product has larger impact, the PAI product of different type, different grades can be prepared, wherein embodiment 9 is made
The comprehensive performance of the PAI product obtained is optimal；Have good processing and forming special using PAI product made from method of the invention
Property, there are the characteristics such as high-intensitive, high-modulus and excellent heat resistance, have aerospace, military equipment, chemical industry equipment,
The potential using value in the fields such as electronic equipments.
Claims (10)
1. a kind of preparation method of polyamidoimide, which comprises the following steps:
(1) non-proton nitrogenous polar organic solvent is added in aromatic diamine, maleimide carboxylic acid and organic bases catalyst
In, heating carries out back flow reaction after stirring, is dried after the reaction was completed, obtains the powder of amino acids list with imide group
Body；
(2) by after step (1) powder of amino acids monomer, that high pressure polymerisation is added in ortho phosphorous acid salt catalyst and deionized water is anti-
It answers and carries out self-condensation reaction in kettle, obtain the suspension of polyamidoimide prepolymer after the reaction was completed, after drying, then carry out
The polyamidoimide of different molecular weight can be obtained in vacuum solid-phase tack producing.
2. preparation method according to claim 1, which is characterized in that in the step (1), the structure of aromatic diamine is logical
Formula is NH2—Z—NH2, wherein Z beX be-O-,-
S—、—CO—、—CH2- or-SO2—；
The general structure of maleimide carboxylic acid isWherein Y is
—(CH2)n- or-(CH2CH2O)nCH2CH2—；
Organic bases catalyst is sodium ethoxide, triethylamine, hexahydropyridine, n-butyl alcohol potassium, Sodamide, at least one in level Four amine base
Kind；
Non-proton nitrogenous polar organic solvent is dimethyl acetamide, dimethylformamide, dimethyl sulfoxide, N- crassitude
At least one of ketone, methyl ethyl ketone, hexamethyl phosphoramide；
The aromatic diamine, maleimide carboxylic acid, organic bases catalyst molar ratio be aromatic diamine: maleimide
Amine carboxylic acid: organic bases catalyst=(1~1.03): 1:(0.2~0.5).
3. preparation method according to claim 1, which is characterized in that powder of amino acids monomer, secondary in the step (2)
The mass ratio of phosphite catalysts and deionized water is powder of amino acids monomer: ortho phosphorous acid salt catalyst: deionized water=
100:(2~5): (200~400)；The ortho phosphorous acid salt catalyst be sodium hypophosphite, ortho phosphorous acid potassium, Lime Hypophosphate,
At least one of ortho phosphorous acid magnesium.
4. preparation method according to claim 1, which is characterized in that in the step (2), self-condensation reaction is in indifferent gas
It is carried out under atmosphere, the heating rate of self-condensation reaction is 1~5 DEG C/min, and reaction temperature is 170~220 DEG C, and the isothermal reaction time is
3~6h, pressure are 1.5~2.2MPa, and stirring is aided in reaction process, and mixing speed is 50~400r/min.
5. the preparation method according to claim 4, which is characterized in that in the step (2), before carrying out self-condensation reaction,
The air in reaction kettle is displaced by way of vacuumizing-leading to inert gas repeatedly, 5-10 times repeatedly, is reacted after the completion of displacement
0.1~0.3MPa pressure is reserved in kettle.
6. preparation method according to claim 1, which is characterized in that in the step (1), 100~120 DEG C are warming up to,
The time of back flow reaction is 8~10 hours.
7. the method according to claim 1, wherein controlling the temperature of vacuum solid-phase tack producing in the step (2)
Be 200~250 DEG C, vacuum degree be -0.06~-0.04MPa, thickening the time be 12~for 24 hours, the number of gained polyamidoimide is equal
Molecular weight is 3 × 104~1.2 × 105。
8. preparation method according to claim 1, which is characterized in that in the step (1), using vacuum spray dehydrator
It is dried, the intake air temperature for controlling vacuum spray dehydrator is 200~220 DEG C, and vacuum degree is -0.06~-0.04MPa；
It in the step (2), is dried using vacuum spray drying granulator, controls the air inlet of vacuum spray drying granulator
Mouth temperature is 120~150 DEG C, and vacuum degree is -0.08~-0.04MPa, and being granulated partial size is 100~1000 μm.
9. preparation method according to claim 1, which is characterized in that in the step (1), the knot of powder of amino acids monomer
Structure general formula is
In the step (2), the general structure of polyimides imide prepolymer is
N is 50~100；
Wherein, Y is—(CH2)n- or-(CH2CH2O)nCH2CH2-, Z isX is-O-,-S-,-CO-,-CH2- or-
SO2—。
10. it is a kind of according to claim 1~any one of 9 described in the polyamidoimide that is prepared of preparation method.
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| CN114573812A (en) * | 2020-12-29 | 2022-06-03 | 深圳市研一新材料有限责任公司 | Binder for lithium ion battery and preparation method thereof |
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| CN117986580A (en) * | 2024-02-05 | 2024-05-07 | 广东硕成科技股份有限公司 | Polyamide imide containing sulfonyl structure, and preparation method and application thereof |
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