CN106279687A - A kind of crystalline thermoplastic copolyimide resin and application - Google Patents
A kind of crystalline thermoplastic copolyimide resin and application Download PDFInfo
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- CN106279687A CN106279687A CN201610656891.5A CN201610656891A CN106279687A CN 106279687 A CN106279687 A CN 106279687A CN 201610656891 A CN201610656891 A CN 201610656891A CN 106279687 A CN106279687 A CN 106279687A
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- 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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Abstract
The invention discloses a kind of crystalline thermoplastic copolyimide resin, prepared by polycondensation reaction by aromatic dianhydride monomer, aromatic diamine monomer, end-capping reagent, use 3,3', 4,4' triphen diether tetracarboxylic acid dianhydride or 2,2', 3,3' triphen diether tetracarboxylic acid dianhydride is as aromatic dianhydride monomer, 1,3 pair of (4 amino-benzene oxygen) benzene is blended as aromatic diamine monomer with conventional aromatic diamine, and phthalic anhydride is as end-capping reagent.This copolyimide resin has higher glass transition temperature, good heat stability, low melt viscosity, excellent melt repeats crystallizing power and easy melt processable, melting range is 300～380 DEG C, and this polymer has in terms of preparing the materials such as composite matrix resin, high temperature adhesive, powdery paints, high performance thin film, 3D printing polymer powder and is widely used.
Description
Technical field
The present invention relates to polyimide resin, be specifically related to a kind of crystalline thermoplastic copolyimide resin and answer
With.
Background technology
Polyimide resin is one of macromolecular material that temperature classification is the highest in the actual application of industry at present, due to it
There is the combination properties such as high thermal stability, solvent resistance, high mechanical properties, excellent insulating properties, radioprotective, the most widely should
It is used in Aero-Space, mechanical chemical industry, the field such as electric.Polyimides is due to the strand of rigidity and intermolecular extremely strong phase
Interreaction force, causes it to be difficult to dissolve and melted, thus most polyimide resin can only use solution molding and hot pressing
Method process, it is impossible to use engineering plastics generally used extrusion, injection mo(u)lding (hereinafter referred to as melt-processed).Melt-processed has
Have complicated shape product can one-shot forming, molding cycle is short, product defects is few and the advantage such as cost-effective reduction, raw in high-volume
Product has significant advantage.Therefore, exploitation has good melt processable, and extrusion, injection moulding method can be used to add
The polyimides of work molding is significant.
Additionally, current most polyimide resin is non-crystalline, use temperature limited in its glass transition
Temperature.When temperature is higher than its glass transition temperature, its mechanical strength can be substantially reduced, it is impossible to meets and uses requirement.And have
There is crystalline polyimides can improve it further heat-resisting at glass transition temperature higher mechanical strength maintained above
Property, solvent resistance and high-temperature mechanical property, in high-temperature applications more prospect.
At present, the polyimide resin having crystallinity and melt processable concurrently is considerably less, is primarily due to prior art main
Have the disadvantage in that strand rigid structure and the intermolecular strong interaction of (1) polyimides cause its fusing point and melt to glue
Du Taigao, processing temperature often beyond 400 DEG C, processing difficulties.(2) majority has crystalline polyimides and ties afterwards through melted
Brilliant Disability or be substantially reduced, product cannot show high-temperature resistant performance.(3) though minority polyimides still table after melted
Revealing crystallizing power, but its crystalline rate is very slow, product just need to can show crystallinity through the high-temperature post-treatment of long period.
As Mitsui chemistry exploitation crystallinity polyimide resin Aurum (US4847349, US4847311,
CN98126912), its glass transition temperature is 250 DEG C, and fusing point is 388 DEG C, although can be molded and extrusion molding, but its
High-melting-point causes the processing temperature will be more than 400 DEG C.And Aurum crystalline rate is relatively slow, the goods generally yielded are amorphous state.To
Obtain crystalline state product, must be through more than 10 hours high-temperature process of more than 220 DEG C.The crystallinity of Mitsui's exploitation
Polyimide resin Super Aurum (US6458912), its can in forming process rapid crystallization, but its fusing point is 395
DEG C, processing temperature reaches 420 DEG C.
Consider from ability to bear and the actual heat decomposition temperature of polymer of process equipment, it is possible to the crystallization of actual melt processing
Property polyimides, its fusing point is preferably lower than 385 DEG C.
In order to reduce the fusing point of crystallinity polyimides, generally can take to introduce flexible chain structure in molecular backbone,
Containing methods such as ether ketone structure long-chained monomer or fatty chain monomers, but while reducing fusing point, flexible structure also causes glass
Change transition temperature significantly to decline, have impact on the hot property of material.In order to, while reducing fusing point, keep higher vitrification
Transition temperature, patent US4820791, US5145937 and document (Journal of Polymer Science:Part A:
Polymer Chemistry, 1989,27,1161-1174) report the crystallinity polyamides that there is long-chain containing ether ketone structure diamidogen
Imines, its fusing point is 350 DEG C, glass transition temperature 222 DEG C, but its crystalline rate after melted is very slow, need to be through high temperature
Post processing just can show crystallinity, and the melt viscosity when 395 DEG C is more than 10000Pa s, and the alkyldiamine synthesis used
Route is complicated, relatively costly.Document (Journal of Applied Polymer Science, 2002,83,2873 2882)
By using 4, it is 320 DEG C that the double phthalic anhydride of 4'-isophthalic dioxy has synthesized fusing point, and glass transition temperature is 204 DEG C
Full fragrance crystallinity polyimides.But this polymer melt crystallizing power is poor, needs to add low molecule nucleator or carbon is received
Rice filler is as just showing repeated crystallinity in the case of nucleator, it is impossible to use directly as crystalline resin.Meanwhile,
For obtaining relatively low melting point in above-mentioned document, the crystallinity polyimides of higher glass transition temperature, it has to use versatility
Low, be difficult to synthesis, monomer that particularity is high, cause cost of material higher, be difficulty with large-scale production and formation has market
The product of competitiveness.
In sum, prior art has glass transition temperature more than 190 DEG C, fusing point fragrance complete less than 385 DEG C knot
It is poor mostly to there is melt crystallization ability in the crystallinity polyimides of structure, the shortcoming that melt viscosity is high.
Summary of the invention
The invention provides a kind of crystalline thermoplastic copolyimide resin, the heat decomposition temperature of this resin is more than
500 DEG C, glass transition temperature is more than 190 DEG C, and fusing point is between 300～380 DEG C, and possesses melt repetition crystallizing power,
The feature of low melt viscosity melt-processable.
It is as follows that the present invention realizes the technical scheme that above-mentioned technical purpose used:
A kind of crystalline thermoplastic copolyimide resin, by aromatic dianhydride monomer, aromatic diamine monomer, end-blocking
Agent reaction prepares, and its formula is as follows:
Wherein, Ar' is aromatic diamine monomer residue, and x is positive integer, and 10≤x≤180.
The theoretical value average molecular weight of described crystalline thermoplastic copolyimide resin is between 104～105Between g/mol,
Logarithmic viscosity number scope is 0.2～5.0dL/g.
The glass transition temperature of described crystalline thermoplastic copolyimide resin is more than 190 DEG C, and fusing point is between 300
～between 380 DEG C, in air atmosphere, 5% thermal weight loss temperature is higher than 500 DEG C.
The minimum melt complex viscosity of described crystalline thermoplastic copolyimide resin is less than 1500Pa s.
Described crystalline thermoplastic copolyimide resin has the melt crystallization ability of excellence, through more than four times repeatedly
Still can rapid crystallization after melted, cooling.
Described aromatic dianhydride monomer is 3,3', the 4,4'-triphen diether tetracarboxylic acid dianhydride shown in structural formula (A-1) or knot
2,2', 3,3'-triphen diether tetracarboxylic acid dianhydride shown in structure formula (A-2).
Described aromatic diamine monomer is by double (4-amino-benzene oxygen) benzene of the 1,3-shown in structural formula (B-1) and following diamidogen
In one or more composition be blended: the 1,4-shown in structural formula (B-2) double (4-amino-benzene oxygen) benzene, structural formula (B-3) institute
Shown in 4,4'-diaminodiphenyl ether shown in the 3,4'-diaminodiphenyl ether that shows, structural formula (B-4), structural formula (B-5) 4,
4,4'-benzidine shown in p-phenylenediamine shown in 4'-diaminodiphenyl sulfide, structural formula (B-6), structural formula (B-7), knot
4,4'-bis-(3-aminobenzene oxygen shown in 4,4 '-two (4-amino-benzene oxygen) biphenyl shown in structure formula (B-8), structural formula (B-9)
Base) biphenyl, shown in 2,2-double [4-(4-amino-benzene oxygen) phenyl] propane, the structural formula (B-11) shown in structural formula (B-10)
Double [the 4-of the double 1,3-shown in [4-(4-amino-benzene oxygen) phenyl]-1,1,1,3,3,3-HFC-236fa, structural formula (B-12) of 2,2-
(4-amino-benzene oxygen) benzoyl] benzene and the 1,4-shown in structural formula (B-13) double [4-(4-amino-benzene oxygen) benzoyl]
Benzene.The mol ratio shared in the mixture of described aromatic diamine monomer of double (4-amino-benzene oxygen) benzene of described 1,3-be 1～
99%.
Described end-capping reagent is phthalic anhydride.
From the angle of Molecular Design, select polyimides crystallization prepared by the dianhydride of ether-containing key or ketonic bond monomer
Property is preferable.As preferably, select the three phenyl ring dianhydride monomer triphen diether tetracarboxylic dianhydrides with ether-containing key, with as ether-containing key
Three phenyl ring diamine monomers 1, double (4-amino-benzene oxygen) benzene of 3-, due to the molecular structure symmetry of dianhydride monomer Yu diamine monomer
Good, make polymer have the crystallinity of excellence；Simultaneously because dianhydride monomer and diamine monomer all contain the ehter bond of flexibility, both groups
Conjunction is conducive to carrying Polymer chain flexibility, thus reduces fusing point and melt viscosity, raising melt processable, and more flexible
Molecular chain structure is conducive to polymer molecular chain regular arrangement in melt cooling process, thus improves melt crystallization.
It addition, add relatively stiff diamine monomer (such as Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene) copolymerization, molecule can be improved
Amylose regularity, be more beneficial for crystallization, by control additional proportion to melting point polymer in wider scope (300～380 DEG C)
Regulate and control, meet different use requirements.The mol ratio of copolymerization aromatic amine monomers has optimal effectiveness within the specific limits,
Owing to diamine monomer selects the cooperative effect with copolymerization ratios, make polymer have rapid melt crystallizing power and low melt simultaneously
Viscosity, it is easy to melt-processed.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene of 3-and Isosorbide-5-Nitrae-bis-(4-aminobenzenes
Epoxide) mixture of benzene, and described aromatic dianhydride monomer is 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydrides.The most excellent
Choosing, in described aromatic diamine monomer, 1,3-double (4-amino-benzene oxygen) benzene and Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene mole
Ratio is between 5/95～40/60.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene and 4 of 3-, 4'-benzidine
Mixture, and described aromatic dianhydride monomer is 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydrides.Further preferably, described fragrance
In race's diamine monomer, 1,3-double (4-amino-benzene oxygen) benzene and 4, the mol ratio of 4'-benzidine between 60/40～95/5 it
Between.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene and 3 of 3-, 4'-diaminourea hexichol
The mixture of ether, and described aromatic dianhydride monomer is 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydrides.Further preferably, described
In aromatic diamine monomer, 1,3-double (4-amino-benzene oxygen) benzene and 3, the mol ratio of 4'-diaminodiphenyl ether between 60/40～
Between 95/5.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene and 4 of 3-, 4'-diaminourea hexichol
The mixture of ether, and described aromatic dianhydride monomer is 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydrides.Further preferably, described
In aromatic diamine monomer, 1,3-double (4-amino-benzene oxygen) benzene and 4, the mol ratio of 4'-diaminodiphenyl ether between 60/40～
Between 95/5.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene and 4 of 3-, 4'-bis-(4-aminobenzene
Epoxide) mixture of two kinds of diamidogen of biphenyl, and described aromatic dianhydride monomer is preferably 3,3', 4,4'-triphen diether tetracarboxylic acids
Dianhydride.Further preferably, in described aromatic diamine monomer, 1,3-double (4-amino-benzene oxygen) benzene and 4,4'-bis-(4-aminobenzene
Epoxide) mol ratio of biphenyl is between 60/40～95/5.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene of 3-and the mixing of p-phenylenediamine
Thing, and described aromatic dianhydride monomer is preferably 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydrides.Further preferably, described fragrance
In race's diamine monomer, the mol ratio of 1,3-double (4-amino-benzene oxygen) benzene and p-phenylenediamine is between 60/40～95/5.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene of 3-and Isosorbide-5-Nitrae-bis-(4-aminobenzenes
Epoxide) mixture of benzene, and described aromatic dianhydride monomer is 2,2', 3,3'-triphen diether tetracarboxylic acid dianhydrides.The most excellent
Choosing, in described aromatic diamine monomer, 1,3-double (4-amino-benzene oxygen) benzene and Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene mole
Ratio is between 5/95～40/60.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene and 3 of 3-, 4'-diaminourea hexichol
The mixture of ether, and described aromatic dianhydride monomer is preferably 2,2', 3,3'-triphen diether tetracarboxylic acid dianhydrides.Further preferably,
In described aromatic diamine monomer, 1,3-double (4-amino-benzene oxygen) benzene and 3, the mol ratio of 4'-diaminodiphenyl ether is between 5/
Between 95～40/60.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene and 4 of 3-, 4'-diaminourea hexichol
The mixture of ether, and described aromatic dianhydride monomer is preferably 2,2', 3,3'-triphen diether tetracarboxylic acid dianhydrides.Further preferably,
In described aromatic diamine monomer, 1,3-double (4-amino-benzene oxygen) benzene and 4, the mol ratio of 4'-diaminodiphenyl ether is between 5/
Between 95～40/60.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene and 4 of 3-, 4'-bis-(4-aminobenzene
Epoxide) mixture of two kinds of diamidogen of biphenyl, and described aromatic dianhydride monomer is preferably 2,2', 3,3'-triphen diether tetracarboxylic acids
Dianhydride.Further preferably, in described aromatic diamine monomer, 1,3-double (4-amino-benzene oxygen) benzene and 4,4'-bis-(4-aminobenzene
Epoxide) mol ratio of biphenyl is between 60/40～95/5.
As preferably, described aromatic diamine monomer is 1, double (4-amino-benzene oxygen) benzene of 3-and the mixing of p-phenylenediamine
Thing, and described aromatic dianhydride monomer is preferably 2,2', 3,3'-triphen diether tetracarboxylic acid dianhydrides.Further preferably, described fragrance
In race's diamine monomer, the mol ratio of 1,3-double (4-amino-benzene oxygen) benzene and p-phenylenediamine is between 60/40～95/5.
The crystalline thermoplastic copolyimide resin that the present invention provides is by aromatic dianhydride monomer, aromatic diamine list
The reaction of body, end-capping reagent prepares, and uses 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydrides or 2,2', 3,3'-triphen diether tetracarboxylic acids
Dianhydride is as aromatic dianhydride monomer, and 1,3-double (4-amino-benzene oxygen) benzene are blended as aromatic series two with conventional aromatic diamine
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 scope is 0.2～5.0dL/g, and glass transition temperature is more than
190 DEG C, fusing point is between 300～380 DEG C, and heat decomposition temperature is higher than 500 DEG C, has the melt crystallization of excellence, tool simultaneously
There is the easy melt processability of low melt viscosity, the extrusion of routine, injection mo(u)lding processing can be used.
Present invention also offers the application of described a kind of crystalline thermoplastic copolyimide resin, this resin can be extensive
Print with poly-for high heat-resistant engineering plastic, composite matrix resin, high temperature adhesive, powdery paints, high performance thin film, 3D
Compound powder or increasing material manufacture resin etc..
Compared with prior art, the method have the advantages that
(1) by Molecular Design, triphen diether tetracarboxylic acid dianhydride monomer is introduced such that it is able to control crystallinity polyamides
Imines fusing point, at suitable scope (300～380 DEG C), keeps higher glass transition temperature (more than 190 DEG C) and heat simultaneously
Decomposition temperature (more than 500 DEG C), compares 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, and beneficially goods exist
Crystallizing in a mold in the courses of processing such as injection and extrusion, goods 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 at fusing point above melt complex viscosity
1500Pa s, can meet the injection molding requirement of melt, be more suitable for industrialized mass.
Accompanying drawing illustrates:
Fig. 1 is the XRD curve chart of the polyimide resin of embodiment 1 preparation；
Fig. 2 is the DSC curve figure of the polyimide resin of embodiment 1 preparation；
Fig. 3 be many times of the DSC of the polyimide resin of embodiment 1 preparation melted after heating curve figure again；
Fig. 4 be embodiment 1 preparation polyimide resin air in TGA curve chart；
Fig. 5 is melt viscosity and the temperature relation rheological curve figure of the polyimide resin of embodiment 1 preparation.
Detailed description of the invention:
The present invention is described in further detail with embodiment below in conjunction with accompanying drawing.
Embodiment 1
To being furnished with agitator, the there-necked flask of reflux condensing tube and nitrogen airway adds 11.6930g (40.0mmol)
1,3-double (4-amino-benzene oxygen) benzene (referred to as TPER), 46.7730g (160.0mmol) Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene
(referred to as TPEQ), 77.2440g (192.0mmol) 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydride (referred to as HQDPA),
2.3700g (16.0mmol) phthalic anhydride (referred to as PA), 526g metacresol, 30 isoquinolin, the most instead
Should, stirring, be warming up to 200 DEG C and react 8 hours, be cooled to room temperature, addition ethanol is as precipitant, and polymer is with powder
Shape separates out, and utilizes a large amount of second alcohol and water to be carried out, and then 150 DEG C dry 10 hours in vacuum drying oven, obtain polyimides
Resin PI-1.
It is the logarithmic viscosity number utilizing Ubbelohde viscometer to record PI-1 in the m-cresol solution of 0.5g/dL 30 DEG C of concentration
For 0.59dL/g.
The X-ray powder diagram of polymer is as it is shown in figure 1, have the sharp-pointed characteristic diffraction peak of crystalline polymer (tool
There is high-crystallinity).
Measure the PI-1 obtained with DSC, polymer is increased to 30 DEG C of constant temperature of more than fusing point with 10 DEG C/min heating rate
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 rate, DSC curve
Figure is as in figure 2 it is shown, result shows to observe dual melting peak T in first time heating curvemIt it is 344 DEG C and 372 DEG C, without clearly seeing
Measure TgAnd Tc(there is high degree of crystallinity).Rise warming middle-JIAO in second time and observe TgIt is 208 DEG C, TmIt is 343 DEG C and 369 DEG C, has
Melt crystallization ability and faster crystalline rate.PI-1 melted, cooling repeatedly is heated up again (heating schedule be set as from 25 DEG C with
10 DEG C/min heating rate is warming up to 400 DEG C, then is rapidly decreased to 25 DEG C with-200 DEG C/min rate of temperature fall, then with 10 DEG C/min liter
Temperature speed is increased to 400 DEG C, is repeated 5 times), measure its DSC curve continuous 5 times, as it is shown on figure 3, protect through repeatedly melted remaining to
Holding rapid crystallization ability, melt repeated crystallinity is excellent.Measure in its air TGA curve as shown in Figure 4,5% thermal weight loss temperature
It it is 524 DEG C.
Rotational rheometer is utilized to measure its melt complex viscosity with temperature curve as it is shown in figure 5, record its eutectic
Body complex viscosity is 1420Pa s (at 370 DEG C).
Embodiment 2
To being furnished with agitator, the there-necked flask of reflux condensing tube and nitrogen airway adds 2.3386g (8.0mmol)
TPER, 3.5080g (12.0mmol) TPEQ, 7.7244g (19.2mmol) HQDPA, 0.2370g (1.6mmol) PA, first between 53g
Phenol, 5 isoquinolin, react in a nitrogen atmosphere, stir, be warming up to 200 DEG C and react 8 hours, be cooled to room temperature, add
Ethanol separates out with powder as precipitant, polymer, utilizes a large amount of second alcohol and water to be carried out, then in vacuum drying oven
150 DEG C are dried 10 hours, obtain polyimide resin PI-2.
Measure the polyimides PI-2 obtained with DSC, result heating curve for the first time observes dual melting peak TmFor
340 DEG C and 368 DEG C, without clearly observing TgAnd Tc(there is high degree of crystallinity).Rise warming middle-JIAO in second time and observe TgIt is 205 DEG C,
TmIt it is 340 DEG C and 368 DEG C.Measuring 5% heat decomposition temperature in its air is 517 DEG C, and logarithmic viscosity number is 0.58dL/g.Utilize
It is 1240Pa s (at 371 DEG C) that rotational rheometer records its minimum melt complex viscosity.
Embodiment 3
To being furnished with agitator, the there-necked flask of reflux condensing tube and nitrogen airway adds 3.5080g (12.0mmol)
TPER, 2.3386g (8.0mmol) TPEQ, 7.7244g (19.2mmol) HQDPA, 0.2370g (1.6mmol) PA, first between 53g
Phenol, 5 isoquinolin, react in a nitrogen atmosphere, stir, be warming up to 200 DEG C and react 8 hours, be cooled to room temperature, add
Ethanol separates out with powder as precipitant, polymer, utilizes a large amount of second alcohol and water to be carried out, then in vacuum drying oven
150 DEG C are dried 10 hours, obtain polyimide resin PI-3.
The polyimides PI-3 obtained is measured, dual melting peak T in result heating curve for the first time with DSCmBe 338 DEG C and
364 DEG C, without clearly observing TgAnd Tc(there is high degree of crystallinity).Rise warming middle-JIAO in second time and observe TgIt is 201 DEG C, TmIt is 339
DEG C and 362 DEG C.Measuring 5% heat decomposition temperature in its air is 520 DEG C, and logarithmic viscosity number is 0.56dL/g.Utilize rotating flow
Become instrument and record its minimum melt complex viscosity into 403Pa s (at 365 DEG C).
Embodiment 4
To being furnished with agitator, the there-necked flask of reflux condensing tube and nitrogen airway adds 4.67730g (16.0mmol)
TPER, 1.1693g (4.0mmol) TPEQ, 7.72440g (19.2mmol) HQDPA, 0.2370g (1.6mmol) PA, first between 53g
Phenol, 5 isoquinolin, react in a nitrogen atmosphere, stir, be warming up to 200 DEG C and react 8 hours, be cooled to room temperature, add
Ethanol separates out with powder as precipitant, polymer, utilizes a large amount of second alcohol and water to be carried out, then in vacuum drying oven
150 DEG C are dried 10 hours, obtain polyimide resin PI-4.
Measure the polyimides PI-4 obtained with DSC, result heating curve for the first time observes fusing point TmBe 332 DEG C and
355 DEG C, without clearly observing TgAnd Tc(there is high degree of crystallinity).Rise warming middle-JIAO in second time and observe TgIt is 194 DEG C, TmIt is 332
DEG C and 355 DEG C.Measuring 5% heat decomposition temperature in its air is 544 DEG C, and logarithmic viscosity number is 0.51dL/g.Utilize rotating flow
Become instrument and record its minimum melt complex viscosity into 300Pa s (at 357 DEG C).
Embodiment 5
To being furnished with agitator, the there-necked flask of reflux condensing tube and nitrogen airway adds 4.3850g (15.0mmol)
TPER, 1.0012g (5.0mmol) 4,4'-diaminodiphenyl ether (referred to as 4,4'-ODA), 7.8048g (19.4mmol)
HQDPA, 0.1777g (1.2mmol) PA, 53g metacresol, 5 isoquinolin, react in a nitrogen atmosphere, stir, be warming up to
200 DEG C are reacted 8 hours, are cooled to room temperature, add ethanol and separate out with powder as precipitant, polymer, utilize a large amount of second
Alcohol and water is carried out, and then 150 DEG C dry 10 hours in vacuum drying oven, obtain polyimide resin PI-5.
Measure the polyimides PI-5 obtained with DSC, result heating curve for the first time only observes fusing point TmIt is 315
DEG C, without clearly observing TgAnd Tc(there is high degree of crystallinity).Rise warming middle-JIAO in second time and observe TgIt is 199 DEG C, TmIt it is 318 DEG C.
Measuring 5% heat decomposition temperature in its air is 526 DEG C, and logarithmic viscosity number is 0.54dL/g.Rotational rheometer is utilized to record it
Minimum melt complex viscosity is 426Pa s (at 346 DEG C).
Embodiment 6
To being furnished with agitator, the there-necked flask of reflux condensing tube and nitrogen airway adds 4.9696g (17.0mmol)
TPER, 0.5527g (3.0mmol) 4,4'-benzidine (referred to as BZD), 7.8048g (19.4mmol) HQDPA, 0.1777g
(1.2mmol) PA, 53g metacresol, 5 isoquinolin, react in a nitrogen atmosphere, stir, be warming up to 200 DEG C and react 8
Hour, it is cooled to room temperature, adds ethanol and separate out with powder as precipitant, polymer, utilize a large amount of second alcohol and water to carry out clearly
Washing, then 150 DEG C dry 10 hours in vacuum drying oven, obtain polyimide resin PI-6.
Measure the polyimides PI-6 obtained with DSC, result heating curve for the first time only observes fusing point TmIt is 339
DEG C, without clearly observing TgAnd Tc(there is high degree of crystallinity).Rise warming middle-JIAO in second time and observe TgIt is 196 DEG C, TmIt it is 340 DEG C.
Measuring 5% heat decomposition temperature in its air is 542 DEG C, and logarithmic viscosity number is 0.57dL/g.Rotational rheometer is utilized to record it
Minimum melt complex viscosity is 1080Pa s (at 374 DEG C).
Embodiment 7
To being furnished with agitator, the there-necked flask of reflux condensing tube and nitrogen airway adds 2.9233g (10.0mmol)
TPER, 2.0024g (10.0mmol) 3,4'-diaminodiphenyl ether (referred to as 3,4'-ODA), 7.8048g (19.4mmol)
HQDPA, 0.1777g (1.2mmol) PA, 53g metacresol, 5 isoquinolin, react in a nitrogen atmosphere, stir, be warming up to
200 DEG C are reacted 8 hours, are cooled to room temperature, add ethanol and separate out with powder as precipitant, polymer, utilize a large amount of second
Alcohol and water is carried out, and then 150 DEG C dry 10 hours in vacuum drying oven, obtain polyimide resin PI-7.
Measure the polyimides PI-7 obtained with DSC, result heating curve for the first time only observes fusing point TmIt is 305
DEG C, without clearly observing TgAnd Tc(there is high degree of crystallinity).Rise warming middle-JIAO in second time and observe TgIt is 205 DEG C, TmIt it is 303 DEG C.
Measuring 5% heat decomposition temperature in its air is 519 DEG C, and logarithmic viscosity number is 0.54dL/g.Rotational rheometer is utilized to record it
Minimum melt complex viscosity is 324Pa s (at 331 DEG C).
Embodiment 8
To being furnished with agitator, the there-necked flask of reflux condensing tube and nitrogen airway adds 2.9233g (10.0mmol)
TPER, 3.6844g (10.0mmol) 4,4 '-two (4-amino-benzene oxygen) 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
Drip isoquinolin, react in a nitrogen atmosphere, stir, be warming up to 200 DEG C and react 8 hours, be cooled to room temperature, add ethanol
As precipitant, polymer separates out with powder, utilizes a large amount of second alcohol and water to be carried out, then in vacuum drying oven 150 DEG C
It is dried 10 hours, obtains polyimide resin PI-8.
Measure the polyimides PI-8 obtained with DSC, result heating curve for the first time only observes fusing point TmIt is 345
DEG C, without clearly observing TgAnd Tc(there is high degree of crystallinity).Rise warming middle-JIAO in second time and observe TgIt is 215 DEG C, TmIt it is 343 DEG C.
Measuring 5% heat decomposition temperature in its air is 525 DEG C, and logarithmic viscosity number is 0.74dL/g.Rotational rheometer is utilized to record it
Minimum melt complex viscosity is 864Pa s (at 380 DEG C).
Embodiment 9
To being furnished with agitator, the there-necked flask of reflux condensing tube and nitrogen airway adds 2.9233g (10.0mmol)
TPER, 5.0055g (10.0mmol) 1,3-are double [4-(4-amino-benzene oxygen) benzoyl] (referred to as BABB), 7.8048g
(19.4mmol) 3,3'-HQDPA, 0.1777g (1.2mmol) PA, 53g metacresol, 5 isoquinolin, react in a nitrogen atmosphere,
Stirring, be warming up to 200 DEG C and react 8 hours, be cooled to room temperature, addition ethanol is as precipitant, and polymer is with powder
Separating out, utilize a large amount of second alcohol and water to be carried out, then 150 DEG C dry 10 hours in vacuum drying oven, obtain polyimides tree
Fat PI-9.
Measure the polyimides PI-9 obtained with DSC, result heating curve for the first time only observes fusing point TmIt is 338
DEG C, without clearly observing TgAnd Tc(there is high degree of crystallinity).Rise warming middle-JIAO in second time and observe TgIt is 206 DEG C, TmIt it is 336 DEG C.
Measuring 5% heat decomposition temperature in its air is 531 DEG C, and logarithmic viscosity number is 0.84dL/g.Rotational rheometer is utilized to record it
Minimum melt complex viscosity is 769Pa s (at 376 DEG C).
Embodiment 10
To being furnished with agitator, the there-necked flask of reflux condensing tube and nitrogen airway adds 2.9233g (10.0mmol)
TPER, 2.0024g (10.0mmol) 4,4'-diaminodiphenyl sulfide (referred to as SDA), 7.8048g (19.4mmol) 3,3'-
HQDPA, 0.1777g (1.2mmol) PA, 53g metacresol, 5 isoquinolin, react in a nitrogen atmosphere, stir, be warming up to
200 DEG C are reacted 8 hours, are cooled to room temperature, add ethanol and separate out with powder as precipitant, polymer, utilize a large amount of second
Alcohol and water is carried out, and then 150 DEG C dry 10 hours in vacuum drying oven, obtain polyimide resin PI-10.
Measure the polyimides PI-10 obtained with DSC, result heating curve for the first time only observes fusing point TmIt is 342
DEG C, without clearly observing TgAnd Tc(there is high degree of crystallinity).Rise warming middle-JIAO in second time and observe TgIt is 206 DEG C, TmIt it is 340 DEG C.
Measuring 5% heat decomposition temperature in its air is 522 DEG C, and logarithmic viscosity number is 0.97dL/g.Rotational rheometer is utilized to record it
Minimum melt complex viscosity is 1158Pa s (at 386 DEG C).
Various embodiments of the present invention feed intake parameter and the performance parameter of polyimide resin for preparing as shown in table 1.
Table 1
Table 1 (Continued)
As shown above, the ratio adding rigidity diamine monomer 2 is the highest, and its fusing point improves, and melt viscosity increases.By control
Rigidity diamidogen ratio processed, in OK range, can obtain the crystalline thermoplastic copolyimide that fusing point is suitable.
Claims (10)
1. a crystalline thermoplastic copolyimide resin, it is characterised in that by aromatic dianhydride monomer, aromatic diamine
The reaction of monomer, end-capping reagent prepares, and its formula is as follows:
Wherein, Ar' is aromatic diamine monomer residue, and x is positive integer, and 10≤x≤180；
Described aromatic dianhydride monomer is 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydride or 2,2', 3,3'-triphen diether tetramethyl
Acid dianhydride；Described aromatic diamine monomer is blended with one or more in following diamidogen by double (4-amino-benzene oxygen) benzene of 1,3-
Composition: 1,4-double (4-amino-benzene oxygen) benzene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminourea two
Diphenyl sulfide, p-phenylenediamine, 4,4'-benzidine, 4,4'-bis-(4-amino-benzene oxygen) biphenyl, 4,4'-bis-(3-amino-benzene oxygen)
Double [4-(4-amino-benzene oxygen) phenyl] propane of biphenyl, 2,2-, double [4-(4-amino-benzene oxygen) phenyl]-1,1,1,3,3 of 2,2-,
Double [4-(4-amino-benzene oxygen) benzoyl] benzene of 3-HFC-236fa, 1,3-and double [4-(4-amino-benzene oxygen) benzoyl of 1,4-
Base] benzene；Described 1,3-double (4-amino-benzene oxygen) benzene mol ratio shared by the mixture of described aromatic diamine monomer is 1
～99%；Described end-capping reagent is phthalic anhydride.
Crystalline thermoplastic copolyimide resin the most according to claim 1, it is characterised in that described crystallinity heat
The theoretical value average molecular weight of plasticity copolyimide resin is between 104～105Between g/mol, logarithmic viscosity number scope is
0.2～5.0dL/g.
Crystalline thermoplastic copolyimide resin the most according to claim 1, it is characterised in that described crystallinity heat
The glass transition temperature of plasticity copolyimide resin be more than 190 DEG C, fusing point between 300～380 DEG C, air atmosphere
In 5% thermal weight loss temperature higher than 500 DEG C.
Crystalline thermoplastic copolyimide resin the most according to claim 1, it is characterised in that described crystallinity heat
The minimum melt complex viscosity of plasticity copolyimide resin is less than 1500Pa s.
Crystalline thermoplastic copolyimide resin the most according to claim 1, it is characterised in that described crystallinity heat
Plasticity copolyimide resin still can rapid crystallization after more than four times repeatedly melted, cooling.
Crystalline thermoplastic copolyimide resin the most according to claim 1, it is characterised in that described aromatic series two
Amine monomers is 1, double (4-amino-benzene oxygen) benzene of 3-and the mixture of Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, and described aromatic series two
Anhydride monomer is 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydride.
Crystalline thermoplastic copolyimide resin the most according to claim 1, it is characterised in that described aromatic series two
Amine monomers is 1, double (4-amino-benzene oxygen) benzene and 4 of 3-, the mixture of 4'-benzidine, and described aromatic dianhydride monomer is
3,3', 4,4'-triphen diether tetracarboxylic acid dianhydride.
Crystalline thermoplastic copolyimide resin the most according to claim 1, it is characterised in that described aromatic series two
Amine monomers is 1, double (4-amino-benzene oxygen) benzene and 3 of 3-, the mixture of 4'-diaminodiphenyl ether, and described aromatic dianhydride list
Body is 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydride.
Crystalline thermoplastic copolyimide resin the most according to claim 1, it is characterised in that described aromatic series two
Amine monomers is 1, double (4-amino-benzene oxygen) benzene and 4 of 3-, the mixture of 4'-diaminodiphenyl ether, and described aromatic dianhydride list
Body is 3,3', 4,4'-triphen diether tetracarboxylic acid dianhydride.
10. the application of the crystalline thermoplastic copolyimide resin described in a claim 1, it is characterised in that described
Crystalline thermoplastic copolyimide resin can be used for high heat-resistant engineering plastic, composite matrix resin, high temperature adhesive,
Powdery paints, high performance thin film, 3D printing polymer powder or increasing material manufacture resin.
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| CN107747519A (en) * | 2017-10-26 | 2018-03-02 | 南通汇平高分子新材料有限公司 | A kind of novel piston and preparation method thereof |
| CN109438702A (en) * | 2018-09-29 | 2019-03-08 | 苏州市新广益电子有限公司 | It is a kind of for the TPI film of FPC industry and its preparation and processing method |
| TWI709592B (en) * | 2018-11-22 | 2020-11-11 | 達勝科技股份有限公司 | Polyimide film, and manufacturing method of polyimide film |
| WO2020228260A1 (en) * | 2019-05-15 | 2020-11-19 | 宁波市医疗中心李惠利医院 | Medical copolyester and preparation method therefor |
| CN113045776A (en) * | 2021-03-19 | 2021-06-29 | 黄山金石木塑料科技有限公司 | High-heat-resistance polyimide powder for 3D printing and preparation method thereof |
| CN114524937A (en) * | 2022-02-16 | 2022-05-24 | 浙江清和新材料科技有限公司 | Polyimide resin and preparation method thereof |
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| CN109438702A (en) * | 2018-09-29 | 2019-03-08 | 苏州市新广益电子有限公司 | It is a kind of for the TPI film of FPC industry and its preparation and processing method |
| TWI709592B (en) * | 2018-11-22 | 2020-11-11 | 達勝科技股份有限公司 | Polyimide film, and manufacturing method of polyimide film |
| WO2020228260A1 (en) * | 2019-05-15 | 2020-11-19 | 宁波市医疗中心李惠利医院 | Medical copolyester and preparation method therefor |
| CN113045776A (en) * | 2021-03-19 | 2021-06-29 | 黄山金石木塑料科技有限公司 | High-heat-resistance polyimide powder for 3D printing and preparation method thereof |
| CN113045776B (en) * | 2021-03-19 | 2023-08-04 | 黄山金石木塑料科技有限公司 | High heat-resistant polyimide powder for 3D printing and preparation method thereof |
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| CN115651404B (en) * | 2022-09-27 | 2024-03-26 | 宁波领科新材料科技有限公司 | Wear-resistant modified polyimide composite material and preparation method thereof |
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