CN107698761A - A kind of preparation method of polyimides - Google Patents
A kind of preparation method of polyimides Download PDFInfo
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- CN107698761A CN107698761A CN201711070119.6A CN201711070119A CN107698761A CN 107698761 A CN107698761 A CN 107698761A CN 201711070119 A CN201711070119 A CN 201711070119A CN 107698761 A CN107698761 A CN 107698761A
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- benzene
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- dianhydride
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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
Abstract
The invention discloses a kind of preparation method of polyimides, comprise the following steps：Synthesizing polyamides acid；Obtained polyamic acid is subjected to cyclization by screw extruder at a certain temperature, obtains cyclisation product；Collect cyclisation product to be post-processed, obtain polyimide powder；And after cyclization, extracted out solvent by the vacuum port of screw extruder, condense, the solvent obtained to condensation is collected and returns to polyamic acid preparation process.Polyimide function admirable, environmental protection and economy, the cost that the present invention is prepared are low, solve the bottleneck problem of polyimides production, have good economic and social benefit.
Description
Technical field
The present invention relates to a kind of preparation method of polyimides, more particularly to a kind of preparation of the polyimides of HMW
Method.
Background technology
Polyimides (Polyimide, abbreviation PI) refers to a kind of polymer that main chain contains imide ring, rigid acid imide
Structure assigns polyimides unique performance, it is had the performance such as good heat resistance and excellent mechanics, electricity, its resistance to spoke
According to, solvent resistant, the excellent performance possessed at high temperature can compare favourably with some metals.In addition, polyimides is also with excellent
Chemical stability, toughness, wearability, anti-flammability, electrical insulating property and other mechanical performances.At present, polyimides conduct
A kind of special engineered material, has been widely used in the fields such as Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, seperation film, laser.
The most common preparation method of polyimides is to use diamines and dianhydride two-step method, specifically by dianhydride and diamines
Two kinds of monomers polymerization generation polyamic acid (Polyamic in polar solvent (such as NMP, DMAc, DMF, DMSO etc.)
Acid, abbreviation PAA) performed polymer, then obtain final products-polyimides (PI) through thermal cyclization or chemical imidization by PAA.Tool
Precursor reactant process is shown below：
In the course of reaction, dianhydride can absorb water to form tetracid, cause polymerisation to terminate, and hinder polymerisation.This
Outside, polyamic acid (PAA) is cyclized into polyimides process (K2) most important to the performances of final PI products, because PAA is cyclized
During, while back reaction (K can be carried out5), dianhydride and diamines are degraded into, or sour (K3) is resolved into, these side reactions can not
Cause final products PI molecular weight small with avoiding, accessory substance is that impurity is more, so as to have impact on PI performance.Therefore, people in order to
High performance PI products are obtained, it is necessary to promote being smoothed out for cyclization (K2), while suppress side reaction (K3, K5) progress.
PAA cyclization methods include：(1) chemical imidization method：The use of dehydrating agent is typically acetic anhydride, with tertiary amines such as pyridine,
Triethylamine is catalyst, is added in PAA systems, and PI powder is separated out under low temperature, but the PI cyclisation that such method obtains is incomplete,
Secondary thermal cyclization is needed to handle, being cyclized the powder of precipitation in addition needs to be washed with a large amount of poor solvents, pollutes environment, and cost drastically increases
Add；(2) thermal cyclization method：Although secondary heat treatment can be avoided, powder is not easy into, and it is degradable during cyclization,
Molecular weight diminishes.Therefore, people add entrainer, such as toluene, dimethylbenzene etc. in system, band water is total to during thermal cyclization
Boiling, reduces the degradation reaction caused by water, but the use of entrainer adds the generation of cost and organic wastewater, can be to ring
Border has a negative impact.
TPI can also carry out high-temperature fusion polymerization simultaneously with dianhydride and diamines directly in screw extruder
It is granulated, it is no longer necessary to which solvent, this method is although environment friendly and pollution-free, can greatly improve efficiency, but because the activity of monomer is inclined
It is low, the product of HMW can not be aggregated within short a few minutes, and due to solvent-free, two kinds of monomers are in the course of the polymerization process
It can not accomplish that molal quantity is equal, more result in molecular weight of product and do less.
In view of the above problems, the technical problem to be solved in the present invention is how to be prepared into by more environmentally-friendly economic means
To the polyimides of HMW.
The content of the invention
In order to overcome the shortcomings of the prior art, the present invention provides a kind of environmental protection and economy, and properties of product are excellent, cost
It is low, the preparation method of the high polyimides of molecular weight.
The technical solution adopted in the present invention is：
A kind of preparation method of polyimides, it is characterised in that comprise the following steps：
(1) preparation of performed polymer：Synthesizing polyamides acid；
(2) cyclization：The performed polymer polyamic acid that step (1) obtains is entered at a certain temperature by screw extruder
Row cyclization, obtains cyclisation product；
(3) post-process：The cyclisation product of collection step (2) is post-processed, and obtains polyimide powder.
Further, polyamic acid is dissolved according to a certain percentage in solvent by dibasic acid anhydride and diamines, and adds end-blocking
Agent, at a certain temperature, react to obtain by certain time.
Wherein, the dibasic acid anhydride for preparing polyamic acid can be aromatic dianhydride；It is preferred that pyromellitic acid anhydride, 3,3 ' 4,
4 '-diphenyl sulphone (DPS) tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA, bisphenol A-type dianhydride, 3,3 ' 4,4 '-benzophenone tetracid two
Acid anhydride, 4, the double phthalic anhydrides of 4 '-oxygen, the phthalandione dianhydride of hexafluoroisopropylidenyl two, isomery diphenyl ether dianhydride, triphen diether four
Acid dianhydride, benzophenone tetracarboxylic acid dianhydride, monoether tetracarboxylic acid dianhydride, 4,4'- (hexafluoro propylidene) double phthalic anhydrides, 4,4'- is double
(3,4- di carboxyl phenyloxy) diphenyl ether dianhydride, 4,4'- double (3,4- di carboxyl phenyloxy) diphenyl sulfide dianhydrides, 1,2,
4,5- acid dianhydrides, 2,3,3', 4'- benzophenone tetracarboxylic dianhydrides, 2,2', 6,6'- biphenyl tetracarboxylic dianhydrides, butane -1,2,
3,4- tetracarboxylic dianhydrides, cyclobutane -1,2,3,4- tetracarboxylic dianhydrides, thiophene -2,3,4,5- tetracarboxylic dianhydrides, pyridine -2,3,5,
One or more in 6- tetracarboxylic dianhydrides.
Wherein, the diamines for preparing polyamic acid can be aromatic diamine, preferably 4,4'- diaminodiphenyl-methanes, 4,4'-
Diaminodiphenyl ether, 3,4'- diaminodiphenyl ethers, 4,4'- diaminodiphenylsulfones, 3,4- diaminodiphenylsulfones, 3,3'- diaminourea
Diphenyl sulphone (DPS), a diaminobenzene, para diaminobenzene, ortho-diaminobenzene, 1,5-diaminonaphthalene, 3,3- dimethylanilines, benzidine,
The methanediamine of benzene two, double (amino-benzene oxygen) fluorenes, 4,4'- double (4- amino-benzene oxygens) biphenyl, 4,4'- double (3- amino-benzene oxygens) connection
Benzene, double (amino-benzene oxygen) fluorenes, 2,6'- diaminotoluenes, 2,4- diaminochlorobenzenes, 3,3'- dimethyl -4,4'- diaminourea connection
Benzene, 4,4'- diaminourea diphenyl sulfides, 1,2- diaminomethane, 1,4-Diaminobutane, tetra-methylenedimine, 1,10- diaminourea ten
Dioxane, Isosorbide-5-Nitrae-diaminocyclohexane, 1,2- diaminocyclohexane, 3,4- diamino-pyridines, Isosorbide-5-Nitrae-diaminourea -2- butanone, 1,3-
Double (3- amino-benzene oxygen -4'- benzoyls) benzene, 4,4'- bis- (3- amino-benzene oxygens benzene) sulfones, 2,2'- bis- (4- amino-benzene oxygens
Benzene) sulfone, 4,4'- bis- (3- amino-benzene oxygens benzene) propane, 4,4'- bis- (4- amino-benzene oxygens benzene) propane, 4,4'- diaminourea two
Benzophenone, double (4- (4- amino-benzene oxygens) phenyl) HFC-236fas, 4,4'- double (aminophenyl) HFC-236fas, 1,3- diaminourea-
4- cumenes, 1,2- double (3- amino-benzene oxygens) ethane, double (p- beta-amino-tert-butyl-phenyl) ethers, 1,3- double (3- (3- ammonia
Phenoxyl) phenoxy group) benzene, 1,3- double (3- (2- amino-benzene oxygens) phenoxy group) benzene, 1,3- double (2- (2- amino-benzene oxygens)
Phenoxy group) benzene, 1,3- double (3- (3- amino-benzene oxygens) phenoxy group) -2- toluene, 1,3- double (3- (3- amino-benzene oxygens) benzene oxygen
Base) -2- chlorobenzenes, double (3- (3- (3- amino-benzene oxygens) phenoxy group) phenyl) ethers, double (3- (3- (2- amino-benzene oxygens) benzene oxygen
Base) phenyl) ether, double (4- (3- (3- amino-benzene oxygens) phenoxy group) phenyl) ethers, α, ω-bis- (methylaminos) poly dimethyl silicon
One or more in oxygen alkane.
Wherein, the solvent for preparing polyamic acid is polar solvent, preferably 4,4 '-dimethylformamide, 4,4 '-dimethyl
Acetamide, dimethyl sulfoxide, N- methyl isophthalic acids-pyrrolidones, the one or more of metacresol.
Wherein, the end-capping reagent for preparing polyamic acid is the molecular weight for controlling polyimides, can be primary monoamines or virtue
At least one of race's dicarboxylic anhydride, the illustrative examples of primary monoamines include aniline, chloroaniline, naphthylamine, perfluoromethyl
It is one or more of；Aromatic dicarboxylic acid anhydride illustrative example includes phthalic anhydride, the phthalic anhydride of substitution, as chloro is adjacent
Phthalate anhydride, the one or more of bromophthalic acid acid anhydride.
Further, in cyclization, the screw extruder is preferably single screw extrusion machine.
Further, in cyclization, the cyclisation temperature is that the screw rod silicon carbide of screw extruder is 150-300
DEG C, preferably 180-250 DEG C, temperature is too low, and cyclisation rate is low, and powder product yield is low, and temperature is too high, and precipitation powder is excessive, can cause
Screw rod local stoppages.
Further, in cyclization, the rotating speed of screw extruder is 10-300r/min, preferably 100-150r/min.Turn
Speed is too low, and cyclisation time length, solvent volatilization excessively causes blocking, and rotating speed is too fast, and the residence time is short, and cyclisation degree is relatively low.
Further, the cyclization time is 1-20 minutes, preferably 2-5 minutes.The cyclization time is determined by screw speed
Fixed, polyamic acid material residence time in screw extruder is short, therefore is not susceptible to degradation reaction, is advantageous to HMW
The generation of polyimides.
Further, the post-processing step includes separation of solid and liquid, washing, drying.
Further, the preparation method of polyimides also includes：After cyclization terminates, pass through the true of screw extruder
Eat dishes without rice or wine to extract out solvent, then condense, to condensing the step of obtained solvent is collected.
Wherein, the obtained solvent that condenses can be returned in pre-polymerization preparation step, reused.
The present invention is for current polyimides preparation method molecular weight is low, cost is high, efficiency is low, pollution etc. be present to environment
Problem, carry out polyamic acid cyclization using screw extruder and obtain polyimides, have the following advantages that：
1. polyamic acid material residence time in screw extruder is short, not degradable, the poly- of HMW can be obtained
Acid imide, while the generation of side reaction is avoided, the purity of polyimides is improved, and the shortening in reaction time substantially increases
Production efficiency.
2. carrying out cyclization using screw extruder, most of solvent can be reclaimed directly, environmental protection and economy, reduce life
Produce cost.
3. carrying out cyclization using this method, it is thin to obtain polyimide powder particle diameter.
Therefore, polyimide function admirable, environmental protection and economy, the cost that the present invention is prepared are low, solve polyamides
The bottleneck problem of imines production, has good economic and social benefit.
Embodiment
Embodiment 1：A kind of method for preparing polyimides, step are as follows：
(1) preparation of performed polymer：
Under nitrogen protection, at room temperature by 210g 4,4'- bis- (3- amino-benzene oxygens benzene) propane be added in 4,4 '-two
In NMF, quick stirring makes its dissolving, is then slowly added 105g pyromellitic acid anhydrides, 2.3g phthalic acids
Acid anhydride, question response 3-6 hours obtain polyamic acid solution；
(2) cyclization：
Using single screw extrusion machine, remove mouth mold, and screw rod silicon carbide is set 180-220 DEG C, then polyamide
Acid solution, which is added in extruder, carries out cyclization, and adjustment rotating speed is 120r/min, after reacting 3 minutes, passes through vacuum port handle
Most of solvent (gas) is taken away, is condensed, and collects solvent.Solid product flows out with a small amount of solvent from head, is collected into
Cyclisation product.
(3) post-process
Centrifuged, washed, vacuum drying, obtain faint yellow PI fine powders, the PI fine powder weight average molecular weight is：
48200, average grain diameter is 21 microns.
Comparative example 1：A kind of method for preparing polyimides, its step (1) is identical with the step of embodiment 1 (1), step (2)
For thermal cyclization method, concretely comprise the following steps：Polyamic acid solution is carried out to be heated to 170 DEG C, insulation is cyclized for 2 hours, is cooled, is obtained
To product.Centrifuged, washed, vacuum drying obtains yellow PI powdered products.The PI powder weight average molecular weight is：25400, grain
Footpath is 38 microns.
Embodiment 2：A kind of method for preparing polyimides, step are as follows：
(1) preparation of performed polymer：
Under nitrogen protection, 200g 4, is added to 4,4 '-dimethyl acetamide at 4'- diaminodiphenyl ethers at room temperature
In, quick stirring makes its dissolving, is then slowly added 215g pyromellitic acid anhydrides, 4.14g phthalic anhydrides, question response 3-
Obtain polyamic acid solution within 6 hours；
(2) cyclization：
Using single screw extrusion machine, remove mouth mold, and screw rod silicon carbide is set 200-230 DEG C, then polyamide
Acid solution, which is added in extruder, carries out cyclization, and adjustment rotating speed is 110r/min, after reacting 4 minutes, passes through vacuum port handle
Most of solvent (gas) is taken away, is condensed, and collects solvent, and the solvent of collection returns to pre- specific preparation section, solid product
Flowed out with a small amount of solvent from head, be collected into cyclisation product.
(3) post-process：
Centrifuged, washed, vacuum drying, obtain faint yellow PI fine powders, the PI fine powder weight average molecular weight is：
36700, particle diameter is 16 microns.
Comparative example 2：A kind of method for preparing polyimides, its step (1) is identical with the step of embodiment 2 (1), step (2)
For thermal cyclization method, concretely comprise the following steps：Polyamic acid solution is carried out to be heated to 160 DEG C, insulation is cyclized for 2 hours, is cooled, is obtained
To product.Centrifuged, washed, vacuum drying obtains yellow PI powdered products.The PI powder weight average molecular weight is：19500, grain
Footpath is 25 microns.
Claims (10)
1. a kind of preparation method of polyimides, it is characterised in that comprise the following steps：
(1) preparation of performed polymer：Synthesizing polyamides acid；
(2) cyclization：The performed polymer polyamic acid that step (1) obtains is subjected to ring at a certain temperature by screw extruder
Change reaction, obtain cyclisation product；
(3) post-process：The cyclisation product of collection step (2) is post-processed, and obtains polyimide powder.
2. the preparation method of a kind of polyimides according to claim 1, it is characterised in that further comprise, be cyclized
After reaction, solvent is extracted out by the vacuum port of screw extruder, condensed, and the step that the solvent obtained to condensation is collected
Suddenly.
3. the preparation method of a kind of polyimides according to claim 2, it is characterised in that described to condense obtained solvent
It can return in pre-polymerization preparation step, be reused.
A kind of 4. preparation method of polyimides according to claim any one of 1-3, it is characterised in that the step
(1) polyamic acid described in is dissolved according to a certain percentage in solvent by dibasic acid anhydride and diamines, and by adding end-capping reagent,
Under certain temperature, react to obtain by certain time.
5. the preparation method of a kind of polyimides according to claim any one of 1-3, it is characterised in that the screw rod squeezes
It is single screw extrusion machine to go out machine.
6. the preparation method of a kind of polyimides according to claim any one of 1-3, it is characterised in that in step (2)
The temperature is 150-300 DEG C, and the rotating speed of the screw extruder is 10-300r/min, and the time of the cyclization is 1-
20 minutes.
A kind of 7. preparation method of polyimides according to claim 6, it is characterised in that temperature described in step (2)
For 180-250 DEG C, the rotating speed of the screw extruder is 100-150r/min, and the time of the cyclization is 2-5 minutes.
8. the preparation method of a kind of polyimides according to claim 4, it is characterised in that the dibasic acid anhydride is aromatics
Dicarboxylic anhydride, the diamines are aromatic diamine, and the solvent is polar solvent, and the end-capping reagent is primary monoamines or aromatic dicarboxylic acid anhydride
At least one.
9. the preparation method of a kind of polyimides according to claim 8, it is characterised in that the aromatic dianhydride is equal
PMDA, 3,3 ' 4,4 '-diphenyl sulphone (DPS) tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA, bisphenol A-type dianhydride, 3,3 '
4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxygen double phthalic anhydride, the phthalandione dianhydride of hexafluoroisopropylidenyl two, isomery diphenyl sulfides
Dianhydride, triphen diether tetracarboxylic dianhydride, benzophenone tetracarboxylic acid dianhydride, monoether tetracarboxylic acid dianhydride, the double adjacent benzene two of 4,4'- (hexafluoro propylidene)
Double (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides of formic anhydride, 4,4'-, double (3,4- di carboxyl phenyloxies) the diphenyl sulphur of 4,4'-
Compound dianhydride, 1,2,4,5- acid dianhydrides, 2,3,3', 4'- benzophenone tetracarboxylic dianhydride, 2,2', 6,6'- biphenyltetracarboxyacid acids two
Acid anhydride, butane -1,2,3,4- tetracarboxylic dianhydrides, cyclobutane -1,2,3,4- tetracarboxylic dianhydrides, thiophene -2,3,4,5- tetracarboxylic dianhydrides,
One or more in pyridine -2,3,5,6- tetracarboxylic dianhydrides；The aromatic diamine be 4,4'- diaminodiphenyl-methanes, 4,
4'- diaminodiphenyl ethers, 3,4'- diaminodiphenyl ethers, 4,4' diaminodiphenyl sulfone, 3,4- diaminodiphenylsulfones, 3,3'- bis-
Aminodiphenyl sulfone, a diaminobenzene, para diaminobenzene, ortho-diaminobenzene, 1,5- diaminonaphthalenes, 3,3- dimethylanilines, biphenyl
Double (4- amino-benzene oxygens) biphenyl of amine, the methanediamine of isophthalic two, double (amino-benzene oxygen) fluorenes, 4,4'-, double (the 3- aminobenzene oxygen of 4,4'-
Base) biphenyl, double (amino-benzene oxygen) fluorenes, 2,6'- diaminotoluenes, 2,4- diaminochlorobenzenes, 3,3'- dimethyl -4,4'- diaminos
Base biphenyl, 4,4'- diaminourea diphenyl sulfide, 1,2- diaminomethanes, 1,4- diaminobutanes, tetra-methylenedimine, 1,10- diaminos
Base dodecane, 1,4- diaminocyclohexanes, 1,2- diaminocyclohexanes, 3,4- diamino-pyridines, 1,4- diaminourea -2- butanone,
1,3- double (3- amino-benzene oxygen -4'- benzoyls) benzene, 4,4'- bis- (3- amino-benzene oxygens benzene) sulfone, (the 4- aminobenzenes of 2,2'- bis-
Epoxide benzene) sulfone, 4,4'- bis- (3- amino-benzene oxygens benzene) propane, 4,4'- bis- (4- amino-benzene oxygens benzene) propane, 4,4'- diaminourea
Benzophenone, double (4- (4- amino-benzene oxygens) phenyl) HFC-236fas, 4,4'- double (aminophenyl) HFC-236fa, 1,3- diaminos
Double (3- amino-benzene oxygens) ethane of base -4- cumenes, 1,2-, double (p- beta-amino-tert-butyl-phenyl) ethers, the double (3- of 1,3-
(3- amino-benzene oxygens) phenoxy group) benzene, double (3- (2- amino-benzene oxygens) phenoxy group) benzene of 1,3-, double (2- (the 2- aminobenzene oxygen of 1,3-
Base) phenoxy group) benzene, double (3- (3- amino-benzene oxygens) the phenoxy group) -2- toluene of 1,3-, double (3- (3- amino-benzene oxygens) benzene of 1,3-
Epoxide) -2- chlorobenzenes, double (3- (3- (3- amino-benzene oxygens) phenoxy group) phenyl) ethers, double (3- (3- (2- amino-benzene oxygens) benzene oxygen
Base) phenyl) ether, double (4- (3- (3- amino-benzene oxygens) phenoxy group) phenyl) ethers, α, ω-bis- (methylaminos) polydimethylsiloxanes
One or more in alkane；The polar solvent be 4,4 '-dimethylformamide, 4,4 '-dimethyl acetamide, dimethyl sulfoxide,
N- methyl isophthalic acids-pyrrolidones, the one or more of metacresol；The primary monoamines are aniline, chloroaniline, naphthylamine, perfluoro-methyl
The one or more of aniline；The aromatic dicarboxylic acid anhydride be phthalic anhydride, substitution phthalic anhydride in one kind or
It is several.
10. the preparation method of a kind of polyimides according to claim any one of 1-3, it is characterised in that after step (3)
Processing includes separation of solid and liquid, washing and drying.
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| CN109627763A (en) * | 2018-11-27 | 2019-04-16 | 万华化学集团股份有限公司 | A kind of method that solid phase prepares polyimide molding powder |
| WO2020040089A1 (en) * | 2018-08-20 | 2020-02-27 | 日産化学株式会社 | Liquid crystal alignment agent, production method thereof, liquid crystal alignment film, and liquid crystal display element |
| CN110885443A (en) * | 2019-12-11 | 2020-03-17 | 万华化学集团股份有限公司 | Thermoplastic polyimide and preparation method thereof |
| WO2021035907A1 (en) * | 2019-08-26 | 2021-03-04 | 武汉华星光电半导体显示技术有限公司 | Fluorine-group-containing polyimide and preparation method therefor, flexible substrate and display device |
| CN113429623A (en) * | 2021-06-17 | 2021-09-24 | 中国科学院山西煤炭化学研究所 | Method for preparing polyamic acid by degrading polyimide resin |
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