CN110373026A - Polyimide resin composition and preparation method thereof and film - Google Patents
Polyimide resin composition and preparation method thereof and film Download PDFInfo
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- CN110373026A CN110373026A CN201910823326.7A CN201910823326A CN110373026A CN 110373026 A CN110373026 A CN 110373026A CN 201910823326 A CN201910823326 A CN 201910823326A CN 110373026 A CN110373026 A CN 110373026A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention relates to a kind of polyimide resin composition and preparation method thereof and films, the composition includes: inorganic particle, polyimide resin, the inorganic particle dispersion is in the polyimide resin, also, the inorganic particle surfaces are handled by the compound of the following general formula (I):Wherein, R1And R2It is identical or different, separately selected from the carbon atom number straight chain for being 1~20 or the alkyl of branching, carbon atom number be 5~20 naphthenic base, carbon atom number be 6~30 aromatic group, alkyl, naphthenic base and the aromatic group, which can be substituted, perhaps contains hetero atom or R1And R2It is connected via chemical bond.
Description
Technical field
This application involves the field of industrial production of heat-conducting insulation material, more particularly to the resin combination comprising polyimides
Heat-conducting insulation material and the heat conducting insulating film based on the composition preparation and processing.
Background technique
Polyimides (polyimide, PI) is known as gold high molecular material, is usually by anhydride compounds and two
Amine compounds carry out imidizate under conditions of thermal dehydration and obtain.Nowadays, various polyimide resins or based on poly-
Imido composition has industrially obtained quick development, and the industrial product as obtained from these materials is extensive
It applies in multiple fields such as variable-frequency motor, military project, aerospace, microelectronics, nano-liquid crystal, seperation films.In order to meet polyamides Asia
The multifarious application demand of amine, various composite polyimide materials have obtained industry and the extensive concern of scholars.
It is well known that polyimides product, such as Kapton etc. have good heat resistance, excellent machine
Tool performance and chemical corrosion resistance.But generally, it is considered that the heat conductivity of various polyimides products is bad.For example, tradition is poly-
The thermal coefficient of imide membrane is between 0.1~0.2W/mK, under the premise of guaranteeing Kapton insulation performance
Improve its heating conduction, current commercialized method mainly by resin Uniform Doped include aluminium oxide, silica, nitrogen
Heat filling including SiClx and boron nitride etc. prepares laminated film.This polyamides for preparing heat filling Uniform Doped method
Imines laminated film generally is difficult to form effective passage of heat, therefore laminated film when filler doping is lower than 30wt%
Heating conduction promoted it is limited.Although theoretically the doping of a large amount of heat fillings can assign film higher thermal conductivity,
Due in film filler be easy to happen reunion cause the mechanical performance of film and being greatly reduced for insulation performance.
In addition, though the heating conduction of raising composite polyimide material and the strategy of insulation performance are doping inorganic insulations
Particle, when the inorganic heat filling dosage being scattered in resin is smaller, although filler is dispersed in resin, but to each other
Fail to be formed and contact with each other and interact, heating conduction improves little；And amount of filler it is larger when, on the one hand led due to inorganic
Hot filler prevents the movement of strand in polymer, and the toughness of matrix itself is caused to decline；Another aspect inorganic heat filling
Crackle extension under plus load effect will lead to material fracture failure between matrix.Therefore, it fills larger amount of inorganic thermally conductive
Although filler can make film heating conduction improve a lot, make the mechanical performances such as the comprehensive performance of film, especially toughness
It is remarkably decreased, leads to the easy embrittlement of polyimides film forming, or even can not casting and stretching film forming.
In addition, largely adulterating inorganic nanoparticles for the thermal conductivity for improving Kapton in practical applications
When, the dispersion that there is also inorganic nanoparticles in polyimide resin, due to the dimensional effect of inorganic nanoparticles, table
Face effect etc. also results in polyimide-based compound so that dispersion of the inorganic nanoparticles in polyimide resin is uneven
The generations such as insulating properties, the mechanical performance of material significantly decline, so as to cause the composite polyimide material of nano particle doping
The problem of performance difference.
Citation 1 discloses a kind of thermally conductive Kapton, and the film is by polyimide matrix, activation heat filling
Two parts composition, the mass fraction of polyimide matrix are 78~98wt%, the mass fraction for activating heat filling is 2~
22wt%；Activating heat filling is the filler being surface-treated by silane coupling agent.Its obtained PI film is removed with good
While good thermal conductivity, higher mechanical property and good insulation performance are also maintained.On the one hand, such to use organosilicon
Alkane coupling agent, which carries out surface treatment, may be confined to physical absorption, and opposite with the Compatibility improvement of resin for inorganic particle have
Limit, meanwhile, optimal thermal conductivity is obtained in scheme and has also been used cooperatively high thermal conductivity graphene, utilizes the two dimension of graphene
Large scale serves as the function served as bridge between aluminum nitride particle, however the graphene that its auxiliary uses overall apparently still has
Reduce the worry of insulating properties.
Citation 2 is related to a kind of high thermal conductivity Kapton and preparation method thereof, belongs to Kapton technology
Field, solves that existing doping method is difficult to construct high-efficiency heat conduction channel in low heat filling loading and polyimides is thin
The problem of film dynamic performance and heating conduction can not get both.Film includes polyimide resin A, polyimide resin B and thermally conductive
Filler；Heat filling is scattered in A phase, and the dissolution interaction parameter difference of polyamic acid resin A and polyamic acid resin B are
2.5~5.0；The passage of heat of Kapton is continuous and perpendicular to thin film planar.Therefore, mainly for polyimides tree
In rouge the case where lower Inorganic Fillers Filled.
In addition, citation 3 has then been attempted to improve polyimide insulative film using the inorganic filler of specific specific surface
The performances such as thermal conductivity, heat resistance, chemical resistance and mechanical property.Disclosing in citation 4 has as Inorganic Fillers Filled
The thermal conductivity inorganic spherical micron filler of micro particles size；Plate, rodlike, fibrous or flakey shape micron filler；
And the resin combination of the thermal conductivity inorganic nano-filler of nano-particles size.
As it can be seen that in the prior art in use inorganic particle, inorganic filler etc. to polyimides product, especially polyimides
The heat conductivity of film improves the leeway that aspect still has raising.In particular, how to be passed in the heat for improving polyimides product
While the property led, excellent insulating properties, mechanical performance etc. is kept still to have the space further inquired into.
Citation:
Citation 1:CN107652432A
Citation 2:CN108610631A
Citation 3:CN109155165A
2013~No. 159748 bulletins of citation 4:JP special open
Summary of the invention
Problems to be solved by the invention
In view of the above-mentioned problems existing in the prior art, technical problem to be solved by the present invention lies in using inorganic particulate
When especially improving to the heat conductivity of Kapton, how effectively grain or inorganic filler are to polyimides product,
Raising polyimides product heat conductivity, and when the loading in inorganic particle or inorganic filler is larger can
Enough without the insulating properties and mechanical performance of reduction polyimides product while obtaining satisfied heat conductivity.
In addition, the technical problems to be solved by the invention also reside in, when inorganic particle using Nano grade or inorganic
Filler is to polyimides product, when especially improving to the heat conductivity of Kapton, how to make these inorganic
Particle or inorganic filler are uniformly scattered in polyimides product, be can be avoided and are dispersed when loading is larger
Non-uniform problem.
The solution to the problem
It concentrates on studies by applicant, discovery, which adopts the following technical scheme that, is able to solve above-mentioned technical problem:
[1] is present invention firstly provides a kind of polyimide resin composition, it includes:
Inorganic particle,
Polyimide resin,
The inorganic particle dispersion is in the polyimide resin, also, the inorganic particle surfaces are by following logical
The compound of formula (I) is handled:
Wherein, R1And R2It is identical or different, separately selected from carbon atom number be 1~20 straight chain or branching alkyl,
The aromatic group that naphthenic base that carbon atom number is 5~20, carbon atom number are 6~30, the alkyl, naphthenic base and fragrance
Race's group can be substituted perhaps contain hetero atom or
R1And R2It is connected via chemical bond.
[2] polyimide resin composition according to [1], the average grain diameter of the inorganic particle is 10~
150nm, preferably 10~100nm；The dosage of the inorganic particle be the composition in polyimide resin quality 1~
25%.
[3] polyimide resin composition according to claim 1 or 2, the inorganic particle are selected from metal, half
One of nitride, oxide or carbide of metal are a variety of, preferably aluminium, silicon, the nitride of boron, oxide or charing
Object.
[4] is according to the described in any item polyimide resin compositions in [1]~[3], the compound of the logical formula (I)
R1And R2In at least one be selected from carbon atom number be 4~10 branching alkyl.
[5] is according to the described in any item polyimide resin compositions in [1]~[4], and the polyimide resin is by binary
Organic acid anhydride compound and binary organic amine compound are prepared, the binary organic amine compound and binary organic acid anhydridization
The molar ratio for closing object is 1:1~1.1:1.
[6] in turn, present invention provides a kind of preparation methods of polyimide resin composition by comprising:
The step of inorganic particle is surface-treated using the compound of logical formula (I)；
The step of preparing polyamic acid solution；
By the inorganic particle dispersion Jing Guo the surface treatment in the polyamic acid solution the step of；
The step of by the polyamic acid solution imidizate for having dispersed inorganic particle；
Wherein, R1And R2It is identical or different, separately selected from carbon atom number be 1~20 straight chain or branching alkyl,
The aromatic group that naphthenic base that carbon atom number is 5~20, carbon atom number are 6~30, the alkyl, naphthenic base and fragrance
Race's group can be substituted perhaps contain hetero atom or
R1And R2It is connected via chemical bond.
[7] method according to [6], the average grain diameter of the inorganic particle are 10~150nm, preferably 10~
100nm；The dosage of the inorganic particle is 1~25% of polyimide resin quality in the composition.
[8] method according to [6] or [7], the inorganic particle are selected from metal, semimetallic nitride, oxide
Or one of carbide or a variety of, preferably aluminium, silicon, the nitride of boron, oxide or carbide.
[9] is according to the described in any item methods in [6]~[8], the R of the compound of the logical formula (I)1And R2In at least one
Alkyl selected from the branching that carbon atom number is 4~10.
[10] is further, and the present invention also provides a kind of Kaptons comprising any according to above [1]~[5]
Polyimide resin composition described in item is prepared by the composition.
The effect of invention
The implementation of above technical scheme through the invention, the present invention can obtain following technical effect:
1) polyimides product provided by the invention, especially Kapton have good thermal conductivity, and i.e.
Make in the case where inorganic particle or inorganic filler have compared with high filler loading capacity, it also can be while significantly improving thermal conductivity
Insulating properties and mechanical performance without damaging polyimides product.
2) in polyimides product provided by the invention, by being used at specific surface to inorganic particle or inorganic filler
Reason, so that these inorganic particles or inorganic filler can uniformly be scattered in polyimides in nano-scale range
In resin system.
3) provided by the present invention easy to implement to inorganic particle or the surface modifying method of inorganic filler, and substantially not
It is limited by polyimides type, therefore, there is wider applicability.
Specific embodiment
Hereinafter, being described in detail for the contents of the present invention.The explanation of documented technical characteristic is based on this hair below
Bright representative embodiment, specific example and carry out, but the present invention is not limited to these embodiments, specific example.It needs
It is noted that
In this specification, the numberical range for using " numerical value A~numerical value B " to indicate refers to the range comprising endpoint value A, B.
In this specification, " inorganic particle " is substantially had the same meaning with " inorganic filler ".
It in this specification, is such as not particularly illustrated, then " % " indicates mass percentage.
In this specification, the meaning for using " can with " to indicate includes carrying out certain processing and handling two without certain
The meaning of aspect.
In this specification, " optional " or " optionally " refer to that the event next described or situation can occur or can not send out
It is raw, and the description includes the case where that there is a situation where do not occur with the event for the event.
In this specification, mentioned " some specific/preferred embodiments ", " other specific/preferred embodiment party
Case ", " embodiment " etc. refer to described specific factor related with the embodiment (for example, feature, structure, property and/
Or characteristic) it include that and may be present in other embodiments or can not at least one embodiment described herein
It is present in other embodiments.In addition, it should be understood that the element can be combined in any suitable manner in various embodiments
In.
In the present invention, needs in order to express easily are unified to use " binary for forming the acrylic monomer of polyimides
Anhydride compound ", it is self-evident, the present invention in the term include in structure with dibasic acid anhydride structure compound with
And its in the form of polyacid existing for precursor.
<first aspect>
In the first aspect of the invention, the application provides a kind of polyimide resin composition, it includes:
Inorganic particle,
Polyimide resin,
The inorganic particle dispersion is in the polyimide resin, also, the inorganic particle surfaces are by following logical
The compound of formula (I) is handled:
Wherein, R1And R2It is identical or different, separately selected from carbon atom number be 1~20 straight chain or branching alkyl,
The aromatic group that naphthenic base that carbon atom number is 5~20, carbon atom number are 6~30, the alkyl, naphthenic base and fragrance
Race's group can be substituted perhaps contain hetero atom or
R1And R2It is connected via chemical bond.
Polyimide resin
Technical solution used in the present invention is suitable for polyimide resin conventional in the art in principle.In general, polyamides
Imines can carry out dehydrating condensation with binary organic amine compound by binary organic acid acid anhydride compound and obtain.
In the present invention, the binary organic acid acid anhydride compound has structure shown in logical formula (II) as follows:
Wherein group Y indicates substituted or unsubstituted hydrocarbyl group, and the hydrocarbon segment of these hydrocarbyl groups can be miscellaneous
Atom is interrupted containing heteroatomic group, the hetero atom or containing heteroatomic group be selected from S, N, O or C=O.In the present invention
In specific embodiment, these above-mentioned hydrocarbyl groups can also be replaced by halogen, it is preferred that the halogen is F or Cl.
In some specific embodiments of the present invention, the Y group can be selected from substituted or unsubstituted: phenyl, connection
Phenyl, naphthalene and have following general formula (II~1) shown in structure:
~Ar~Q~Ar~(II~1)
Wherein Ar indicates aromatic hydrocarbyl or heteroaromatic group；Q indicates that carbon atom number is 1~10 alkyl, and this
The hydrocarbon segment of a little alkyl can by hetero atom or containing heteroatomic group interrupt or the hydrocarbon segment of these alkyl in carbon can
To be selected from S, N, O or C=O by these hetero atoms or containing heteroatomic group substitution, the hetero atom or containing heteroatomic group；
Ar or Q can also be replaced by halogen, it is preferred that the halogen is F or Cl.
In other specific embodiment of the present invention, the Y group can be selected from shown in following general formula (II~2)
Structure:
~Ar '~(II~2)
Wherein, Ar ' is selected from S, N, O or C=O selected from heteroaromatic group, hetero atom therein or containing heteroatomic group；
Ar ' can also be replaced by halogen, it is preferred that the halogen is F or Cl.
Further, in a preferred embodiment of the present invention, the binary organic acid acid anhydride compound can be selected from: equal benzene four
Formic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone
Tetracarboxylic acid dianhydride, 2,3,6,7- naphthalenetetracarbacidic acidic dianhydrides, 2,2- bis- (3,4- dicarboxyphenyi) ether dianhydrides, pyridine -2,3,5,6- tetra-
Four acid compounds of formic acid dianhydride or these aforementioned acid anhydrides.
For the binary organic amine compound in the present invention, formula (III) compound represented can be led to as follows selected from having,
H2N-Z-NH2
(III)
Wherein, Z is selected from substituted or unsubstituted hydrocarbyl group, and the hydrocarbon segment of these hydrocarbyl groups can be by hetero atom
Or interrupted containing heteroatomic group, the hetero atom or containing heteroatomic group be selected from S, N, O or C=O.Of the invention specific
Embodiment in, these above-mentioned hydrocarbyl groups can also be replaced by halogen, it is preferred that the halogen be F or Cl.
In some specific embodiments of the present invention, aromatic hydrocarbyl and/or heteroaromatic group are contained in Z, it is described
Hetero atom in heteroaromatic group can be selected from S, N, O or C=O containing heteroatomic group.
Further, in a preferred embodiment of the present invention, the binary organic amine compound can selected from p-phenylenediamine,
M-phenylene diamine (MPD), benzidine, p dimethylamine, 4,4 '-diamino-diphenyl ethers, 3,4 '-diamino-diphenyl ethers, 4,4 '-diaminos
Base diphenyl methane, 4,4 '-diaminodiphenylsulfones, 3,3 '-dimethyl -4,4 '-diaminodiphenyl-methane, 1,5 '-diamino
Naphthalene, 3,3 '-dimethoxy benzidines, 1,4 '-bis- (3- methyl -5- aminophenyl) benzene.
The polyimides being applicable in the present invention can be above-mentioned binary organic amine compound and binary organic acid anhydridization closes
Object is obtained with molar ratio for the condensation reaction of 1:1~1.1:1.
Inorganic particle
In the present invention, by polyimides product, especially Kapton dispersed inorganic particles it is poly- to improve
The thermal conductivity of imide articles.
It, can be selected from one in metal, semimetallic nitride, oxide or carbide for inorganic particle in the present invention
Kind is a variety of, preferably aluminium, silicon, the nitride of boron, oxide or carbide.It can enumerate are as follows: oxide, silica, oxygen
Change aluminium, titanium oxide, magnesia, iron oxide, cobalt oxide, copper oxide or zinc oxide；Nitride is selected from silicon nitride, aluminium nitride or nitrogen
Change boron；Carbide is selected from silicon carbide, titanium carbide or boron carbide.
The average grain diameter of the inorganic particle is 10~150nm, preferably 10~100nm.
In some preferred embodiments of the present invention, the inorganic particle can be selected from aluminium oxide, silica, nitridation
One of aluminium, silicon nitride and boron nitride are a variety of.
In the present invention, for avoiding while improving the thermal conductivity of polyimides product to the insulating properties of the product and
The loss of mechanical performance, the present invention in, the inorganic particle be by as described below lead to formula (I) compound surface it is processed
Inorganic particle:
Wherein, R1And R2It is identical or different, separately selected from carbon atom number be 1~20 straight chain or branching alkyl,
The aromatic group that naphthenic base that carbon atom number is 5~20, carbon atom number are 6~30, the alkyl, naphthenic base and fragrance
Race's group can be substituted or contain hetero atom, and the hetero atom is selected from N, S, O or halogen atom, alternatively,
R1And R2It is connected via chemical bond.
In some preferred embodiments of the present invention, lead in compound represented by formula (I), R1Or R2It independent can select
The naphthenic base for being 5~10 from the carbon atom number straight chain for being 4~10 or the alkyl of branching, carbon atom number, further preferably methyl,
Ethyl, isopropyl, tert-butyl or cyclohexyl.Typically, logical formula (I) compound of the present invention can be selected from the tertiary fourth of two carbonic acid
One of ester methyl ester, di-tert-butyl dicarbonate, two t-butyl carbonate isopropyl esters are a variety of.
In the present invention, being surface-treated using compound represented by above-mentioned logical formula (I) to inorganic particle can be obvious
Ground improves the compatibility of inorganic particle and polyimide resin matrix, therefore, even if carrying out in inorganic particle to polyimides high
When filling (for example, based on polyimide resin weight in polyimide resin composition, inorganic particle content is 1~25%),
Also can not mechanical performance to polyimides product, especially Kapton and insulating properties cause adverse effect.
Wherein, when being surface-treated with compound represented by above-mentioned general formula (I) to inorganic particle, the logical formula (I)
The molar ratio of represented compound and inorganic particle can be 1~1.2:1.
In addition, in the present invention, for the mode for using the compound of logical formula (I) to be surface-treated above-mentioned inorganic particle
There is no particular limitation.In some preferred embodiments of the present invention, first inorganic particle can will be dried, so
It is reacted under the effect of the catalyst with the compound of logical formula (I) again afterwards.
Above-mentioned catalyst, the present invention in basic catalyst can be used, in some preferred embodiments, these catalysis
Agent can be selected from aminopyridine series catalysts, it is preferred that can be selected from 4-dimethylaminopyridine, 3- dimethylamino naphthyridine, 4- first
At least one of base ethylamino pyridine.
Surface modification by above-mentioned drying process and in the presence of a catalyst can significantly improve inorganic receive
The dispersibility of rice grain also further improves the compatibility of inorganic nanoparticles and polyimide resin.Therefore, even if making
It is the inorganic particle of nanometer scale with average grain diameter, can also preferably avoids under the high occupied state of inorganic nanoparticles, gathers
Occur inorganic nanoparticles dispersion non-uniform phenomenon in imide articles, especially Kapton and occurs undesirable
The phenomenon that crackle, so that good insulating properties and mechanical performance can still be maintained while providing heat conductivity.
In polyimide resin composition of the invention, for the dosage of inorganic particle, combined with polyimide resin
The quality meter of polyimides in object, inorganic particle dosage are 1~25%, preferably 2~20%, further preferably 5~15%
Or 5~10%.When additive amount is lower than 1%, inorganic particle is unobvious for the raising of the heat conductivity of polyimide resin；When
When additive amount is higher than 25%, dispersibility of the inorganic particle in polyimide resin has the tendency that variation.
<other compositions>
In the polyimide resin composition of the invention, in addition to including above-mentioned polyimide resin and inorganic particulate
It is unrestricted other than grain, can also comprising can be adapted in this field other resins of polyimide resin composition at
Point, functional aid etc..
It is unrestricted for other resin components, can be used with polyimides have certain compatibility resin at
Point, including but not limited to following polymer: polyphenylsulfone, polyetherimide, polysulfones, polycarbonate, polyphenylene oxide, poly- methyl-prop
E pioic acid methyl ester, acrylonitrile~butadiene~styrol copolymer, polystyrene, polyvinyl chloride, perfluoroalkoxyalkane polymer,
The copolymer of tetrafluoroethene and perfluoroalkyl vinyl ether, fluorinated ethylene-propylene polymer, polyphenylene sulfide, poly- (ether ketone), poly- (ether~ether
Ketone), ethylene chlorotrifluoroethylene polymer, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), polyethylene terephthalate, polyacetals,
Polyamide, polypropylene, polyethylene, high density polyethylene (HDPE), low density polyethylene (LDPE), polybenzimidazoles, gathers ultra-high molecular weight polyethylene
(amide~acid imide), poly- (ether sulfone), poly- (aryl sulfone), polyphenylene, polybenzimidazoles, polybenzothiozole and its blending
Object and copolymer.
When in polyimide resin composition containing above-mentioned other resin components, with polyimide resin composition
Total weight, the content of these other resins is 0% or more, and is lower than 50%, preferably 0~30%, more preferably 0~
10%.
It, can be for selected from weather resisting agent, antioxidant, ultraviolet absorbing agent, antistatic agent, plasticising for functional aid
Agent, lubricant etc..Its dosage, it is self-evident, conventional amount used range in the prior art can be followed.
In general, being needed for arbitrary other than present invention inorganic filler type disclosed above, not influencing this hair
In the case where obvious results fruit, carbon system particle also can be used, for example, graphite, graphene, carbon nanotube etc..But for insulating properties
The considerations of, in the preferred embodiment of the invention, do not use these carbon system particles.
<second aspect>
In the second aspect of the present invention, a kind of method for preparing polyimide resin composition is provided comprising:
The step of inorganic particle is surface-treated using the compound of logical formula (I)；
The step of preparing polyamic acid solution；
By the inorganic particle dispersion Jing Guo the surface treatment in the polyamic acid solution the step of；
The step of by the polyamic acid solution imidizate for having dispersed inorganic particle；
Wherein, R1And R2It is identical or different, separately selected from carbon atom number be 1~20 straight chain or branching alkyl,
The aromatic group that naphthenic base that carbon atom number is 5~20, carbon atom number are 6~30, the alkyl, naphthenic base and fragrance
Race's group can be substituted or contain hetero atom, and the hetero atom is selected from N, S, O or halogen atom, alternatively,
R1And R2It is connected via chemical bond.
For " polyimide resin ", " inorganic particle " involved in second aspect of the present invention and its relational language, such as
Without Special Statement, had the same meaning with the content disclosed in the above-mentioned first aspect of the present invention.
For the step of using the compound of logical formula (I) to be surface-treated inorganic particle
It is unrestricted in principle, as long as at least part of surface of the inorganic particle is enabled to adhere to logical formula (I) table
The compound shown.
Contain in general, the compound that logical formula (I) can be used is blended with inorganic particle or is impregnated in inorganic particle
Have in solution or the lotion of the compound of logical formula (I), is then dried and obtains.
In a preferred embodiment of the present invention, following method can be used to carry out:
I. the inorganic particle is dried.
Ii. the compound by the inorganic particle being dried under the effect of the catalyst with logical formula (I) mixes
Reaction is closed, the catalyst is identical as the catalyst in the first aspect of the present invention.It is preferably for the mixed mode
Use mixing machine or ball mill etc..
In addition, can be arranged in step i or step ii using stirring, heating, inert gas shielding etc. as ancillary measure
It applies.
In some preferred embodiments of the present invention, the step i typically can be in inert gas such as N2It protects
Under shield, at 110~130 DEG C and in the environment of humidity 1~20%, inorganic particle is dried, preferably when processing
Between be at least 10 hours, to remove free moisture；
In some preferred embodiments of the present invention, the step ii typically can be in inert gas such as N2It protects
It, will be through two t-butyl carbonate class chemical combination of dried inorganic particle at 60~80 DEG C in the presence of shield and catalyst
The compound of the logical formula (I) such as object is surface-treated.Handling the time can be 8~15 hours, preferably 10~12 hours.Later
Carry out ball-milling treatment, it is preferable that the ball-milling treatment is carried out in the presence of dispersing agent, and dispersing agent can be used for example
The substances such as tetrahydrofuran, n-hexane, benzene, chloroform.In some specific embodiments of the invention, before ball-milling treatment,
The average grain diameter of inorganic particle is 20~150nm, and the average grain diameter of inorganic particle becomes smaller after ball milling, can be 10~150nm, excellent
It is selected as 10~100nm.
In above-mentioned surface treatment process, can make inorganic particle surfaces under the effect of the catalyst with logical formula (I)
Compound generate following graft reaction, to complete the surface treatment to inorganic particle:
Wherein M indicates inorganic filler or inorganic particle.
For the step of preparing polyamic acid solution
There is no limit as long as use binary organic acid acid anhydride compound, binary disclosed in first aspect present invention in principle
Organic amine compound carries out condensation reaction in polar solvent and obtains polyamic acid solution.
For polar solvent, consider from the dissolubility angle to reaction monomers and reaction product, can be used polarity compared with
Those of strong solvent, typically can be used N-Methyl pyrrolidone (NMP), n,N-Dimethylformamide (DMF), dimethyl second
Amide (DMAc) etc..In addition, toluene, dimethyl sulfoxide can also be used cooperatively according to the difference of the monomer of wanted solvent or polymer
Equal solvent.
For the reaction ratio of binary organic amine compound and binary organic acid acid anhydride compound, with molar ratio computing, the two ratio
Example can be referred to the common behaviour for preparing polyamic acid in this field for the temperature and time of reaction for 1:1~1.1:1
Make mode.
In some specific embodiments of the present invention, the solid content of the polyamic acid solution obtained by condensation reaction is
15~25%, it is preferred that viscosity of the polyamic acid solution at 25 DEG C be 50000Cps or more, more preferably 200000Cps with
On.
For the inorganic particle dispersion of the surface treatment will be passed through in the polyamic acid solution the step of
After having obtained surface treated inorganic particle and polyamic acid solution as described above, by the inorganic particle
It is mixed with polyamic acid solution.There is no limit can be used the common hybrid mode in this field to mixed mode.In the present invention one
In a little specific embodiments, can by modes such as stirrings so that surface treated inorganic particle be uniformly scattered in it is poly-
In amide acid solution.
In some specific embodiments of the present invention, above-mentioned dispersion can carry out in the presence of dispersing agent, and described point
Powder can be selected from the mixing of one or both of γ~butyrolactone (GBL) or propylene glycol methyl ether acetate (PGMEA).
The dosage of the surface treated inorganic particle can be binary organic acid acid anhydride compound and binary organic amine
The 1~25% of compound total weight, preferably 2~20%, further preferably 5~15% or 5~10%.
The step of polyamic acid solution imidizate for inorganic particle will have been dispersed
The polyamic acid solution for having dispersed inorganic particle is placed in optional mold, or by the solution in optional branch
Film is carried out on support body.
It may then pass through heat temperature raising and carry out desolventizing, hot imidization, demoulding/removing obtains high thermal conductivity polyimides
Molded product or film.It can be in some specific embodiments of the present invention, the step of the heat temperature raising desolventizing are as follows: 60
1~2 hour removing solvent of~85 DEG C of bakings after being warming up to 230~260 DEG C with 1~2 DEG C/min of speed, keeps the temperature 1~3 hour.
The step of hot imidization are as follows: after substantially removing solvent, 340~360 DEG C are warming up to 3~4 DEG C/min of speed,
And keep the temperature 1~2 hour.
The above content provides the typical method for preparing polyimide compositions in the second aspect of the present invention.But this
Invention can also select other modes according to the actual situation in preparing polyimide compositions, for example, depending on polyamides
The processability of imines can be realized to obtain solution or the tree of polyimides according to the preparation method of the common polyimides in this field
Rouge, then again by such solution or resin and surface treated inorganic particle carry out solution mix or melting mixing and obtain
To polyimide compositions of the invention.
In addition, for equipment used in preparation method described in the above-mentioned second aspect of the present invention, there is no limit can be with
The common process equipment in this field is arbitrarily chosen according to actual needs.
<third aspect>
In the third aspect of the invention, the present invention provides a kind of polyimides products, and especially polyimides is thin
Membrane product, the Kapton product being prepared especially by the tape casting.
For the product of polyimides, can according to the second aspect of the invention in it is mixed by polyamic acid and inorganic particle
Conjunction is placed in mold or film, later carry out desolventizing, imidizate mode and obtain these products.It is unrestricted,
These products can be able to be typically plate or membrane material for any required molded product.
In addition, as previously mentioned, with inorganic particle by solvent or heating, can also be carried out molten after obtaining polyimides
Liquid mixing or melting mixing obtain composition, and then obtain required product by optional molding mode.
For example, these compositions can be shaped to product by arbitrary method.Preferred method includes, for example, being molded, blowing
Modeling, compression moulding, profile extrusion, sheet material or film extrusion, sintering, gas-assisted molding, structural foam moding and thermoforming.This
The example of the product of sample includes, but are not limited to film, pipe, compound, semiconductor processing tools, wire coatings and big envelope, fluid behaviour
Vertical component, cooker, food service items, medical instrument, plate, handle, the helmet, animal cage, electric connector, electrical appliance enclosure,
Engine components, automotive engine component, bearing, light socket and reflector, electrical components, controller switching equipment, communication equipment, meter
Calculation machine etc..
In addition, carry out the composition that solution mixing or melting mixing obtain can be used common thermoplastic method such as film and
Sheet material extrusion is changed into product.Film and sheet extrusion processes may include but be not limited to melting curtain coating, blown-film extrusion and pressure
Prolong.In some cases, film can have 0.1~1000 micron preferably 0.5~800 micron of thickness.Coextrusion can be used
Complex multi layer films or sheet material are formed with laminating method.Single-layer or multi-layer coating can be also applied on single-layer or multi-layer substrate,
To assign additional property such as resistance to scraping, ultraviolet resistance, aesthstic attractive force etc..Coating can be by standard method of application for example
Roller coating, spraying, drop coating, brushing or flow coat apply.Alternatively, film and sheet material can by by above-mentioned composition suitable
Solution or suspension in solvent are cast on substrate, band or roller, are then removed solvent and are prepared.Standard side also can be used in film
Method as sputtering, vacuum deposition and with layers of foil press and metallize.
Further, can also by blown-film extrusion, or by using conventional drawing process in heat distortion temperature
Nearby the film of curtain coating or calendering is stretched, oriented film can be prepared.For example, it is more that the progress of radial drawing pantogragh can be used
Axis stretches simultaneously；The direction x~y stretching pantogragh can be used simultaneously or sequentially to stretch on the direction x~y of plane.May be used also
To use the equipment with successive coaxial tensile part, uniaxial and biaxial stretch-formed to realize, the equipment is for example equipped with use
In the differential roller member stretched in a machine direction and for the machine of tenter frame section stretching in the transverse direction.
Polyimides molded product obtained from according to the present invention, especially Kapton have excellent thermal conductivity,
It is also avoided that the damage to the insulating properties and mechanical performance of film simultaneously.
In some preferred embodiments of the invention, the Kapton obtained through the invention has 280MPa
Above tensile strength, meanwhile, Kapton produced by the present invention has good electrical insulating property, and breakdown strength is
220kv/mm or more, thermal coefficient 0.36W/m.k or more.
Embodiment
Hereinafter, will be illustrated to specific embodiments of the present invention:
Embodiment 1
In N2Under protection, by 200g inorganic nanoparticles boron nitride (120nm) in the environment of 120 DEG C, humidity 20% mistake
Night carries out except water process.
In N2Under protection, in solvents tetrahydrofurane, 20g catalyst 4-dimethylaminopyridine is added, adds after evenly dispersed
Enter above-mentioned water removal treated inorganic nanoparticles boron nitride and bis- t-butyl carbonate methyl esters of 1758.66g, it is small in 70 DEG C of reactions 10
When more than.Then it using tetrahydrofuran as decentralized medium ball milling in the ball mill, obtains boron nitride nanometer particle (100nm)；It takes
Boron nitride nanometer particle after the surface treatment of the above-mentioned acquisition of 148.34g is dispersed in GBL (γ~butyrolactone), obtains inorganic receive
Rice grain dispersion liquid.
By 882.66g 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride of (3mol) dibasic anhydride and 600.72g (3mol) diamine 4,
The reaction in appropriate polar organic solvent n,N-Dimethylformamide (DMF) of 4 '-diamino-diphenyl ethers, is made solid content 20%
Polyamic acid solution, viscosity 50000Cps (25 DEG C)；Inorganic nanoparticles obtained above point are added into polyamic acid solution
Dispersion liquid, imidizate (in 80 DEG C of bakings, 2 hours removing solvents, after being warming up to 240 DEG C with 2 DEG C/min of speed, 2 hours are kept the temperature,
After substantially removing solvent, 340 DEG C are warming up to 3 DEG C/min of speed, and keep the temperature 2 hours), Kapton is made.
Embodiment 2-9 and comparative example 1-2
Same operation is carried out with embodiment 1, but is carried out according to condition shown in table 1.
Table 1
Following tests are carried out to the Kapton of above-described embodiment and comparative example, test result is as shown in table 2.
Test item and condition are as follows:
<Mechanics Performance Testing>
Composite membrane of the invention is fabricated to the membrane material that length and width dimensions are 25.4mm × 3.2mm respectively, uses universal test
Machine (being manufactured by Shimadzu scientific instrument limited liability company (SHIMADZU), the entitled AG-1S of equipment) is strong to measure the tension of membrane material
It spends (MPa).
<breakdown strength test>
Breakdown strength is tested using Air China's epoch ZJC-50KV voltage breakdown experiment apparatus, rate of pressure rise 0.5kV/s, and medium is
Air.
<Determination of conductive coefficients>
It is tested according to the measurement heat-pole method of GB/T22588-2008 thermal coefficient；
Table 2
Particular embodiments described above has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that the above description is only an embodiment of the present invention, is not intended to restrict the invention, all at this
Within the principle and spirit of invention, any modification, equivalent substitution, improvement and etc. done should be included in protection model of the invention
Within enclosing.
Industrial applicibility
Polyimide resin composition provided by the present invention and preparation method thereof and film can be carried out industrially
Production and application.
Claims (10)
1. a kind of polyimide resin composition, characterized by comprising:
Inorganic particle,
Polyimide resin,
The inorganic particle dispersion is in the polyimide resin, also, the inorganic particle surfaces pass through the following general formula (I)
Compound processing:
Wherein, R1And R2Identical or different, the alkyl, carbon separately selected from the carbon atom number straight chain for being 1~20 or branching are former
The aromatic group that naphthenic base that subnumber is 5~20, carbon atom number are 6~30, the alkyl, naphthenic base and aromatic series base
Group can be substituted perhaps contain hetero atom or
R1And R2It is connected via chemical bond.
2. polyimide resin composition according to claim 1, which is characterized in that the average grain diameter of the inorganic particle
For 10~150nm, preferably 10~100nm；The dosage of the inorganic particle is polyimide resin quality in the composition
1~25%.
3. polyimide resin composition according to claim 1 or 2, which is characterized in that the inorganic particle is selected from gold
One of category, semimetallic nitride, oxide or carbide are a variety of, preferably aluminium, silicon, the nitride of boron, oxide
Or carbide.
4. described in any item polyimide resin compositions according to claim 1~3, which is characterized in that the logical formula (I)
The R of compound1And R2In at least one be selected from carbon atom number be 4~10 branching alkyl.
5. polyimide resin composition according to any one of claims 1 to 4, which is characterized in that the polyimides
Resin is prepared by binary organic acid acid anhydride compound and binary organic amine compound, the binary organic amine compound and binary
The molar ratio of organic acid anhydride compound is 1:1~1.1:1.
6. a kind of preparation method of polyimide resin composition characterized by comprising
The step of inorganic particle is surface-treated using the compound of logical formula (I)；
The step of preparing polyamic acid solution；
By the inorganic particle dispersion Jing Guo the surface treatment in the polyamic acid solution the step of；
The step of by the polyamic acid solution imidizate for having dispersed inorganic particle；
Wherein, R1And R2Identical or different, the alkyl, carbon separately selected from the carbon atom number straight chain for being 1~20 or branching are former
The aromatic group that naphthenic base that subnumber is 5~20, carbon atom number are 6~30, the alkyl, naphthenic base and aromatic series base
Group can be substituted perhaps contain hetero atom or
R1And R2It is connected via chemical bond.
7. according to the method described in claim 6, it is characterized in that, the average grain diameter of the inorganic particle be 10~150nm, it is excellent
It is selected as 10~100nm；The dosage of the inorganic particle is 1~25% of polyimide resin quality in the composition.
8. method according to claim 6 or 7, which is characterized in that the inorganic particle is selected from metal, semimetallic nitridation
One of object, oxide or carbide are a variety of, preferably aluminium, silicon, the nitride of boron, oxide or carbide.
9. according to the described in any item methods of claim 6~8, which is characterized in that the R of the compound of the logical formula (I)1And R2
In at least one be selected from carbon atom number be 4~10 branching alkyl.
10. a kind of Kapton, which is characterized in that it includes described in any item polyimides according to claim 1~5
Resin combination is prepared by the composition.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116355523A (en) * | 2023-03-03 | 2023-06-30 | 北京理工大学 | Polyimide-based composite material coating and preparation method thereof |
| CN116355523B (en) * | 2023-03-03 | 2024-05-28 | 北京理工大学 | Polyimide-based composite material coating and preparation method thereof |
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| CN106700685A (en) * | 2015-07-21 | 2017-05-24 | 魏忠 | Preservative of metal structure part |
| CN107652432A (en) * | 2017-09-28 | 2018-02-02 | 无锡顺铉新材料有限公司 | A kind of heat conduction Kapton |
| CN108610631A (en) * | 2018-05-07 | 2018-10-02 | 中国科学院化学研究所 | A kind of high heat conduction Kapton and preparation method thereof |
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| CN1637034A (en) * | 2004-01-08 | 2005-07-13 | 日立化成工业株式会社 | Polyurethane-imide resin,adhesive composition and adhesive composition for circuit connection |
| US20110137009A1 (en) * | 2009-12-08 | 2011-06-09 | Samsung Electronics Co., Ltd. | Polyamic acid, polyimide, manufacturing method thereof, and polyimide film |
| CN106700685A (en) * | 2015-07-21 | 2017-05-24 | 魏忠 | Preservative of metal structure part |
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| CN116355523B (en) * | 2023-03-03 | 2024-05-28 | 北京理工大学 | Polyimide-based composite material coating and preparation method thereof |
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