CN106279687B - A kind of crystalline thermoplastic copolyimide resin and application - Google Patents

A kind of crystalline thermoplastic copolyimide resin and application Download PDF

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CN106279687B
CN106279687B CN201610656891.5A CN201610656891A CN106279687B CN 106279687 B CN106279687 B CN 106279687B CN 201610656891 A CN201610656891 A CN 201610656891A CN 106279687 B CN106279687 B CN 106279687B
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benzene
bis
amino
aromatic
crystalline thermoplastic
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CN106279687A (en
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方省众
张鸿飞
王玮
陈国飞
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a kind of crystalline thermoplastic copolyimide resins, it is made by polycondensation reaction by aromatic dianhydride monomer, aromatic diamine monomer, end-capping reagent, using 3,3', 4,4' triphen diether tetracarboxylic acid dianhydrides or 2,2', 3,3' triphen diether tetracarboxylic acid dianhydrides are as aromatic dianhydride monomer, 1,3 bis- (4 amino-benzene oxygen) benzene are blended with common aromatic diamine is used as aromatic diamine monomer, and phthalic anhydride is as end-capping reagent.The copolyimide resin has higher glass transition temperature, good thermal stability, low melt viscosity, excellent melt repeats crystallizing power and easy melt processable, melting range is 300~380 DEG C, which has extensive use in terms of preparing the materials such as composite matrix resin, high temperature adhesive, powdery paints, high performance thin film, 3D printing polymer powder.

Description

A kind of crystalline thermoplastic copolyimide resin and application
Technical field
The present invention relates to polyimide resins, and in particular to a kind of crystalline thermoplastic copolyimide resin and answers With.
Background technology
Polyimide resin is one of highest high molecular material of temperature classification in industrial practical application at present, due to it With comprehensive performances such as high thermal stability, solvent resistance, high mechanical properties, excellent insulating properties, radioresistances, widely answer Used in the fields such as aerospace, mechanical chemical industry, electric.Strand and intermolecular extremely strong phase of the polyimides due to rigidity Interreaction force, it is difficult dissolving and melting to lead to it, thus most polyimide resins can only use solution molding and hot pressing Method is processed, and the usually used extrusion of engineering plastics, injection molding (hereinafter referred to as melt-processed) can not be used.Melt-processed has Have the advantages that complicated shape product can one-pass molding, short molding cycle, the few and cost-effective reduction of product defects, it is raw in high-volume There is significant advantage in production.Therefore, exploitation has good melt processable, extrusion can be used, injection moulding method is added The molding polyimides of work is of great significance.
In addition, most of polyimide resin is non-crystalline at present, temperature in use is limited to its glass transition Temperature.When temperature is higher than its glass transition temperature, mechanical strength can substantially reduce, and cannot be satisfied requirement.And have There is crystalline polyimides that can keep higher mechanical strength more than glass transition temperature, it is heat-resisting to further increase its Property, solvent resistance and high-temperature mechanical property, foreground is had more in high-temperature applications.
Currently, the polyimide resin for having both crystallinity and melt processable is considerably less, it is main to be primarily due to the prior art It has the following disadvantages：(1) the strand rigid structure of polyimides and intermolecular strong interaction cause its fusing point and melt viscous Du Taigao, processing temperature is often beyond 400 DEG C, processing difficulties.(2) most that there is crystalline polyimides to be tied after melting Brilliant Disability substantially reduces, and product can not show high temperature tolerance energy.(3) even if a small number of polyimides still table after melting Reveal crystallizing power, but its crystalline rate is very slow, product, which need to pass through the high-temperature post-treatment of long period, can just show crystallinity.
As Mitsui chemistry develop crystallinity polyimide resin Aurum (US4847349, US4847311, CN98126912), glass transition temperature is 250 DEG C, and fusing point is 388 DEG C, although can be molded and extrusion molding, its High-melting-point causes processing temperature to be more than 400 DEG C.And Aurum crystalline rates are slower, the product generally yielded is amorphous state.To Crystalline state product is obtained, it must be by the high-temperature process of more than 10 220 DEG C of hours or more.The crystallinity of Mitsui's exploitation Polyimide resin Super Aurum (US6458912), can in forming process rapid crystallization, but its fusing point be 395 DEG C, processing temperature reaches 420 DEG C.
Consider from the practical heat decomposition temperature of the ability to bear and polymer of process equipment, is capable of the crystallization of practical melt processing Property polyimides, fusing point are preferably lower than 385 DEG C.
In order to reduce the fusing point of crystallinity polyimides, it can usually take and introduce flexible chain structure in molecular backbone, The methods of long-chained monomer containing ether ketone structure or fatty chain monomer, but while reduction fusing point, flexible structure also leads to glass Change transition temperature significantly to decline, affects the hot property of material.In order to while reducing fusing point, keep higher vitrifying Transition temperature, patent US4820791, US5145937 and document (Journal of Polymer Science:Part A: Polymer Chemistry, 1989,27,1161-1174) report the crystallinity polyamides with long-chain diamines containing ether ketone structure Imines, fusing point are 350 DEG C, 222 DEG C of glass transition temperature, however its crystalline rate after melting is very slow, need to pass through high temperature Post-processing can just show crystallinity, and the melt viscosity at 395 DEG C is more than 10000Pas, and the alkyldiamine synthesis used Route is complicated, and cost is higher.Document (Journal of Applied Polymer Science, 2002,83,2873-2882) It is 320 DEG C to have synthesized fusing point by using the double phthalic anhydrides of 4,4'- isophthalic dioxy, and glass transition temperature is 204 DEG C Full fragrance crystallinity polyimides.However the polymer melt crystallizing power is poor, needs that low molecule nucleating agent is added or carbon is received Rice filler as nucleating agent in the case of can just show repeated crystallinity, can not be used directly as crystalline resin.Meanwhile It is to obtain compared with low melting point, the crystallinity polyimides of higher glass transition temperature in above-mentioned document, it has to use versatility It is low, be difficult to the monomer synthesized, particularity is high, cause cost of material higher, difficult to realize mass produce simultaneously is formed with market The product of competitiveness.
In conclusion there is glass transition temperature to be more than 190 DEG C in the prior art, less than 385 DEG C full fragrance knots of fusing point The crystallinity polyimides of structure mostly has that melt crystallization ability is poor, the high disadvantage of melt viscosity.
Invention content
The present invention provides a kind of crystalline thermoplastic copolyimide resin, the heat decomposition temperature of the resin is more than 500 DEG C, glass transition temperature is more than 190 DEG C, and fusing point has melt and repeat crystallizing power between 300~380 DEG C, The feature of low melt viscosity melt-processable.
Technical solution is as follows used by the present invention realizes above-mentioned technical purpose：
A kind of crystalline thermoplastic copolyimide resin, by aromatic dianhydride monomer, aromatic diamine monomer, sealing end Agent reaction is made, and general formula is as follows：
Wherein, Ar' is aromatic diamine monomer residue, and x is positive integer, and 10≤x≤180.
The theoretical number-average molecular weight of the crystalline thermoplastic copolyimide resin is between 104~105Between g/mol, Logarithmic viscosity number ranging from 0.2~5.0dL/g.
The glass transition temperature of the crystalline thermoplastic copolyimide resin is more than 190 DEG C, and fusing point is between 300 Between~380 DEG C, 5% thermal weight loss temperature is higher than 500 DEG C in air atmosphere.
The minimum melt complex viscosity of the crystalline thermoplastic copolyimide resin is less than 1500Pas.
The crystalline thermoplastic copolyimide resin has excellent melt crystallization ability, repeatedly through four times or more It still can rapid crystallization after melting, cooling.
The aromatic dianhydride monomer is 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides or knot shown in structural formula (A-1) 2,2' shown in structure formula (A-2), 3,3'- triphen diether tetracarboxylic acid dianhydride.
Bis- (4- amino-benzene oxygens) benzene of aromatic diamine monomer 1,3- shown in structural formula (B-1) and following diamines One or more of be blended composition：Bis- (4- amino-benzene oxygens) benzene of 1,4- shown in structural formula (B-2), structural formula (B-3) institute 4 shown in 4,4'- diaminodiphenyl ethers, structural formula (B-5) shown in the 3,4'- diaminodiphenyl ethers that show, structural formula (B-4), 4,4'- benzidines shown in p-phenylenediamine, structural formula (B-7) shown in 4'- diaminodiphenyl sulfides, structural formula (B-6), knot (4- amino-benzene oxygens) biphenyl 4,4 '-two shown in structure formula (B-8), (the 3- aminobenzene oxygen of 4,4'- bis- shown in structural formula (B-9) Base) biphenyl, shown in bis- [4- (4- amino-benzene oxygens) phenyl] propane of 2,2-, structural formula (B-11) shown in structural formula (B-10) Bis- [the 4- of 1,3- shown in bis- [4- (4- amino-benzene oxygens) the phenyl] -1,1,1,3,3,3- hexafluoropropane of 2,2-, structural formula (B-12) (4- amino-benzene oxygens) benzoyl] 1,4- bis- [4- (4- amino-benzene oxygens) benzoyls] shown in benzene and structural formula (B-13) Benzene.Bis- (4- amino-benzene oxygens) benzene of 1,3- molar ratio shared in the mixture of the aromatic diamine monomer is 1~ 99%.
The end-capping reagent is phthalic anhydride.
From the angle of Molecular Design, the polyimides crystallization for selecting the dianhydride of ether-containing key or ketonic bond monomer to prepare Property is preferable.Preferably, three phenyl ring dianhydride monomer triphen diether tetracid dianhydrides of the selection with ether-containing key, with same ether-containing key Three phenyl ring diamine monomers 1, bis- (4- amino-benzene oxygens) benzene of 3-, due to the molecular structure symmetry of dianhydride monomer and diamine monomer It is good, make polymer that there is excellent crystallinity；Simultaneously because dianhydride monomer and diamine monomer all contain ehter bond flexible, the two group Conjunction is conducive to carry Polymer chain flexibility, to reduce fusing point and melt viscosity, improves melt processable, and more flexible Molecular chain structure is conducive to polymer molecular chain regular arrangement in melt cooling process, to improve melt crystallization.
In addition, relatively stiff diamine monomer (bis- (4- amino-benzene oxygens) benzene of such as Isosorbide-5-Nitrae -) copolymerization is added, molecule can be improved Amylose regularity is more advantageous to crystallization, by control additional proportion to melting point polymer in a wider scope (300~380 DEG C) Regulated and controled, meets different requirements.The molar ratio for being copolymerized aromatic amine monomers has optimal effectiveness in a certain range, Due to the synergistic effect of diamine monomer selection and copolymerization ratios, makes polymer while there is rapid melt crystallizing power and low melt Viscosity is easy to melt-processed.
Preferably, the aromatic diamine monomer is bis- (4- amino-benzene oxygens) benzene of 1,3- and bis- (the 4- aminobenzenes of Isosorbide-5-Nitrae- Oxygroup) benzene mixture, and the aromatic dianhydride monomer be 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides.It is further excellent It selects, in the aromatic diamine monomer, mole of 1,3- bis- (4- amino-benzene oxygens) benzene and bis- (4- amino-benzene oxygens) benzene of Isosorbide-5-Nitrae- Than between 5/95~40/60.
Preferably, the aromatic diamine monomer is bis- (4- amino-benzene oxygens) benzene and 4 of 1,3-, 4'- benzidines Mixture, and the aromatic dianhydride monomer is 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides.Further preferably, the fragrance In race's diamine monomer, 1,3- bis- (4- amino-benzene oxygens) benzene and 4, the molar ratios of 4'- benzidines between 60/40~95/5 it Between.
Preferably, the aromatic diamine monomer is bis- (4- amino-benzene oxygens) benzene and 3 of 1,3-, 4'- diamino hexichol The mixture of ether, and the aromatic dianhydride monomer is 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides.Further preferably, described In aromatic diamine monomer, 1,3- bis- (4- amino-benzene oxygens) benzene and 3, the molar ratios of 4'- diaminodiphenyl ethers between 60/40~ Between 95/5.
Preferably, the aromatic diamine monomer is bis- (4- amino-benzene oxygens) benzene and 4 of 1,3-, 4'- diamino hexichol The mixture of ether, and the aromatic dianhydride monomer is 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides.Further preferably, described In aromatic diamine monomer, 1,3- bis- (4- amino-benzene oxygens) benzene and 4, the molar ratios of 4'- diaminodiphenyl ethers between 60/40~ Between 95/5.
Preferably, the aromatic diamine monomer is bis- (4- amino-benzene oxygens) benzene and 4 of 1,3-, (the 4- aminobenzenes of 4'- bis- Oxygroup) two kinds of diamines of biphenyl mixture, and the aromatic dianhydride monomer is preferably 3,3', 4,4'- triphen diether tetracarboxylic acids Dianhydride.Further preferably, in the aromatic diamine monomer, 1,3- bis- (4- amino-benzene oxygens) benzene and 4, (the 4- aminobenzenes of 4'- bis- Oxygroup) biphenyl molar ratio between 60/40~95/5.
Preferably, the aromatic diamine monomer is the mixing of 1,3- bis- (4- amino-benzene oxygens) benzene and p-phenylenediamine Object, and the aromatic dianhydride monomer is preferably 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides.Further preferably, the fragrance In race's diamine monomer, the molar ratio of 1,3- bis- (4- amino-benzene oxygens) benzene and p-phenylenediamine is between 60/40~95/5.
Preferably, the aromatic diamine monomer is bis- (4- amino-benzene oxygens) benzene of 1,3- and bis- (the 4- aminobenzenes of Isosorbide-5-Nitrae- Oxygroup) benzene mixture, and the aromatic dianhydride monomer be 2,2', 3,3'- triphen diether tetracarboxylic acid dianhydrides.It is further excellent It selects, in the aromatic diamine monomer, mole of 1,3- bis- (4- amino-benzene oxygens) benzene and bis- (4- amino-benzene oxygens) benzene of Isosorbide-5-Nitrae- Than between 5/95~40/60.
Preferably, the aromatic diamine monomer is bis- (4- amino-benzene oxygens) benzene and 3 of 1,3-, 4'- diamino hexichol The mixture of ether, and the aromatic dianhydride monomer is preferably 2,2', 3,3'- triphen diether tetracarboxylic acid dianhydrides.Further preferably, In the aromatic diamine monomer, 1,3- bis- (4- amino-benzene oxygens) benzene and 3, the molar ratio of 4'- diaminodiphenyl ethers is between 5/ Between 95~40/60.
Preferably, the aromatic diamine monomer is bis- (4- amino-benzene oxygens) benzene and 4 of 1,3-, 4'- diamino hexichol The mixture of ether, and the aromatic dianhydride monomer is preferably 2,2', 3,3'- triphen diether tetracarboxylic acid dianhydrides.Further preferably, In the aromatic diamine monomer, 1,3- bis- (4- amino-benzene oxygens) benzene and 4, the molar ratio of 4'- diaminodiphenyl ethers is between 5/ Between 95~40/60.
Preferably, the aromatic diamine monomer is bis- (4- amino-benzene oxygens) benzene and 4 of 1,3-, (the 4- aminobenzenes of 4'- bis- Oxygroup) two kinds of diamines of biphenyl mixture, and the aromatic dianhydride monomer is preferably 2,2', 3,3'- triphen diether tetracarboxylic acids Dianhydride.Further preferably, in the aromatic diamine monomer, 1,3- bis- (4- amino-benzene oxygens) benzene and 4, (the 4- aminobenzenes of 4'- bis- Oxygroup) biphenyl molar ratio between 60/40~95/5.
Preferably, the aromatic diamine monomer is the mixing of 1,3- bis- (4- amino-benzene oxygens) benzene and p-phenylenediamine Object, and the aromatic dianhydride monomer is preferably 2,2', 3,3'- triphen diether tetracarboxylic acid dianhydrides.Further preferably, the fragrance In race's diamine monomer, the molar ratio of 1,3- bis- (4- amino-benzene oxygens) benzene and p-phenylenediamine is between 60/40~95/5.
Crystalline thermoplastic copolyimide resin provided by the invention is by aromatic dianhydride monomer, aromatic diamine list Body, blocking agent reaction are made, using 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides or 2,2', 3,3'- triphen diether tetracarboxylic acids For dianhydride as aromatic dianhydride monomer, 1,3- bis- (4- amino-benzene oxygens) benzene are blended with common aromatic diamine is used as aromatic series two Amine monomers, phthalic anhydride is as end-capping reagent.The theoretical value of obtained crystalline thermoplastic copolyimide resin is equal Molecular weight is between 104~105Between g/mol, logarithmic viscosity number ranging from 0.2~5.0dL/g, glass transition temperature is more than 190 DEG C, for fusing point between 300~380 DEG C, heat decomposition temperature is higher than 500 DEG C, while having excellent melt crystallization, has There is the easy melt processability of low melt viscosity, conventional extrusion, injection molding processing can be used.
The present invention also provides a kind of applications of crystalline thermoplastic copolyimide resin, which can be extensive It is used for high heat-resistant engineering plastic, composite matrix resin, high temperature adhesive, powdery paints, high performance thin film, 3D printing poly- Close object powder or increasing material manufacturing resin etc..
Compared with prior art, the invention has the advantages that：
(1) by Molecular Design, triphen diether tetracarboxylic acid dianhydride monomer is introduced, so as to control crystallinity polyamides Imines fusing point keeps higher glass transition temperature (being more than 190 DEG C) and heat at suitable range (300~380 DEG C) Decomposition temperature (is more than 500 DEG C), compared to other crystallinity polyimides reported at present, significantly reduces processing temperature and melt Viscosity, it is easier to melt-processed.
(2) polyimides prepared has crystalline rate quickly, can crystallize in cooling procedure, be conducive to product and exist It is crystallized in a mold in the process such as injection molding and extrusion, product need not use the high-temperature post-treatment of long period can be only achieved Higher crystallinity significantly improves production efficiency.
(3) polyimides prepared has good fluidity of molten, is less than in the above melt complex viscosity of fusing point 1500Pas can meet the injection molding requirement of melt, be more suitable for industrial mass production.
Description of the drawings：
Fig. 1 is the XRD curve graphs of polyimide resin prepared by embodiment 1；
Fig. 2 is the DSC curve figure of polyimide resin prepared by embodiment 1；
Fig. 3 be polyimide resin prepared by embodiment 1 more times of DSC meltings after heating curve figure again；
Fig. 4 be embodiment 1 prepare polyimide resin air in TGA curve graphs；
Fig. 5 is the melt viscosity and temperature relation rheological curve figure of polyimide resin prepared by embodiment 1.
Specific implementation mode：
Below in conjunction with attached drawing, present invention is further described in detail with embodiment.
Embodiment 1
To equipped with blender, 11.6930g (40.0mmol) is added in the three-necked flask of reflux condensing tube and nitrogen gas-guide tube 1,3- bis- (4- amino-benzene oxygens) benzene (referred to as TPER), bis- (4- amino-benzene oxygens) benzene of 46.7730g (160.0mmol) Isosorbide-5-Nitrae- (referred to as TPEQ), 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides of 77.2440g (192.0mmol) (referred to as HQDPA), 2.3700g (16.0mmol) phthalic anhydride (referred to as PA), 526g metacresols, 30 drop isoquinolin, in a nitrogen atmosphere instead It answers, stirs evenly, be warming up to 200 DEG C of 8 hours of reaction, be cooled to room temperature, ethyl alcohol is added as precipitating reagent, polymer is with powder Shape is precipitated, and is cleaned using a large amount of second alcohol and waters, and then 150 DEG C of dryings 10 hours in vacuum drying oven, obtain polyimides Resin PI-1.
The logarithmic viscosity number of PI-1 is measured using Ubbelohde viscometer in the m-cresol solution of 30 DEG C of a concentration of 0.5g/dL For 0.59dL/g.
The X-ray powder diffraction figure of polymer is as shown in Figure 1, with crystalline polymer sharp characteristic diffraction peak (tool There is high-crystallinity).
Polymer is increased to 30 DEG C of constant temperature of fusing point or more by the PI-1 measured with DSC with 10 DEG C/min heating rates 3min is rapidly decreased to 25 DEG C with -200 DEG C/min rate of temperature fall, then is increased to 420 DEG C with 10 DEG C/min heating rates, DSC curve Figure is as shown in Figure 2, the results showed that dual melting peak T is observed in first time heating curvemFor 344 DEG C and 372 DEG C, nothing is clearly seen Measure TgAnd Tc(there is high degree of crystallinity).T is observed in heating up at secondgIt is 208 DEG C, TmFor 343 DEG C and 369 DEG C, have Melt crystallization ability and faster crystalline rate.PI-1 is melted repeatedly, cool down and heat up again (temperature program be set as from 25 DEG C with 10 DEG C/min heating rates are warming up to 400 DEG C, then are rapidly decreased to 25 DEG C with -200 DEG C/min rate of temperature fall, then with 10 DEG C/min liters Warm rate is increased to 400 DEG C, is repeated 5 times), its DSC curve is measured continuous 5 times, as shown in figure 3, remaining to protect by repeatedly melting Rapid crystallization ability is held, melt repeated crystallinity is excellent.TGA curves in its air are measured as shown in figure 4,5% thermal weight loss temperature It is 524 DEG C.
Its melt complex viscosity is measured with temperature curve as shown in figure 5, measuring its most eutectic using rotational rheometer Body complex viscosity is 1420Pas (at 370 DEG C).
Embodiment 2
To equipped with blender, 2.3386g (8.0mmol) is added in the three-necked flask of reflux condensing tube and nitrogen gas-guide tube First between TPER, 3.5080g (12.0mmol) TPEQ, 7.7244g (19.2mmol) HQDPA, 0.2370g (1.6mmol) PA, 53g Phenol, 5 drop isoquinolin, reacts, stirs evenly in a nitrogen atmosphere, is warming up to 200 DEG C of 8 hours of reaction, is cooled to room temperature, is added Ethyl alcohol is cleaned, then in vacuum drying oven as precipitating reagent, polymer with powdered precipitation using a large amount of second alcohol and waters 150 DEG C of dryings 10 hours, obtain polyimide resin PI-2.
As a result the polyimides PI-2 measured with DSC observes dual melting peak T in first time heating curvemFor 340 DEG C and 368 DEG C, nothing clearly observes TgAnd Tc(there is high degree of crystallinity).T is observed in heating up at secondgIt is 205 DEG C, TmFor 340 DEG C and 368 DEG C.It is 517 DEG C to measure 5% heat decomposition temperature in its air, logarithmic viscosity number 0.58dL/g.It utilizes It is 1240Pas that rotational rheometer, which measures its minimum melt complex viscosity, (at 371 DEG C).
Embodiment 3
To equipped with blender, 3.5080g (12.0mmol) is added in the three-necked flask of reflux condensing tube and nitrogen gas-guide tube First between TPER, 2.3386g (8.0mmol) TPEQ, 7.7244g (19.2mmol) HQDPA, 0.2370g (1.6mmol) PA, 53g Phenol, 5 drop isoquinolin, reacts, stirs evenly in a nitrogen atmosphere, is warming up to 200 DEG C of 8 hours of reaction, is cooled to room temperature, is added Ethyl alcohol is cleaned, then in vacuum drying oven as precipitating reagent, polymer with powdered precipitation using a large amount of second alcohol and waters 150 DEG C of dryings 10 hours, obtain polyimide resin PI-3.
The polyimides PI-3 measured with DSC, as a result dual melting peak T in first time heating curvemFor 338 DEG C and 364 DEG C, nothing clearly observes TgAnd Tc(there is high degree of crystallinity).T is observed in heating up at secondgIt is 201 DEG C, TmIt is 339 DEG C and 362 DEG C.It is 520 DEG C to measure 5% heat decomposition temperature in its air, logarithmic viscosity number 0.56dL/g.Utilize rotating flow Become instrument and measure its minimum melt complex viscosity as 403Pas (at 365 DEG C).
Embodiment 4
To equipped with blender, 4.67730g (16.0mmol) is added in the three-necked flask of reflux condensing tube and nitrogen gas-guide tube First between TPER, 1.1693g (4.0mmol) TPEQ, 7.72440g (19.2mmol) HQDPA, 0.2370g (1.6mmol) PA, 53g Phenol, 5 drop isoquinolin, reacts, stirs evenly in a nitrogen atmosphere, is warming up to 200 DEG C of 8 hours of reaction, is cooled to room temperature, is added Ethyl alcohol is cleaned, then in vacuum drying oven as precipitating reagent, polymer with powdered precipitation using a large amount of second alcohol and waters 150 DEG C of dryings 10 hours, obtain polyimide resin PI-4.
The polyimides PI-4 measured with DSC, as a result observes fusing point T in first time heating curvemFor 332 DEG C and 355 DEG C, nothing clearly observes TgAnd Tc(there is high degree of crystallinity).T is observed in heating up at secondgIt is 194 DEG C, TmIt is 332 DEG C and 355 DEG C.It is 544 DEG C to measure 5% heat decomposition temperature in its air, logarithmic viscosity number 0.51dL/g.Utilize rotating flow Become instrument and measure its minimum melt complex viscosity as 300Pas (at 357 DEG C).
Embodiment 5
To equipped with blender, 4.3850g (15.0mmol) is added in the three-necked flask of reflux condensing tube and nitrogen gas-guide tube TPER, 1.0012g (5.0mmol) 4,4'- diaminodiphenyl ethers (referred to as 4,4'-ODA), 7.8048g (19.4mmol) HQDPA, 0.1777g (1.2mmol) PA, 53g metacresol, 5 drop isoquinolin, reacts, stirs evenly, be warming up in a nitrogen atmosphere It 200 DEG C of 8 hours of reaction, is cooled to room temperature, ethyl alcohol is added as precipitating reagent, polymer utilizes a large amount of second with powdered precipitation Alcohol and water is cleaned, and then 150 DEG C of dryings 10 hours in vacuum drying oven, obtain polyimide resin PI-5.
The polyimides PI-5 measured with DSC, as a result only observes fusing point T in first time heating curvemIt is 315 DEG C, nothing clearly observes TgAnd Tc(there is high degree of crystallinity).T is observed in heating up at secondgIt is 199 DEG C, TmIt is 318 DEG C. It is 526 DEG C to measure 5% heat decomposition temperature in its air, logarithmic viscosity number 0.54dL/g.It is measured using rotational rheometer Minimum melt complex viscosity is 426Pas (at 346 DEG C).
Embodiment 6
To equipped with blender, 4.9696g (17.0mmol) is added in the three-necked flask of reflux condensing tube and nitrogen gas-guide tube TPER, 0.5527g (3.0mmol) 4,4'- benzidines (referred to as BZD), 7.8048g (19.4mmol) HQDPA, 0.1777g (1.2mmol) PA, 53g metacresols, 5 drop isoquinolin, react, stir evenly in a nitrogen atmosphere, are warming up to 200 DEG C and react 8 Hour, it is cooled to room temperature, ethyl alcohol is added as precipitating reagent, polymer is carried out clear with powdered precipitation using a large amount of second alcohol and waters It washes, then 150 DEG C of dryings 10 hours in vacuum drying oven, obtain polyimide resin PI-6.
The polyimides PI-6 measured with DSC, as a result only observes fusing point T in first time heating curvemIt is 339 DEG C, nothing clearly observes TgAnd Tc(there is high degree of crystallinity).T is observed in heating up at secondgIt is 196 DEG C, TmIt is 340 DEG C. It is 542 DEG C to measure 5% heat decomposition temperature in its air, logarithmic viscosity number 0.57dL/g.It is measured using rotational rheometer Minimum melt complex viscosity is 1080Pas (at 374 DEG C).
Embodiment 7
To equipped with blender, 2.9233g (10.0mmol) is added in the three-necked flask of reflux condensing tube and nitrogen gas-guide tube TPER, 2.0024g (10.0mmol) 3,4'- diaminodiphenyl ethers (referred to as 3,4'-ODA), 7.8048g (19.4mmol) HQDPA, 0.1777g (1.2mmol) PA, 53g metacresol, 5 drop isoquinolin, reacts, stirs evenly, be warming up in a nitrogen atmosphere It 200 DEG C of 8 hours of reaction, is cooled to room temperature, ethyl alcohol is added as precipitating reagent, polymer utilizes a large amount of second with powdered precipitation Alcohol and water is cleaned, and then 150 DEG C of dryings 10 hours in vacuum drying oven, obtain polyimide resin PI-7.
The polyimides PI-7 measured with DSC, as a result only observes fusing point T in first time heating curvemIt is 305 DEG C, nothing clearly observes TgAnd Tc(there is high degree of crystallinity).T is observed in heating up at secondgIt is 205 DEG C, TmIt is 303 DEG C. It is 519 DEG C to measure 5% heat decomposition temperature in its air, logarithmic viscosity number 0.54dL/g.It is measured using rotational rheometer Minimum melt complex viscosity is 324Pas (at 331 DEG C).
Embodiment 8
To equipped with blender, 2.9233g (10.0mmol) is added in the three-necked flask of reflux condensing tube and nitrogen gas-guide tube TPER, 3.6844g (10.0mmol) 4,4 '-two (4- amino-benzene oxygens) biphenyl (referred to as BAPB), 7.8048g (19.4mmol) 2,2', 3,3'- triphen diether tetracarboxylic acid dianhydrides (referred to as 3,3'-HQDPA), 0.1777g (1.2mmol) PA, 53g metacresol, 5 Isoquinolin is dripped, reacts, stirs evenly in a nitrogen atmosphere, 200 DEG C of 8 hours of reaction is warming up to, is cooled to room temperature, ethyl alcohol is added As precipitating reagent, polymer is cleaned with powdered precipitation using a large amount of second alcohol and waters, then 150 DEG C in vacuum drying oven It is 10 hours dry, obtain polyimide resin PI-8.
The polyimides PI-8 measured with DSC, as a result only observes fusing point T in first time heating curvemIt is 345 DEG C, nothing clearly observes TgAnd Tc(there is high degree of crystallinity).T is observed in heating up at secondgIt is 215 DEG C, TmIt is 343 DEG C. It is 525 DEG C to measure 5% heat decomposition temperature in its air, logarithmic viscosity number 0.74dL/g.It is measured using rotational rheometer Minimum melt complex viscosity is 864Pas (at 380 DEG C).
Embodiment 9
To equipped with blender, 2.9233g (10.0mmol) is added in the three-necked flask of reflux condensing tube and nitrogen gas-guide tube TPER, 5.0055g (10.0mmol) 1,3- bis- [4- (4- amino-benzene oxygens) benzoyls] (referred to as BABB), 7.8048g (19.4mmol) 3,3'-HQDPA, 0.1777g (1.2mmol) PA, 53g metacresol, 5 drop isoquinolin, reacts in a nitrogen atmosphere, It stirs evenly, is warming up to 200 DEG C of 8 hours of reaction, is cooled to room temperature, ethyl alcohol is added as precipitating reagent, polymer is with powdered It is precipitated, is cleaned using a large amount of second alcohol and waters, then 150 DEG C of dryings 10 hours in vacuum drying oven, obtain polyimides tree Fat PI-9.
The polyimides PI-9 measured with DSC, as a result only observes fusing point T in first time heating curvemIt is 338 DEG C, nothing clearly observes TgAnd Tc(there is high degree of crystallinity).T is observed in heating up at secondgIt is 206 DEG C, TmIt is 336 DEG C. It is 531 DEG C to measure 5% heat decomposition temperature in its air, logarithmic viscosity number 0.84dL/g.It is measured using rotational rheometer Minimum melt complex viscosity is 769Pas (at 376 DEG C).
Embodiment 10
To equipped with blender, 2.9233g (10.0mmol) is added in the three-necked flask of reflux condensing tube and nitrogen gas-guide tube TPER, 2.0024g (10.0mmol) 4,4'- diaminodiphenyl sulfides (referred to as SDA), 7.8048g (19.4mmol) 3,3'- HQDPA, 0.1777g (1.2mmol) PA, 53g metacresol, 5 drop isoquinolin, reacts, stirs evenly, be warming up in a nitrogen atmosphere It 200 DEG C of 8 hours of reaction, is cooled to room temperature, ethyl alcohol is added as precipitating reagent, polymer utilizes a large amount of second with powdered precipitation Alcohol and water is cleaned, and then 150 DEG C of dryings 10 hours in vacuum drying oven, obtain polyimide resin PI-10.
The polyimides PI-10 measured with DSC, as a result only observes fusing point T in first time heating curvemIt is 342 DEG C, nothing clearly observes TgAnd Tc(there is high degree of crystallinity).T is observed in heating up at secondgIt is 206 DEG C, TmIt is 340 DEG C. It is 522 DEG C to measure 5% heat decomposition temperature in its air, logarithmic viscosity number 0.97dL/g.It is measured using rotational rheometer Minimum melt complex viscosity is 1158Pas (at 386 DEG C).
The performance parameter of feed intake parameter and the polyimide resin being prepared of various embodiments of the present invention is as shown in table 1.
Table 1
1 (Continued) of table
As shown above, the ratio that rigid diamine monomer 2 is added is higher, and fusing point improves, and melt viscosity increases.Pass through control The rigid diamines ratio of system can obtain the suitable crystalline thermoplastic copolyimide of fusing point in OK range.

Claims (8)

1. a kind of crystalline thermoplastic copolyimide resin, which is characterized in that by aromatic dianhydride monomer, aromatic diamine Monomer, blocking agent reaction are made, and general formula is as follows：
Wherein, Ar' is aromatic diamine monomer residue, and x is positive integer, and 10≤x≤180；
The aromatic dianhydride monomer is 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides or 2,2', 3,3'- triphen diether tetramethyl Acid dianhydride；The aromatic diamine monomer is blended by one or more of bis- (4- amino-benzene oxygens) benzene of 1,3- and following diamines Composition：Bis- (4- amino-benzene oxygens) benzene of 1,4-, 3,4'- diaminodiphenyl ethers, 4,4'- benzidines, (the 4- aminobenzenes of 4,4'- bis- Oxygroup) biphenyl, 4,4'- bis- (3- amino-benzene oxygens) biphenyl, bis- [4- (4- amino-benzene oxygens) benzoyl] benzene of 1,3- and 1,4- Bis- [4- (4- amino-benzene oxygens) benzoyl] benzene；Bis- (4- amino-benzene oxygens) benzene of 1,3- are in the aromatic diamine monomer Mixture in shared molar ratio be 1~99%；The end-capping reagent is phthalic anhydride；
The crystalline thermoplastic copolyimide resin still can rapid crystallization after four times or more repeatedly melting, cooling.
2. crystalline thermoplastic copolyimide resin according to claim 1, which is characterized in that the crystallinity heat The theoretical number-average molecular weight of plasticity copolyimide resin is between 104~105Between g/mol, logarithmic viscosity number is ranging from 0.2~5.0dL/g.
3. crystalline thermoplastic copolyimide resin according to claim 1, which is characterized in that the crystallinity heat The glass transition temperature of plasticity copolyimide resin is more than 190 DEG C, and fusing point is between 300~380 DEG C, air atmosphere In 5% thermal weight loss temperature be higher than 500 DEG C.
4. crystalline thermoplastic copolyimide resin according to claim 1, which is characterized in that the crystallinity heat The minimum melt complex viscosity of plasticity copolyimide resin is less than 1500Pas.
5. crystalline thermoplastic copolyimide resin according to claim 1, which is characterized in that the aromatic series two Amine monomers are the mixture of bis- (4- amino-benzene oxygens) benzene of 1,3- and bis- (4- amino-benzene oxygens) benzene of Isosorbide-5-Nitrae-, and the aromatic series two Anhydride monomer is 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides.
6. crystalline thermoplastic copolyimide resin according to claim 1, which is characterized in that the aromatic series two Amine monomers are bis- (4- amino-benzene oxygens) benzene and 4 of 1,3-, the mixture of 4'- benzidines, and the aromatic dianhydride monomer is 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydride.
7. crystalline thermoplastic copolyimide resin according to claim 1, which is characterized in that the aromatic series two Amine monomers are bis- (4- amino-benzene oxygens) benzene and 3 of 1,3-, the mixture of 4'- diaminodiphenyl ethers, and the aromatic dianhydride list Body is 3,3', 4,4'- triphen diether tetracarboxylic acid dianhydrides.
8. a kind of application of crystalline thermoplastic copolyimide resin described in claim 1, which is characterized in that the knot Crystalline substance thermoplastic co-polymer polyimide resin can be used for high heat-resistant engineering plastic, composite matrix resin, high temperature adhesive, powder Last coating, high performance thin film, 3D printing polymer powder or increasing material manufacturing resin.
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