CN104231268A - Polyimide and preparation method thereof - Google Patents

Polyimide and preparation method thereof Download PDF

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Publication number
CN104231268A
CN104231268A CN201410530748.2A CN201410530748A CN104231268A CN 104231268 A CN104231268 A CN 104231268A CN 201410530748 A CN201410530748 A CN 201410530748A CN 104231268 A CN104231268 A CN 104231268A
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Prior art keywords
polyimide
present
formula
diamine
prepares
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阎敬灵
吉晓东
王震
刘敬峰
范卫锋
孟祥胜
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a polyimide. The polyimide is of a structure shown in a formula I; in the formula I, R is the residue group of aromatic di-anhydride with terminating-oxyl eliminated or the residue group of aliphatic di-anhydride with terminating-oxyl eliminated; n is the degree of polymerization and is greater than or equal to 1 and smaller than or equal to 1000. The invention also discloses a preparation method of the polyimide. The method comprises subjecting diamine and di-anhydride to reaction at a temperature higher than or equal to 150 DEG C inside solvent to obtain the polyimide. The invention also provides a polyimide membrane manufactured through the technical scheme above of the preparation method of the polyimide. The polyimide is high transparency, environmental-pollution-free, good in heat stability and high in glass transition temperature and mechanical performance. The diamine utilized in the preparation method of the polyimide is a renewable resource and is environmentally friendly; the preparation method is simple in process and operation.

Description

A kind of polyimide and preparation method thereof
Technical field
The present invention relates to technical field of polymer, particularly relate to a kind of polyimide and preparation method thereof.
Background technology
Polyimide resin has good thermotolerance, oxidation-resistance, radiation resistance, chemical resistant properties and good machinery and electrical specification.Many premium propertiess of polyimide make it be widely applied at industrial circles such as aerospace material, electronics and microelectronics, optics and communications and transportation.
According to the chemical structure of polyimide repeating unit, polyimide can be divided into aliphatic polyimide, semi-aromatic polyimide and aromatic polyimide three kinds.According to the thermal properties of polyimide, polyimide can be divided into thermoplastic polyimide and Thermocurable polyimide.According to the preparation method of polyimide, polyimide can be divided into condensation polymer type polyimide and polyaddition type polyimide.Wherein, condensation polymer type polyimide normally reacts obtained by diamine and dianhydride, tetracarboxylic acid or tetracarboxylic acid dialkyl, and condensation polymer type polyimide is mainly used to manufacture Kapton, fiber and engineering plastics etc.
Application number be 201210082313.7 Chinese patent disclose a kind of preparation method of polyimide, comprise the following steps: dehydration polymerization reaction a), by diamines and organic acid acid anhydrides occurs in non-polar solvent, obtain mixture, described non-polar solvent is one or more in aromatic hydrocarbon, aliphatic hydrocarbon, halogenated aromatic or halogenated aliphatic hydrocarbon, and described organic acid acid anhydrides is one or more in dianhydride and single acid anhydride; B) polyimide is obtained after the mixture filtration, described step a) obtained, drying.
The preparation method of this polyimide that prior art provides; make diamines and organic acid acid anhydrides that dehydration polymerization directly occur in non-polar solvent and be obtained by reacting polyimide; polyimide is insoluble to non-polar solvent; therefore; can by obtain reaction product direct filtration, drying, without the need to washing, the polyimide powder that particle is tiny can be obtained; this method preparing polyimide is with short production cycle, production cost is low, is conducive to large-scale production.But this polyimide that prior art provides is for yellow or brown, and color is comparatively dark, and the transparency is poor; And it is comparatively large to prepare the diamine monomer toxicity adopted in polyimide process, is Nonrenewable resources.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of polyimide and preparation method thereof, polyimide provided by the invention has the good transparency; And the diamine adopted when preparing polyimide is renewable resources.Environmentally friendly.
The invention provides a kind of polyimide, there is the structure shown in formula I:
In formula I, R is that after aromatic diacid acid anhydride removes end oxygen base, remaining group or aliphatic diacid acid anhydride remove remaining group after end oxygen base;
N is the polymerization degree, 1≤n≤1000.
Preferably, the R in described formula I is for having the one in the group of structure shown in formula 1 ~ formula 17:
The invention provides a kind of preparation method of polyimide, comprising:
Diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide, temperature >=150 DEG C of described reaction; Described diamine for having one or more in structural compounds shown in formula II ~ formula IV,
Preferably, the reaction times of polyimide is prepared in temperature >=200 DEG C is 1 hour ~ 5 hours.
The invention provides a kind of preparation method of polyimide, comprising:
Diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide; Temperature≤40 DEG C of described reaction; Described diamine for having one or more in the structural compounds shown in formula II ~ formula IV,
Preferably, the reaction times of polyimide is prepared in temperature≤40 DEG C is 10 hours ~ 24 hours.
The invention provides a kind of preparation method of polyimide, comprising:
Under the effect of catalyzer, diamine and dibasic acid anhydride are reacted in a solvent, obtain polyimide, described diamine for having one or more in the structural compounds shown in formula II ~ formula IV,
Preferably, the reaction times of catalyst preparing polyimide is 8 hours ~ 15 hours.
Preferably, described catalyzer is triethylamine or pyridine.
The invention provides a kind of polyimide film, prepared by polyimide described in technique scheme; Or the polyimide to be prepared by method described in technique scheme prepares.
The invention provides a kind of polyimide, have the structure shown in formula I, in formula I, R is that after aromatic diacid acid anhydride removes end oxygen base, remaining group or aliphatic diacid acid anhydride remove remaining group after end oxygen base; N is the polymerization degree, 1≤n≤1000.Polyimide transparent provided by the invention is better.Experimental result shows, polyimide provided by the invention is prepared into the Kapton that thickness is 15 microns ~ 25 microns, the transmittance > 80% of described Kapton.
In addition, polyimide environmentally safe provided by the invention; Better heat stability; Second-order transition temperature is higher; Mechanical property is better.Experimental result shows, second-order transition temperature >=200 DEG C of polyimide provided by the invention, thermal weight loss temperature >=400 DEG C of 5%; Tensile strength is for reaching as high as 130MPa, and Young's modulus reaches as high as 3.6GPa, and elongation at break is up to 51%.
The invention provides a kind of preparation method of polyimide, comprising: diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide, temperature >=150 DEG C of described reaction; Described diamine is for having one or more in structural compounds shown in formula II ~ formula IV.The invention provides a kind of preparation method of polyimide, comprising: diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide; Temperature≤40 DEG C of described reaction; Described diamine is for having one or more in the structural compounds shown in formula II ~ formula IV.The invention provides a kind of preparation method of polyimide, comprise: under the effect of catalyzer, diamine and dibasic acid anhydride are reacted in a solvent, obtain polyimide, described diamine is for having one or more in the structural compounds shown in formula II ~ formula IV.The polyimide transparent that method provided by the invention prepares is better.In addition, the diamine that method provided by the invention adopts in the process preparing polyimide is renewable resources, environmentally friendly; And the polyimide environmentally safe prepared; Better heat stability; Second-order transition temperature is higher; Mechanical property is better; Preparation method's technique of polyimide provided by the invention is simple, easy and simple to handle in addition.
The invention provides a kind of polyimide film, prepared by polyimide described in technique scheme; Or polyimide prepared by method described in technique scheme prepares.The polyimide film transparency provided by the invention better.Experimental result shows, the transmittance > 80% of Kapton provided by the invention.In addition, polyimide film provided by the invention is prepared by reproducible diamine, environmentally friendly; And polyimide film environmentally safe provided by the invention; Better heat stability; Second-order transition temperature is higher; Mechanical property is better.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the nmr spectrum of the diamine that the embodiment of the present invention 1 prepares;
Fig. 2 is the ultraviolet-visible light spectrogram of the polyimide that the embodiment of the present invention 2 prepares;
Fig. 3 is the hot weightless picture of the polyimide that the embodiment of the present invention 2 prepares;
Fig. 4 is the infrared spectrum of the polyimide that the embodiment of the present invention 2 prepares.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of polyimide, there is the structure shown in formula I:
In formula I, R is that after aromatic diacid acid anhydride removes end oxygen base, remaining group or aliphatic diacid acid anhydride remove remaining group after end oxygen base;
N is the polymerization degree, 1≤n≤1000.
Polyimide transparent provided by the invention is better.In addition, polyimide environmentally safe provided by the invention; Better heat stability; Second-order transition temperature is higher; Mechanical property is better.
In the present invention, the R in described formula I is that after aromatic diacid acid anhydride removes end oxygen base, remaining group or aliphatic diacid acid anhydride remove remaining group after end oxygen base; Preferably there is the one in the group of structure shown in formula 1 ~ formula 17:
Be more preferably the one in the group with structure shown in formula 1, formula 3, formula 6, formula 7 or formula 13.
In the present invention, described n is the polymerization degree, 1≤n≤1000.Preferably, 50≤n≤800; Preferred, 100≤n≤500; Most preferred, 200≤n≤300.
The invention provides a kind of preparation method of polyimide, comprising:
Diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide, temperature >=200 DEG C of described reaction; Described diamine for having one or more in structural compounds shown in formula II ~ formula IV,
The polyimide transparent that method provided by the invention prepares is better.In addition, the diamine that method provided by the invention adopts in the process preparing polyimide is renewable resources, environmentally friendly; And the environmentally safe of the polyimide prepared; Better heat stability; Second-order transition temperature is higher; Mechanical property is better; Preparation method's technique of polyimide provided by the invention is simple, easy and simple to handle in addition.
Diamine and dibasic acid anhydride react by the present invention in a solvent, obtain polyimide, temperature >=150 DEG C of described reaction, and described solvent is designated as the first solvent, and described reaction is designated as the first reaction.The present invention preferably carries out described first reaction under the condition of protective gas.In the present invention, described protective gas is preferably nitrogen or rare gas element, is more preferably nitrogen.The present invention preferably carries out described first reaction under the condition stirred.The method of the present invention to described stirring does not have special restriction, adopts stirring technique scheme well known to those skilled in the art.In the present invention, the speed of described stirring is preferably 500 revs/min ~ 1500 revs/min, is more preferably 1000 revs/min.In the present invention, the temperature of described first reaction is more preferably 160 DEG C ~ 250 DEG C, most preferably is 180 DEG C ~ 220 DEG C.In the present invention, the time of described first reaction is preferably 8 hours ~ 20 hours, is more preferably 10 hours ~ 15 hours.
In the present invention, described diamine is for having one or more in structural compounds shown in formula II ~ formula IV.In the present invention, the preparation method of described diamine is preferably:
By Isosorbide-5-Nitrae: the two dewatering hexitol of 3,6-carries out drop cloth riel primary amine (Gabriel) building-up reactions, obtains diamine.
The present invention is more preferably by Isosorbide-5-Nitrae: the two dewatering hexitol of 3,6-and sulfonyl compound carry out sulfonylation, obtain the first intermediate product; Described first intermediate product and imide salts are carried out imidization reaction, obtains the second intermediate product; Described second intermediate product is hydrolyzed, alkaline purification, obtain diamine.
The present invention is preferably by Isosorbide-5-Nitrae: the two dewatering hexitol of 3,6-and sulfonyl compound carry out sulfonylation, obtain the first intermediate product.In the present invention, the temperature of described sulfonylation is preferably 0 DEG C ~ 10 DEG C, is more preferably 1 DEG C ~ 5 DEG C.In the present invention, the time of described sulfonylation is preferably 10 hours ~ 20 hours, is more preferably 15 hours ~ 18 hours.The present invention preferably carries out described sulfonylation under the condition of protective gas.In the present invention, described protective gas is preferably nitrogen or rare gas element, is more preferably nitrogen.
The source of the present invention to the two dewatering hexitol of described Isosorbide-5-Nitrae: 3,6-does not have special restriction, can be bought obtain by market, can prepare according to the preparation method of the two dewatering hexitol of Isosorbide-5-Nitrae well known to those skilled in the art: 3,6-yet.In the present invention, the two dewatering hexitol of described Isosorbide-5-Nitrae: 3,6-comprises one or more in Isosorbide, isomannite and iditol.In the present invention, the two dewatering hexitol of described Isosorbide-5-Nitrae: 3,6-is preferably Isosorbide-5-Nitrae: the two anhydrohexose alcoholic solution of 3,6-.In the present invention, the solvent in the two anhydrohexose alcoholic solution of described Isosorbide-5-Nitrae: 3,6-is preferably one or more in pyridine, methylene dichloride and triethylamine.In the present invention, the mass concentration of the two anhydrohexose alcoholic solution of described Isosorbide-5-Nitrae: 3,6-is preferably 0.5g/mL ~ 1.5g/mL, is more preferably 0.8g/mL ~ 1.2g/mL, most preferably is 1g/mL.
In the present invention, the sulfonyl group in described sulfonyl compound is preferably Methyl benzenesulfonyl base, tnBuoromethyl-benzenesulfonyl or Methyl benzenesulfonyl base.In the present invention, described sulfonyl compound is preferably toluene sulfonyl chloride.The source of the present invention to described sulfonyl compound does not have special restriction, can be bought obtain by market.In the present invention, described sulfonyl compound is preferably sulfonyl compound solution.In the present invention, the solvent in described sulfonyl compound solution is preferably one or more in pyridine, methylene dichloride and triethylamine.In the present invention, the mass concentration of described sulfonyl compound solution is preferably 2g/mL ~ 3g/mL, is more preferably 2.4g/mL ~ 2.8g/mL, most preferably is 2.6g/mL.
In the present invention, the mass ratio of the two dewatering hexitol of described Isosorbide-5-Nitrae: 3,6-and sulfonyl compound is preferably 1:(2 ~ 3), be more preferably 1:2.5.
After described sulfonylation completes, the reaction product obtained preferably extracts by the present invention, recrystallization, obtains the first intermediate product.In the present invention, the solvent of described extraction is preferably methylene dichloride.In the present invention, the reagent of described recrystallization is preferably one or more in ketone compounds and alcohol compound, is more preferably acetone, methyl alcohol, ethanol or Virahol.Before being extracted by sulfonylation product, sulfonylation product preferably processes by the present invention in frozen water.
After obtaining the first intermediate product, described first intermediate product and imide salts are preferably carried out imidization reaction by the present invention, obtain the second intermediate product.The present invention preferably carries out described imidization reaction under the condition of organic solvent.In the present invention, the organic solvent of described imidization reaction is preferably one or more in DMF, N,N-dimethylacetamide and dimethyl sulfoxide (DMSO).The consumption of the present invention to described organic solvent does not have special restriction, can provide liquid environment for described imidization reaction.The present invention preferably carries out described imidization reaction under the condition of protective gas.In the present invention, described protective gas is consistent with protective gas described in technique scheme, does not repeat them here.
In the present invention, the temperature of described imidization reaction is preferably 110 DEG C ~ 130 DEG C, is more preferably 120 DEG C.In the present invention, the time of described imidization reaction is preferably 8 hours ~ 20 hours, is more preferably 10 hours ~ 15 hours.In the present invention, the mass ratio of described first intermediate product and imide salts is preferably (0.5 ~ 1.5): 1, is more preferably (0.8 ~ 1.2): 1, most preferably is 1:1.
In the present invention, described imide salts is preferably one or more in phthalimide potassium, N-bromo-succinimide and N-N-iodosuccinimide, is more preferably phthalimide potassium, N-bromo-succinimide or N-N-iodosuccinimide.The source of the present invention to described imide salts does not have special restriction, can be bought obtain by market.
After described imidization reaction completes, the imidization reaction product obtained preferably carries out extracting, revolving steaming, recrystallization by the present invention, obtains the second intermediate product.In the present invention, the reagent of described extraction and recrystallization extract with described in technique scheme and the reagent of recrystallization consistent, do not repeat them here.The present invention does not have special restriction to described method of revolving steaming, adopts well known to those skilled in the artly to revolve steaming technique scheme.
After obtaining the second intermediate product, described second intermediate product is preferably hydrolyzed by the present invention, alkaline purification, obtains diamine.In the present invention, described hydrolysis is preferably acidolysis or alkaline hydrolysis, is more preferably acidolysis.In the present invention, the acid of described acidolysis is preferably one or more in hydrochloric acid, phosphoric acid, acetic acid and formic acid, is more preferably hydrochloric acid.In the present invention, the alkali of described alkaline hydrolysis is preferably one or more in hydrazine hydrate, sodium hydroxide and potassium hydroxide.
In the present invention, the temperature of described hydrolysis is preferably 110 DEG C ~ 140 DEG C, is more preferably 120 DEG C ~ 130 DEG C.In the present invention, the time of described hydrolysis is preferably 10 hours ~ 24 hours, is more preferably 15 hours ~ 30 hours.After described hydrolysis completes, the hydrolysate obtained preferably filters by the present invention, wash, revolve steaming, oven dry.The present invention to described filtration, wash, revolve steam and dry method there is no special restriction, adopt filtration well known to those skilled in the art, wash, revolve steam and dry technical scheme.In the present invention, the reagent washing described hydrolysate is preferably ether.
After described hydrolysis completes, the hydrolysate obtained preferably is carried out alkaline purification by the present invention, obtains diamine.Described hydrolysate deacidite is more preferably carried out alkaline purification by the present invention, obtains diamine.The source of the present invention to described deacidite does not have special restriction, can be bought obtain by market.In an embodiment of the present invention, described deacidite can be 201 × 7 strongly basic anion exchange resins, also can be 717 strongly basic anion exchange resins, can also be D301 strongly basic anion exchange resin, can also be D201 strongly basic anion exchange resin.
In the present invention, the temperature of described alkaline purification is preferably 20 DEG C ~ 40 DEG C, is more preferably 30 DEG C.In the present invention, the time of described alkaline purification is preferably 1 hour ~ 5 hours, is more preferably 2 hours ~ 4 hours.
Before described hydrolysate is carried out alkaline purification, the present invention is preferably by soluble in water for described hydrolysate.
After described alkaline purification completes, the alkaline purification product obtained preferably filters, revolves steaming, recrystallization by the present invention, obtains diamine.The present invention to described filtration, revolve steaming and the method for recrystallization does not have special restriction, adopt filtration well known to those skilled in the art, revolve the technical scheme of steaming and recrystallization.In the present invention, the reagent of recrystallization alkaline purification product is preferably alcoholic solvent.
In the present invention, described dibasic acid anhydride preferably has the one in structural compounds shown in formula 18 ~ 34:
Be more preferably the one had in structural compounds shown in formula 18, formula 23, formula 24 or formula 30.The source of the present invention to described dibasic acid anhydride does not have special restriction, can be bought obtain by market.
In the present invention, described first solvent is preferably one or more in phenolic compound and sulfone compound, is more preferably one or more in meta-cresol, para-chlorophenol and tetramethylene sulfone.In the present invention, the mol ratio of described diamine and dibasic acid anhydride is preferably (0.5 ~ 1.5): 1, is more preferably (0.8 ~ 1.2): 1, most preferably is 1:1.The consumption of the present invention to described first solvent does not have special restriction, and the consumption of described first solvent can make diamine and dibasic acid anhydride dissolve.
Described first reacted after, the first reaction product precipitation agent obtained preferably is separated out by the present invention, washing, dry, obtains polyimide.In the present invention, described precipitation agent is preferably ketone compounds or alcohol compound, is more preferably acetone, ethanol or methyl alcohol.In the present invention, the reagent washing described first reaction product is preferably one or more in alcohol compound, is more preferably one or more in methyl alcohol, ethanol and Virahol.The method of the present invention to described first reaction product of drying does not have special restriction, adopts dry technology scheme well known to those skilled in the art.
Before being separated out by described first reaction product precipitation agent, described first reaction product is preferably carried out cooling process by the present invention.In the present invention, the temperature of cooling process first reaction product is preferably 80 DEG C ~ 100 DEG C, is more preferably 90 DEG C.
The invention provides a kind of preparation method of polyimide, comprising:
Diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide; Temperature≤40 DEG C of described reaction; Described diamine for having one or more in the structural compounds shown in formula II ~ formula IV,
The polyimide transparent that method provided by the invention prepares is better.In addition, the diamine that method provided by the invention adopts in the process preparing polyimide is renewable resources, environmentally friendly; And the polyimide environmentally safe prepared; Better heat stability; Second-order transition temperature is higher; Mechanical property is better; Preparation method's technique of polyimide provided by the invention is simple, easy and simple to handle in addition.
Diamine and dibasic acid anhydride react by the present invention in a solvent, obtain polyimide; Temperature≤40 DEG C of described reaction, are designated as the second solvent by described solvent, and described reaction is designated as the second reaction.In the present invention, the temperature of described second reaction is more preferably 10 DEG C ~ 30 DEG C, most preferably is 15 DEG C ~ 25 DEG C.In the present invention, the time of described second reaction is preferably 10 hours ~ 24 hours, is more preferably 15 hours ~ 20 hours.
In the present invention, described second solvent is preferably one or more in chloroform, DMF, N,N-dimethylacetamide and N-Methyl pyrrolidone.The consumption of the present invention to described second solvent does not have special restriction, can provide liquid environment for described second reaction.In the present invention, the kind of the kind of described diamine and dibasic acid anhydride and source and diamine described in technique scheme and dibasic acid anhydride with originate consistent, do not repeat them here.In the present invention, described diamine is consistent with the mol ratio of diamine described in technique scheme and dibasic acid anhydride with the mol ratio of dibasic acid anhydride, does not repeat them here.
Described second reacted after, the second reaction product that the present invention preferably will obtain is dry, obtains polyimide.The method of the present invention to described second reaction product of drying does not have special restriction, adopts dry technology scheme well known to those skilled in the art.
The invention provides a kind of preparation method of polyimide, comprising:
Under the effect of catalyzer, diamine and dibasic acid anhydride are reacted in a solvent, obtain polyimide, described diamine for having one or more in the structural compounds shown in formula II ~ formula IV,
The polyimide transparent that method provided by the invention prepares is better.In addition, the diamine that method provided by the invention adopts in the process preparing polyimide is renewable resources, environmentally friendly; And the polyimide environmentally safe prepared; Better heat stability; Second-order transition temperature is higher; Mechanical property is better; Preparation method's technique of polyimide provided by the invention is simple, easy and simple to handle in addition.
Diamine and dibasic acid anhydride, under the effect of catalyzer, react, obtain polyimide by the present invention in a solvent, and described solvent is designated as the 3rd solvent, and described reaction is designated as the 3rd reaction.In the present invention, the temperature of described 3rd reaction is preferably 20 DEG C ~ 30 DEG C, is more preferably 24 DEG C ~ 26 DEG C.In the present invention, the time of described 3rd reaction is preferably 8 hours ~ 15 hours, is more preferably 10 hours ~ 12 hours.The present invention preferably carries out described 3rd reaction under the condition of protective gas.In the present invention, described protective gas is preferably nitrogen or rare gas element, is more preferably rare gas element, most preferably is argon gas.
In the present invention, described catalyzer is preferably triethylamine or pyridine.In the present invention, described 3rd solvent is preferably one or more in chloroform, DMF, N,N-dimethylacetamide and N-Methyl pyrrolidone.In the present invention, the kind of the kind of described diamine and dibasic acid anhydride and source and diamine described in technique scheme and dibasic acid anhydride with originate consistent, do not repeat them here.
Diamine, dibasic acid anhydride and diacetyl oxide, preferably under the effect of catalyzer, react, obtain polyimide by the present invention in a solvent.In the present invention, the volume ratio of described catalyzer and diacetyl oxide is preferably (1 ~ 2): 1, is more preferably (1.2 ~ 1.8): 1, most preferably is 1.5:1.In the present invention, the mole number of described diacetyl oxide is preferably 2 times ~ 3 times of catalyzer and the total mole number of diamine.In the present invention, described diamine is consistent with the mol ratio of diamine described in technique scheme and dibasic acid anhydride with the mol ratio of dibasic acid anhydride, does not repeat them here.
Described 3rd reacted after, the 3rd reaction product precipitation agent obtained preferably is separated out by the present invention, washing, dry, obtains polyimide.In the present invention, described precipitation agent is consistent with precipitation agent described in technique scheme, does not repeat them here.The method of the present invention to washing and dry 3rd reaction product does not have special restriction, adopts washing well known to those skilled in the art and dry technical scheme.
The invention provides a kind of polyimide film, prepared by polyimide described in technique scheme; Or polyimide prepared by method described in technique scheme prepares.
The polyimide film transparency provided by the invention better.In addition, polyimide film provided by the invention is prepared by reproducible diamine, environmentally friendly; And polyimide film environmentally safe provided by the invention; Better heat stability; Second-order transition temperature is higher; Mechanical property is better.
In the present invention, the preparation method of described polyimide film is preferably:
Polyimide is dissolved in organic solvent, obtains polyimide solution;
Described polyimide solution is coated in substrate dry, obtains polyimide film.
In the present invention, described polyimide is consistent with polyimide described in technique scheme, or consistent with the polyimide that method described in technique scheme prepares, and does not repeat them here.In the present invention, the organic solvent dissolving described polyimide is preferably DMF or N,N-dimethylacetamide.In the present invention, the mass concentration of described polyimide solution is preferably 10% ~ 15%, is more preferably 12%.
After obtaining polyimide solution, described polyimide solution is preferably coated in substrate dry by the present invention, obtains polyimide film.In the present invention, described matrix is preferably glass, is more preferably clean glass.In the present invention, described polyimide solution is coated in suprabasil thickness and is preferably 15 microns ~ 25 microns, is more preferably 20 microns.In the present invention, the method for described coating preferably scrapes embrane method.In the present invention, the method for the polyimide solution after dry coating is preferably dries.In the present invention, the temperature of the polyimide solution after dry coating is preferably 60 DEG C ~ 100 DEG C, is more preferably 70 DEG C ~ 90 DEG C, most preferably is 100 DEG C.In the present invention, the time of the polyimide solution after dry coating is preferably 20 hours ~ 30 hours, is more preferably 24 hours ~ 26 hours.
Be coated in substrate after drying by described polyimide solution, the desciccate obtained preferably is heat-treated by the present invention, obtains polyimide film.In the present invention, described heat treated temperature is preferably 80 DEG C ~ 260 DEG C, is more preferably 150 DEG C ~ 200 DEG C.In the present invention, the described heat treated time is preferably 4 hours ~ 8 hours, is more preferably 6 hours.
The present invention is preferably segmented carries out described thermal treatment, by described desciccate in the first temperature very first time, obtains the first process product, and described first temperature is 80 DEG C ~ 120 DEG C, and the described very first time is 1 hour ~ 3 hours; By described first process product in the second temperature second time, obtain the second process product, described second temperature is 130 DEG C ~ 170 DEG C, and described second time is 1 hour ~ 3 hours; By described second process product in the 3rd temperature the 3rd time, obtain the 3rd process product, described 3rd temperature is 180 DEG C ~ 220 DEG C, and described 3rd time is 0.5 hour ~ 1.5 hours; By described 3rd process product in the 4th temperature the 4th time, obtain polyimide film, described 4th temperature is 240 DEG C ~ 260 DEG C, and described 4th time is 0.5 hour ~ 1.5 hours.
In the present invention, described first temperature is more preferably 90 DEG C ~ 110 DEG C, most preferably is 100 DEG C.In the present invention, the described very first time is more preferably 2 hours.In the present invention, described second temperature is more preferably 140 DEG C ~ 160 DEG C, most preferably is 150 DEG C.In the present invention, described second time is more preferably 2 hours.In the present invention, described 3rd temperature is more preferably 190 DEG C ~ 210 DEG C, most preferably is 200 DEG C.In the present invention, described 3rd time is more preferably 1 hour.In the present invention, described 4th temperature is more preferably 245 DEG C ~ 255 DEG C, most preferably is 250 DEG C.In the present invention, described 4th time is more preferably 1 hour.
After described thermal treatment completes, the present invention preferably by obtain heat-treated products cooling, demoulding, drying, obtain polyimide film.In the present invention, the cooling temperature of described heat-treated products is preferably 20 DEG C ~ 30 DEG C, is more preferably 25 DEG C.Heat-treated products after cooling is preferably carried out the demoulding with water by the present invention.In the present invention, the method for dry demoulding after product is preferably and dries.
Adopt the method for infrared detection, test the structure of polyimide provided by the invention, test result is, polyimide provided by the invention has the structure shown in formula I.Polyimide provided by the invention is prepared into according to the method described in technique scheme the polyimide film that thickness is 15 microns ~ 25 microns, the method of uv-vis spectra is adopted to test its transparency, test result is, the transmittance > 80% of the polyimide film that polyimide provided by the invention prepares.Carry out thermogravimetric analysis test to polyimide provided by the invention, test result is, second-order transition temperature >=200 DEG C of polyimide provided by the invention, thermal weight loss temperature >=400 DEG C of 5%.Adopt universal testing machine to test the mechanical property of polyimide provided by the invention, test result is, the tensile strength of polyimide provided by the invention reaches as high as 130MPa, and Young's modulus reaches as high as 3.6 GPa, and elongation at break reaches as high as 51%.
The invention provides a kind of polyimide, have the structure shown in formula I, in formula I, R is that after aromatic diacid acid anhydride removes end oxygen base, remaining group or aliphatic diacid acid anhydride remove remaining group after end oxygen base; N is the polymerization degree, 1≤n≤1000.Polyimide transparent provided by the invention is better.In addition, polyimide environmentally safe provided by the invention; Better heat stability; Second-order transition temperature is higher; Mechanical property is better.
The invention provides a kind of preparation method of polyimide, comprising: diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide, temperature >=150 DEG C of described reaction; Described diamine is for having one or more in structural compounds shown in formula II ~ formula IV.The invention provides a kind of preparation method of polyimide, comprising: diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide; Temperature≤40 DEG C of described reaction; Described diamine is for having one or more in the structural compounds shown in formula II ~ formula IV.The invention provides a kind of preparation method of polyimide, comprise: under the effect of catalyzer, diamine and dibasic acid anhydride are reacted in a solvent, obtain polyimide, described diamine is for having one or more in the structural compounds shown in formula II ~ formula IV.The polyimide transparent that method provided by the invention prepares is better.In addition, the diamine that method provided by the invention adopts in the process preparing polyimide is renewable resources, environmentally friendly; And the polyimide environmentally safe prepared; Better heat stability; Second-order transition temperature is higher; Mechanical property is better; Preparation method's technique of polyimide provided by the invention is simple, easy and simple to handle in addition.
The invention provides a kind of polyimide film, prepared by polyimide described in technique scheme; Or polyimide prepared by method described in technique scheme prepares.The polyimide film transparency provided by the invention better.In addition, polyimide film provided by the invention is prepared by reproducible diamine, environmentally friendly; And polyimide film environmentally safe provided by the invention; Better heat stability; Second-order transition temperature is higher; Mechanical property is better.
Raw material used by following examples of the present invention is commercial goods.
Embodiment 1
Under the protection of nitrogen, to with magnetic agitation three-necked bottle in, add the different mannitol of 50g, the pyridine of 100mL, the p-methyl benzene sulfonic chloride of 130g carries out the sulfonylation of 3 hours, the reaction product obtained is contained in frozen water, with water and dilute hydrochloric acid washing, with acetone recrystallization, obtains the first intermediate product;
Under the protection of nitrogen, in the three-necked bottle of 1000mL, add the phthalimide potassium of above-mentioned first intermediate product of 50g and 50g, then in described three-necked bottle, add the dimethyl sulfoxide (DMSO) of 500mL, at 110 DEG C, carry out the imidization reaction of 20 hours; The reaction product obtained is cooled to 25 DEG C, contains in deionized water; By 200mL dichloromethane extraction 3 times, dried over mgso, filter, revolve steaming, obtain the second intermediate product;
To in the three-necked bottle of 250mL being furnished with magnetic agitation, to add above-mentioned second intermediate product of 20g and 125mL volumetric molar concentration be 2mol/L volume ratio is the acetic acid of 1:1 and the mixed aqueous solution of hydrochloric acid, the acidolysis of 15h is carried out at 120 DEG C, the acid hydrolysate obtained is cooled to 25 DEG C, filters, the ethyl acetate of the filtrate 100mL obtained is washed 2 times, aqueous phase after washing is revolved steaming, carrying out reflow treatment by revolving the product ethanol after steaming, filtering, the filter cake obtained is carried out vacuum drying;
Filter cake D301 strongly basic anion exchange resin after vacuum drying is carried out alkaline purification, is that the methyl alcohol of 1:1 and the mixture of ethanol carry out recrystallization by the alkaline purification product volume ratio obtained, obtains diamine.
The diamine embodiment of the present invention 1 prepared carries out nucleus magnetic resonance test, test result as shown in Figure 1, Fig. 1 is the nmr spectrum of the diamine that the embodiment of the present invention 1 prepares, and as shown in Figure 1, the diamine that the embodiment of the present invention 1 prepares has the structure shown in formula II.
Embodiment 2
In the polymerization bottle that mechanical stirring, nitrogen protection are housed, the diamine that the embodiment 1 adding 0.4342g prepares, the triethylamine of 0.5g, then in described polymerization bottle, add the meta-cresol of 4.3500g, be stirred at 25 DEG C and dissolve completely; In the solution obtained, add the compound with structure shown in formula 18 of 1.0410g, stir 2h at 80 DEG C after, at 200 DEG C, carry out the reaction of 10h; The reaction product obtained is cooled to 100 DEG C, separates out with ethanol, by the precipitate obtained 100 DEG C, dry under vacuum, obtain polyimide.
The above-mentioned polyimide N,N-dimethylacetamide prepared is mixed with the polyimide solution that mass content is 15%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 15 microns; Described sheet glass is dried 24 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 200 DEG C, be incubated 1h, at 250 DEG C, be incubated 1h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that the embodiment of the present invention 2 prepares, according to the method described in technique scheme, test its transparency, as shown in Figure 2, Fig. 2 is the ultraviolet-visible light spectrogram of the polyimide that the embodiment of the present invention 2 prepares to test result.As shown in Figure 2, the transmittance > 80% of polyimide film prepared by the polyimide that the embodiment of the present invention 2 provides, the transparency better.
According to method described in technique scheme, carry out thermogravimetic analysis (TGA) to the polyimide that the embodiment of the present invention 2 prepares, as shown in Figure 3, Fig. 3 is the hot weightless picture of the polyimide that the embodiment of the present invention 2 obtains to test result.As shown in Figure 3, the second-order transition temperature of the polyimide that the embodiment of the present invention 2 prepares is 219 DEG C, and the thermal weight loss temperature of 5% is 459 DEG C, better heat stability.
According to the method described in technique scheme, the structure of the polyimide that the test embodiment of the present invention 2 prepares, as shown in Figure 4, Fig. 4 is the infrared spectrum of the polyimide that the embodiment of the present invention 2 prepares to test result.As shown in Figure 4, the polyimide that the embodiment of the present invention 2 prepares has the structure shown in formula 35:
In formula 35, n is 55.
According to the method described in technique scheme, the mechanical property of the polyimide that the test embodiment of the present invention 2 prepares, test result is, the tensile strength of the polyimide that the embodiment of the present invention 2 prepares is 103.23MPa, Young's modulus is 3.43GPa, elongation at break is 44.39%, and mechanical property is better.
Embodiment 3
In the polymerization bottle that mechanical stirring, nitrogen protection are housed, the diamine that the embodiment 1 adding 0.6513g prepares, the triethylamine of 0.6g, then in described polymerization bottle, add the meta-cresol of 4.7600g, be stirred at 25 DEG C and dissolve completely; In the solution obtained, add the compound with structure shown in formula 23 of 0.8827g, after stirring 2h at 90 DEG C, at 180 DEG C, carry out the reaction of 10h; The reaction product obtained is cooled to 80 DEG C, separates out with ethanol, by the precipitate obtained 100 DEG C, dry under vacuum, obtain polyimide.
The above-mentioned polyimide meta-cresol prepared is mixed with the polyimide solution that mass content is 10%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 20 microns; Described sheet glass is dried 24 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 200 DEG C, be incubated 1h, at 250 DEG C, be incubated 1h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that the embodiment of the present invention 3 prepares, according to the method described in technique scheme, test its transparency, test result is, the transmittance of polyimide film prepared by the polyimide that the embodiment of the present invention 3 provides is 82%, and the transparency better.
According to method described in technique scheme, carry out thermogravimetic analysis (TGA) to the polyimide that the embodiment of the present invention 3 prepares, test result is, the second-order transition temperature of the polyimide that the embodiment of the present invention 3 prepares is 318 DEG C, the thermal weight loss temperature of 5% is 448 DEG C, better heat stability.
According to the method described in technique scheme, the structure of the polyimide that the test embodiment of the present invention 3 prepares, test result is, the polyimide that the embodiment of the present invention 3 prepares has the structure shown in formula 36:
In formula 36, n is 60.
According to the method described in technique scheme, the mechanical property of the polyimide that the test embodiment of the present invention 3 prepares, test result is, the tensile strength of the polyimide that the embodiment of the present invention 3 obtains is 89.7MPa, Young's modulus is 3.54GPa, elongation at break is 50.94%, and mechanical property is better.
Embodiment 4
In the polymerization bottle that mechanical stirring, nitrogen protection are housed, the diamine that the embodiment 1 adding 0.6513g prepares, the triethylamine of 1.0g, then in described polymerization bottle, add the meta-cresol of 4.600g, be stirred at 25 DEG C and dissolve completely; In the solution obtained, add the compound with structure shown in formula 30 of 0.6725g, stir 2h at 85 DEG C after, at 185 DEG C, carry out the reaction of 10h; The reaction product obtained is cooled to 90 DEG C, separates out with ethanol, by the precipitate obtained 120 DEG C, dry under vacuum, obtain polyimide.
The above-mentioned polyimide N,N-dimethylacetamide prepared is mixed with the polyimide solution that mass content is 15%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 25 microns; Described sheet glass is dried 24 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 250 DEG C, be incubated 1h, at 280 DEG C, be incubated 1h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that the embodiment of the present invention 4 prepares, according to the method described in technique scheme, test its transparency, test result is, the transmittance of polyimide film prepared by the polyimide that the embodiment of the present invention 4 provides is 84%, and the transparency better.
According to method described in technique scheme, carry out thermogravimetic analysis (TGA) to the polyimide that the embodiment of the present invention 4 prepares, test result is, the second-order transition temperature of the polyimide that the embodiment of the present invention 4 prepares is 322 DEG C, the thermal weight loss temperature of 5% is 397 DEG C, better heat stability.
According to the method described in technique scheme, the structure of the polyimide that the test embodiment of the present invention 4 prepares, test result is, the polyimide that the embodiment of the present invention 4 prepares has the structure shown in formula 37:
In formula 37, n is 85.
According to the method described in technique scheme, the mechanical property of the polyimide that the test embodiment of the present invention 4 prepares, test result is, the tensile strength of the polyimide that the embodiment of the present invention 4 prepares is 101.77MPa, Young's modulus is 2.53GPa, elongation at break is 9.21%, and mechanical property is better.
Embodiment 5
In the polymerization bottle that mechanical stirring, nitrogen protection are housed, the diamine that the embodiment 1 adding 0.8684g prepares, the triethylamine of 2.0g, then in described polymerization bottle, add the meta-cresol of 6g, be stirred at 25 DEG C and dissolve completely; In the solution obtained, add the compound with structure shown in formula 24 of 1.770g, stir 2h at 90 DEG C after, at 210 DEG C, carry out the reaction of 10h; The reaction product obtained is cooled to 70 DEG C, separates out with ethanol, will obtain precipitate 150 DEG C, dry under vacuum, obtain polyimide.
The above-mentioned polyimide N,N-dimethylacetamide prepared is mixed with the polyimide solution that mass content is 10%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 20 microns; Described sheet glass is dried 24 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 200 DEG C, be incubated 1h, at 250 DEG C, be incubated 1h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that the embodiment of the present invention 5 prepares, according to the method described in technique scheme, test its transparency, test result is, the transmittance of polyimide film prepared by the polyimide that the embodiment of the present invention 5 provides is 88%, and the transparency better.
According to method described in technique scheme, carry out thermogravimetic analysis (TGA) to the polyimide that the embodiment of the present invention 5 prepares, test result is, the second-order transition temperature of the polyimide that the embodiment of the present invention 5 prepares is 291 DEG C, the thermal weight loss temperature of 5% is 457 DEG C, better heat stability.
According to the method described in technique scheme, the structure of the polyimide that the test embodiment of the present invention 5 prepares, test result is, the polyimide that the embodiment of the present invention 5 prepares has the structure shown in formula 38:
In formula 38, n is 95.
According to the method described in technique scheme, the mechanical property of the polyimide that the test embodiment of the present invention 5 prepares, test result is, the tensile strength of the polyimide that the embodiment of the present invention 5 prepares is 113.67MPa, Young's modulus is 3.16GPa, elongation at break is 6.23%, and mechanical property is better.
Embodiment 6
In the polymerization bottle that mechanical stirring, nitrogen protection are housed, the diamine that the embodiment 1 adding 0.4342g prepares, the triethylamine of 0.6g, then in described polymerization bottle, add the meta-cresol of 4.3g, be stirred at 25 DEG C and dissolve completely; In the solution obtained, add the compound with structure shown in formula 18 of 1.0409g, stir 2h at 80 DEG C after, at 220 DEG C, carry out the reaction of 10h; The reaction product obtained is cooled to 80 DEG C, separates out with ethanol, by the precipitate obtained 180 DEG C, dry under vacuum, obtain polyimide.
The above-mentioned polyimide N,N-dimethylacetamide prepared is mixed with the polyimide solution that mass content is 10%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 20 microns; Described sheet glass is dried 24 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 200 DEG C, be incubated 1h, at 250 DEG C, be incubated 1h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that the embodiment of the present invention 6 prepares, according to the method described in technique scheme, test its transparency, test result is, the transmittance of polyimide film prepared by the polyimide that the embodiment of the present invention 6 provides is 85%, and the transparency better.
According to method described in technique scheme, carry out thermogravimetic analysis (TGA) to the polyimide that the embodiment of the present invention 6 prepares, test result is, the second-order transition temperature of the polyimide that the embodiment of the present invention 6 prepares is 214 DEG C, the thermal weight loss temperature of 5% is 462 DEG C, better heat stability.
According to the method described in technique scheme, the structure of the polyimide that the test embodiment of the present invention 6 prepares, test result is, the polyimide that the embodiment of the present invention 6 prepares has the structure shown in formula 39:
In formula 39, n is 78.
According to the method described in technique scheme, the mechanical property of the polyimide that the test embodiment of the present invention 6 prepares, test result is, the tensile strength of the polyimide that the embodiment of the present invention 6 prepares is 102.84MPa, Young's modulus is 3.25GPa, elongation at break is 10.35%, and mechanical property is better.
Embodiment 7
In the polymerization bottle that mechanical stirring, nitrogen protection are housed, the diamine that the embodiment 1 adding 0.6513g prepares, the triethylamine of 1.8g, then in described polymerization bottle, add the meta-cresol of 4.76g, be stirred at 25 DEG C and dissolve completely; In the solution obtained, add the compound with structure shown in formula 23 of 0.8827g, stir 2h at 80 DEG C after, at 200 DEG C, carry out the reaction of 10h; The reaction product obtained is cooled to 100 DEG C, separates out with ethanol, by the precipitate obtained 100 DEG C, dry under vacuum, obtain polyimide.
The above-mentioned polyimide N,N-dimethylacetamide prepared is mixed with the polyimide solution that mass content is 10%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 20 microns; Described sheet glass is dried 24 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 200 DEG C, be incubated 1h, at 250 DEG C, be incubated 1h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that the embodiment of the present invention 7 prepares, according to the method described in technique scheme, test its transparency, test result is, the transmittance of polyimide film prepared by the polyimide that the embodiment of the present invention 7 provides is 84%, and the transparency better.
According to method described in technique scheme, carry out thermogravimetic analysis (TGA) to the polyimide that the embodiment of the present invention 7 prepares, test result is, the second-order transition temperature of the polyimide that the embodiment of the present invention 7 prepares is 312 DEG C, the thermal weight loss temperature of 5% is 452 DEG C, better heat stability.
According to the method described in technique scheme, the structure of the polyimide that the test embodiment of the present invention 7 prepares, test result is, the polyimide that the embodiment of the present invention 7 prepares has the structure shown in formula 40:
In formula 40, n is 85.
According to the method described in technique scheme, the mechanical property of the polyimide that the test embodiment of the present invention 7 prepares, test result is, the tensile strength of the polyimide that the embodiment of the present invention 7 prepares is 129MPa, Young's modulus is 3.24GPa, elongation at break is 9.18%, and mechanical property is better.
Embodiment 8
In the polymerization bottle that mechanical stirring, nitrogen protection are housed, the diamine that the embodiment 1 adding 0.6513g prepares, the triethylamine of 2.0g, then in described polymerization bottle, add the meta-cresol of 4.6g, be stirred at 25 DEG C and dissolve completely; In the solution obtained, add the compound with structure shown in formula 30 of 0.6725g, stir 2h at 100 DEG C after, at 205 DEG C, carry out the reaction of 10h; The reaction product obtained is cooled to 90 DEG C, separates out with ethanol, by the precipitate obtained 100 DEG C, dry under vacuum, obtain polyimide.
The above-mentioned polyimide N,N-dimethylacetamide prepared is mixed with the polyimide solution that mass content is 15%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 20 microns; Described sheet glass is dried 24 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 200 DEG C, be incubated 1h, at 250 DEG C, be incubated 1h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that the embodiment of the present invention 8 prepares, according to the method described in technique scheme, test its transparency, test result is, the transmittance of polyimide film prepared by the polyimide that the embodiment of the present invention 8 provides is 85%, and the transparency better.
According to method described in technique scheme, carry out thermogravimetic analysis (TGA) to the polyimide that the embodiment of the present invention 8 prepares, test result is, the second-order transition temperature of the polyimide that the embodiment of the present invention 8 prepares is 320 DEG C, the thermal weight loss temperature of 5% is 378 DEG C, better heat stability.
According to the method described in technique scheme, the structure of the polyimide that the test embodiment of the present invention 8 prepares, test result is, the polyimide that the embodiment of the present invention 8 prepares has the structure shown in formula 41:
In formula 41, n is 90.
According to the method described in technique scheme, the mechanical property of the polyimide that the test embodiment of the present invention 8 prepares, test result is, the tensile strength of the polyimide that the embodiment of the present invention 8 obtains is 90MPa, Young's modulus is 3.5GPa, and elongation at break is 51%, and mechanical property is better.
Embodiment 9
In the polymerization bottle that mechanical stirring, nitrogen protection are housed, the diamine that the embodiment 1 adding 0.8684g prepares, the triethylamine of 2.5g, then in described polymerization bottle, add the meta-cresol of 6g, be stirred at 25 DEG C and dissolve completely; In the solution obtained, add the compound with structure shown in formula 24 of 1.7769g, stir 2h at 80 DEG C after, at 200 DEG C, carry out the reaction of 10h; The reaction product obtained is cooled to 100 DEG C, separates out with ethanol, by the precipitate obtained 100 DEG C, dry under vacuum, obtain polyimide.
The above-mentioned polyimide N,N-dimethylacetamide prepared is mixed with the polyimide solution that mass content is 15%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 20 microns; Described sheet glass is dried 24 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 200 DEG C, be incubated 1h, at 250 DEG C, be incubated 1h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that the embodiment of the present invention 9 prepares, according to the method described in technique scheme, test its transparency, test result is, the transmittance of polyimide film prepared by the polyimide that the embodiment of the present invention 9 provides is 89%, and the transparency better.
According to method described in technique scheme, carry out thermogravimetic analysis (TGA) to the polyimide that the embodiment of the present invention 9 prepares, test result is, the second-order transition temperature of the polyimide that the embodiment of the present invention 9 prepares is 250 DEG C, the thermal weight loss temperature of 5% is 400 DEG C, better heat stability.
According to the method described in technique scheme, the structure of the polyimide that the test embodiment of the present invention 9 prepares, test result is, the polyimide that the embodiment of the present invention 9 prepares has the structure shown in formula 42:
In formula 42, n is 8.
According to the method described in technique scheme, the mechanical property of the polyimide that the test embodiment of the present invention 9 prepares, test result is, the tensile strength of the polyimide that the embodiment of the present invention 9 prepares is 100MPa, Young's modulus is 2.5GPa, elongation at break is 4.5%, and mechanical property is better.
Embodiment 10
In the polymerization bottle that mechanical stirring, nitrogen protection are housed, the diamine that the embodiment 1 adding 0.6513g prepares, the triethylamine of 1.8g, then in described polymerization bottle, add the N,N-dimethylacetamide of 8g, be stirred at 25 DEG C and dissolve completely; In the solution obtained, add the compound with structure shown in formula 22 of 0.8827g, stir after 12 hours dry, obtain polyimide.
The above-mentioned polyimide N,N-dimethylacetamide prepared is mixed with the polyimide solution that mass content is 10%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 20 microns; Described sheet glass is dried 24 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 200 DEG C, be incubated 1h, at 250 DEG C, be incubated 1h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that the embodiment of the present invention 10 prepares, according to the method described in technique scheme, test its transparency, test result is, the transmittance of polyimide film prepared by the polyimide that the embodiment of the present invention 10 provides is 87%, and the transparency better.
According to method described in technique scheme, carry out thermogravimetic analysis (TGA) to the polyimide that the embodiment of the present invention 10 prepares, test result is, the second-order transition temperature of the polyimide that the embodiment of the present invention 10 prepares is 260 DEG C, the thermal weight loss temperature of 5% is 395 DEG C, better heat stability.
According to the method described in technique scheme, the structure of the polyimide that the test embodiment of the present invention 10 prepares, test result is, the polyimide that the embodiment of the present invention 10 prepares has the structure shown in formula 43:
In formula 43, n is 75.
According to the method described in technique scheme, the mechanical property of the polyimide that the test embodiment of the present invention 10 prepares, test result is, the tensile strength of the polyimide that the embodiment of the present invention 10 prepares is 101MPa, Young's modulus is 2.6GPa, elongation at break is 4.9%, and mechanical property is better.
Embodiment 11
In the polymerization bottle that mechanical stirring, nitrogen protection are housed, the diamine that the embodiment 1 adding 0.6513g prepares, the triethylamine of 1.6g, then in described polymerization bottle, add the N,N-dimethylacetamide of 10.55g, be stirred at 25 DEG C and dissolve completely; What in the solution obtained, add 0.9306g has the compound of structure shown in formula 20, the diacetyl oxide of 20mL, stir 10 hours at 25 DEG C, the reaction product obtained is cooled to 100 DEG C, separates out with ethanol, by the precipitate obtained 100 DEG C, dry under vacuum, obtain polyimide.
The above-mentioned polyimide N,N-dimethylacetamide prepared is mixed with the polyimide solution that mass content is 10%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 20 microns; Described sheet glass is dried 10 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 200 DEG C, be incubated 1h, at 250 DEG C, be incubated 2h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that the embodiment of the present invention 11 prepares, according to the method described in technique scheme, test its transparency, test result is, the transmittance of polyimide film prepared by the polyimide that the embodiment of the present invention 11 provides is 88%, and the transparency better.
According to method described in technique scheme, carry out thermogravimetic analysis (TGA) to the polyimide that the embodiment of the present invention 11 prepares, test result is, the second-order transition temperature of the polyimide that the embodiment of the present invention 11 prepares is 280 DEG C, the thermal weight loss temperature of 5% is 435 DEG C, better heat stability.
According to the method described in technique scheme, the structure of the polyimide that the test embodiment of the present invention 11 prepares, test result is, the polyimide that the embodiment of the present invention 11 prepares has the structure shown in formula 44:
In formula 44, n is 80.
According to the method described in technique scheme, the mechanical property of the polyimide that the test embodiment of the present invention 11 prepares, test result is, the tensile strength of the polyimide that the embodiment of the present invention 11 prepares is 105MPa, Young's modulus is 2.7GPa, elongation at break is 6.4%, and mechanical property is better.
Comparative example 1
Be the method disclosed in the Chinese patent of 201210082313.7 according to application number, prepare polyimide, detailed process is:
In the reactor with water trap and agitator, measure the dimethylbenzene of 300mL, open and stir, the triphen diether tetracarboxylic acid of 43.8 grams is poured in reactor, be heated to 144 DEG C of backflow band water; When in water trap anhydrous separate time, be cooled to 25 DEG C, be parsed into acid anhydride effect; When being greater than 98% as acid anhydride rate, add 20.00 grams 4,4 '-diaminodiphenyl oxide, continue to stir and be heated to 144 DEG C of band water; When in water trap anhydrous separate time, be cooled to normal temperature, the reaction mixture that obtains filtered, filter cake vacuum-drying after 1 hour at 200 DEG C, discharging, to sieve, obtain bis ether acid anhydride type polyimide.
The above-mentioned polyimide N,N-dimethylacetamide prepared is mixed with the polyimide solution that mass content is 10%, and employing is scraped embrane method and is spread over by described polyimide solution on clean sheet glass, and sprawling thickness is 20 microns; Described sheet glass is dried 10 hours at 80 DEG C; Sheet glass after described oven dry is incubated 2h successively at 100 DEG C, at 150 DEG C, is incubated 2h, at 200 DEG C, be incubated 1h, at 250 DEG C, be incubated 2h, then described sheet glass is cooled to 25 DEG C, use water demoulding, the film obtained is dried in an oven, obtains polyimide film.
By the polyimide film that comparative example 1 of the present invention prepares, according to the method described in technique scheme, test its transparency, test result is, the transmittance of polyimide film prepared by the polyimide that comparative example 1 of the present invention provides is 70%, and the transparency is poor.
According to method described in technique scheme, thermogravimetic analysis (TGA) is carried out to the polyimide that comparative example 1 of the present invention prepares, test result is, the second-order transition temperature of the polyimide that comparative example 1 of the present invention prepares is 210 DEG C, and the thermal weight loss temperature of 5% is 466 DEG C.
According to the method described in technique scheme, test the mechanical property of the polyimide that comparative example 1 of the present invention prepares, test result is, the tensile strength of the polyimide that comparative example 1 of the present invention prepares is 89MPa, Young's modulus is 2.1GPa, and elongation at break is 5.0%.
As seen from the above embodiment, the invention provides a kind of polyimide, have the structure shown in formula I, in formula I, R is that after aromatic diacid acid anhydride removes end oxygen base, remaining group or aliphatic diacid acid anhydride remove remaining group after end oxygen base; N is the polymerization degree, 1≤n≤1000.Polyimide transparent provided by the invention is better.In addition, polyimide environmentally safe provided by the invention; Better heat stability; Second-order transition temperature is higher; Mechanical property is better.
The invention provides a kind of preparation method of polyimide, comprising: diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide, temperature >=150 DEG C of described reaction; Described diamine is for having one or more in structural compounds shown in formula II ~ formula IV.The invention provides a kind of preparation method of polyimide, comprising: diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide; Temperature≤40 DEG C of described reaction; Described diamine is for having one or more in the structural compounds shown in formula II ~ formula IV.The invention provides a kind of preparation method of polyimide, comprise: under the effect of catalyzer, diamine and dibasic acid anhydride are reacted in a solvent, obtain polyimide, described diamine is for having one or more in the structural compounds shown in formula II ~ formula IV.The polyimide transparent that method provided by the invention prepares is better.In addition, the diamine that method provided by the invention adopts in the process preparing polyimide is renewable resources, environmentally friendly; And the polyimide environmentally safe prepared; Better heat stability; Second-order transition temperature is higher; Mechanical property is better; Preparation method's technique of polyimide provided by the invention is simple, easy and simple to handle in addition.
The invention provides a kind of polyimide film, prepared by polyimide described in technique scheme; Or polyimide prepared by method described in technique scheme prepares.The polyimide film transparency provided by the invention better.In addition, polyimide film provided by the invention is prepared by reproducible diamine, environmentally friendly; And polyimide film environmentally safe provided by the invention; Better heat stability; Second-order transition temperature is higher; Mechanical property is better.

Claims (10)

1. a polyimide, has the structure shown in formula I:
In formula I, R is that after aromatic diacid acid anhydride removes end oxygen base, remaining group or aliphatic diacid acid anhydride remove remaining group after end oxygen base;
N is the polymerization degree, 1≤n≤1000.
2. polyimide according to claim 1, is characterized in that, the R in described formula I is for having the one in the group of structure shown in formula 1 ~ formula 17:
3. a preparation method for polyimide, comprising:
Diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide, temperature >=150 DEG C of described reaction; Described diamine for having one or more in structural compounds shown in formula II ~ formula IV,
4. method according to claim 3, is characterized in that, the time of described reaction is 1 hour ~ 5 hours.
5. a preparation method for polyimide, comprising:
Diamine and dibasic acid anhydride are reacted in a solvent, obtains polyimide; Temperature≤40 DEG C of described reaction; Described diamine for having one or more in the structural compounds shown in formula II ~ formula IV,
6. method according to claim 5, is characterized in that, the time of described reaction is 10 hours ~ 24 hours.
7. a preparation method for polyimide, comprising:
Under the effect of catalyzer, diamine and dibasic acid anhydride are reacted in a solvent, obtain polyimide, described diamine for having one or more in the structural compounds shown in formula II ~ formula IV,
8. method according to claim 7, is characterized in that, the time of described reaction is 8 hours ~ 15 hours.
9. method according to claim 7, is characterized in that, described catalyzer is triethylamine or pyridine.
10. a polyimide film, is prepared by the polyimide described in claim 1 or 2; Or the polyimide to be prepared by method described in any one in claim 3 ~ 9 prepares.
CN201410530748.2A 2014-10-09 2014-10-09 Polyimide and preparation method thereof Pending CN104231268A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100410256C (en) * 2005-07-01 2008-08-13 清华大学 Optical diamine monomer containing di-dehydrated-hexitol unit and process for preparing same
JP2014172911A (en) * 2013-03-05 2014-09-22 Nagase & Co Ltd Polyimides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100410256C (en) * 2005-07-01 2008-08-13 清华大学 Optical diamine monomer containing di-dehydrated-hexitol unit and process for preparing same
JP2014172911A (en) * 2013-03-05 2014-09-22 Nagase & Co Ltd Polyimides

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