CN1900164A - Blend of polyimide polymer and its use as high temperature resisting dipping glue - Google Patents
Blend of polyimide polymer and its use as high temperature resisting dipping glue Download PDFInfo
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- CN1900164A CN1900164A CN 200610103608 CN200610103608A CN1900164A CN 1900164 A CN1900164 A CN 1900164A CN 200610103608 CN200610103608 CN 200610103608 CN 200610103608 A CN200610103608 A CN 200610103608A CN 1900164 A CN1900164 A CN 1900164A
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Abstract
The present invention discloses a kind of heat resistant dipping glue comprising two kinds of blended polyimide polymer. The first polyimide polymer is prepared with aromatic fluoric diamine and aromatic tetracid dihydride and through a two-step condensation reaction in organic solvent and under the action of catalyst. The second polyimide polymer is prepared with aromatic tetracid dihydride and aromatic diisocyanate and through a one-step condensation reaction in organic solvent and under the action of catalyst. These two kinds of polyimide polymer are blended in the weight ratio of 2-10 to 1. The heat resistant dipping glue is used in dipping carbon fiber honeycomb material, glass fiber honeycomb material and paper honeycomb material to obtain reinforced heat resistant sandwiched material.
Description
Technical field
The invention provides the preparation method and the dipping method of the dipping glue of making by the blend of two kinds of polyimide with resistance to elevated temperatures.
Background technology
Flood the synthetic of glue and be applied in domestic many patent reports (Chinese patent: 02233769.5,03151268.2,03178347.3,200410028458.4,200510070308.4) that has, but these patents all are to do organic bond with phenolic resinoid, though the advantage of being convenient to process is arranged, but obviously existence can not be high temperature resistant, thermal stability is poor, the shortcoming of dielectric properties difference, has limited use range.Polyimide is the thermotolerance macromolecular material that class has excellent comprehensive performance.From the sixties since U.S. exploitation and industrialization, be applied in every field.Because making, the characteristics of polyimide self are insoluble to general organic solvent, so, process with the presoma polyamic acid of favorable solubility usually, and then the acquisition polyimide is handled in the imines cyclisation of dewatering.But polyamic acid can not be stored for a long time to water sensitive, so that has limited its application on some occasion.So various modified polyimides that occur.In recent years, the patent of relevant fluorine-containing type polyimide is seen in report (Chinese patent: 85101150A, 95100239.2), and the fluorine-containing type polyimide becomes the high performance material with unique advantage and development prospect.Contain fluorine-based introducing, increased the kindliness of molecular chain, a CF
3Side group increases distance between macromolecular chain, has reduced Intermolecular Forces, thereby has made it can be dissolved in multiple organic solvent.Aspect dielectric properties, in all macromolecular materials, the specific inductivity of tetrafluoroethylene (2.0) is minimum.Also show after deliberation, in polyimide, introduce fluorine atom, can reduce the electronic polarization effect.Along with the increase of fluorine content, the specific inductivity of fluorine-containing type polyimide is linear decline with the increase of fractional free volume.In addition, a CF
3Be hydrophobic grouping, reduce the water-absorbent of material, reduce the polarization of electronic polarization effect and dipole orientation, favourable to improving dielectric properties.The specific inductivity of fluorine-containing type polyimide is generally less than 3.0.Compare with common polyimide, it has premium propertiess such as agent of low hygroscopicity, low refractive index and low-k, receives much concern at Aeronautics and Astronautics, microelectronics and military industry field.But owing to fluorochemical monomer costs an arm and a leg, so limited range of application.Patent report (the Chinese patent: 96104106.4), polyimide has been opened up the research frontier that has occurred the commixed type polyimide for reducing cost.
Summary of the invention
The purpose of this invention is to provide the dipping glue of making by the blend of two kinds of polyimide polymers with resistance to elevated temperatures.
First kind of polyimide polymer is aromatic series fluorinated diamine and aromatic series tetracarboxylic dianhydride, and in organic solvent, under the effect of catalyzer, the two-step approach condensation reaction prepares.
Second kind of polyimide polymer is aromatic series tetracarboxylic dianhydride and aromatic diisocyanate, and in organic solvent, under the effect of catalyzer, the single stage method condensation reaction prepares.
With first kind of polyimide polymer and second kind of polyimide polymer 2-10 in proportion: 1 blend obtains high temperature resisting dipping glue.Described ratio better is 3-8: 1.
This high temperature resisting dipping glue is used for glass fibre cellular material or Nomex cellular material, the type that is enhanced cellular material.
Described first kind of polyimide polymer adopts following component synthetic:
(1) have the aromatic series tetracarboxylic dianhydride of following structure:
Wherein Ar is aromatic quaternary groups, comprises the non-condensed nucleus aromatic group that condensed nucleus aromatic group or other linking group are connected.
Described aromatic series tetracarboxylic dianhydride comprises pyromellitic acid anhydride, 3,3`, 4,4`-bibenzene tetracarboxylic dianhydride, 3,3`, 4,4`-diphenyl ether tetraformic dianhydride, 3,3`, 4,4`-benzophenone tetracarboxylic dianhydride, dihydroxyphenyl propane dianhydride and 2,2`-two (3,4-two carboxyphenyls) hexafluoropropane dianhydride is chosen any one kind of them or several mixing is formed.
(2) the aromatic series fluorinated diamine has following general structure:
H
2N-R-NH
2
Wherein R is aromatic divalent group.
Described aromatic series fluorinated diamine comprises: 1, and two (4-amino-2-trifluoromethyl phenolic group) benzene, 4 of 4`-, two (4-amino-2-trifluoromethyl phenolic group) biphenyl, 4 of 4`-, two (3-amino-5-trifluoromethyl phenolic group) biphenyl of 4`-are chosen any one kind of them or several mixing is formed.
(3) organic solvent is N-Methyl pyrrolidone or N, chooses any one kind of them in the N`-dimethyl formamide or two kinds of solvents that mixing is formed.N-Methyl pyrrolidone/N, the weight ratio of N`-dimethyl formamide is 1: 1-5, ratio is 1 preferably: 2-4.
(4) catalyzer is the mixture of acetic anhydride and triethylamine, the perhaps mixture of acetic anhydride and pyridine, and consumption is the 0.1-2% weight percent of total charging capacity.
Described first kind of polyimide polymer prepares as follows:
Under nitrogen or argon shield, fluorinated diamine of the present invention under agitation is dissolved in the organic solvent system, after dissolving finishes, under 0-25 ℃, add the aromatic series tetracarboxylic dianhydride in batches, obtained thick liquid in sustained reaction 1-24 hour.Add down catalyzer at 0-25 ℃, react again under the continuously stirring and continue 1-24 hour, obtain clear solution.
Described second kind of polyimide polymer adopts following component synthetic:
(1) have the aromatic series tetracarboxylic dianhydride of following structure:
Wherein Ar is aromatic quaternary groups, comprises the non-condensed nucleus aromatic group that condensed nucleus aromatic group or other linking group are connected.
The aromatic series tetracarboxylic dianhydride comprises pyromellitic acid anhydride, 3,3`, and 4,4`-bibenzene tetracarboxylic dianhydride, 3,3`, 4,4`-diphenyl ether tetraformic dianhydride, 3,3`, 4,4`-benzophenone tetracarboxylic dianhydride and dihydroxyphenyl propane dianhydride are chosen any one kind of them or several composition.
(2) aromatic diisocyanate has following general structure:
OCN-R-NCO
Wherein R is aromatic divalent group.
Described aromatic diisocyanate comprises: 2, and 4`-tolylene diisocyanate, 4, the 4`-'-diphenylmethane diisocyanate is chosen any one kind of them or two kinds of mixing are formed.
(3) organic solvent is N-Methyl pyrrolidone or N, and the N`-dimethyl formamide is chosen any one kind of them or two kinds of solvents that mixing is formed.N-Methyl pyrrolidone/N, the weight ratio of N`-dimethyl formamide is 1: 1-5, ratio is 1 preferably: 2-4.
(4) catalyzer is an aluminum isopropylate, and consumption is the 0.1-2% weight percent of total charging capacity.
Described second kind of polyimide polymer prepares as follows:
Under nitrogen or argon shield, aromatic series tetracarboxylic dianhydride of the present invention under agitation is dissolved in the organic solvent system.After dissolving finishes, under 0-25 ℃, add aromatic diisocyanate and catalyzer in batches, be reflected under the continuously stirring and continue 4-6 hour, be warming up to 55-140 ℃ of reaction 4-11 hour, be cooled to room temperature and obtain clear solution.
Described two kinds of polyimide blend as follows obtain polyimide dipping glue:
With first kind of polyimide polymer and second kind of polyimide polymer 2-10 in proportion: 1 blend in organic solvent obtains commixed type polyimide high temperature-resistant dipping glue.
Described blend ratio better is 3-8: 1.
Described organic solvent is N, the N`-dimethyl formamide.
Described commixed type polyimide dipping glue uses by following dipping method:
Glass fibre cellular material or Nomex cellular material be impregnated in the glue behind the uniformly penetrating, and in 80-95 ℃ of baking 2-4 hour, 110-140 ℃ of baking 2-4 hour 160-180 ℃ of baking 3-5 hour, made resin enhanced cellular material.
Cellular material behind described commixed type polyimide dipping glue and the dipping has following excellent comprehensive performance:
1) good solubility property.Dissolve in common polarity, weakly polar organic solvent, especially in low boiling point organic solvent, have good solubility.
2) good heat-resisting oxidative stability.Second-order transition temperature is at 220-260 ℃, and heat decomposition temperature is higher than 500 ℃.
3) superior mechanical property and dielectric properties.Glass fibre cellular material through dipping: heat resisting temperature has surpassed 400 ℃, and after 400 ℃/20min test, the concora crush intensity of honeycomb is still greater than 1MPa.Nomex cellular material through dipping: heat resisting temperature surpasses 200 ℃, and after 200 ℃/120min test, concora crush intensity is still up to more than the 1MPa.Record the specific inductivity average out to 2.5 (waveguide short method) of honeycomb under the room temperature.
4) lower solidification value.The solidification value of copoly type polyimide dipping glue is lower than 200 ℃.
5) You Yi resistance to low temperature and agent of low hygroscopicity energy.(55 ℃) cellular material concora crush intensity is constant under the low temperature, and shearing resistance is constant; Water-intake rate is less than 1%.
Embodiment
The following examples further specify the present invention, but do not limit the present invention.
Embodiment 1
Prepare first kind of polyimide polymer: with 45 part 1, two (4-amino-2-trifluoromethyl phenolic group) benzene of 4`-add in 850 parts of N-Methyl pyrrolidone under protection of inert gas is stirred.After dissolving finishes, under 0-25 ℃, add 50 parts of pyromellitic acid anhydrides in batches, reacted 1-24 hour.Obtain the homogeneous phase thick liquid.The mixture of 50 parts of acetic anhydride and triethylamine (1: 1) is added under continuously stirring in the aforesaid liquid, and 0-25 ℃ was reacted 1-24 hour down, obtains clear solution.With infrared absorption spectrometry at 1720cm
-1And 1780cm
-1Imido grpup and carbonyl charateristic avsorption band occur, prove by building-up reactions to obtain corresponding polyimide target product.
Prepare second kind of polyimide polymer: with 50 part 3,3`, 4,4`-diphenyl ether tetraformic dianhydride and 3,3`, 4, the mixture of 4`-benzophenone tetracarboxylic dianhydride adds in 850 parts of N-Methyl pyrrolidone under protection of inert gas is stirred.After dissolving finishes, under 0-5 ℃, add 50 part 2 in batches, 4`-tolylene diisocyanate and 4, the mixture of 4`-'-diphenylmethane diisocyanate (1: 1) reacted 4-6 hour, 5 parts of aluminum isopropylates are added in the aforesaid liquid under continuously stirring, be warming up to 55-140 ℃ of reaction 4-11 hour.Be cooled to room temperature and obtain clear solution.With infrared absorption spectrometry at 1720cm
-1And 1780cm
-1Imido grpup and carbonyl charateristic avsorption band occur, prove by building-up reactions to obtain corresponding polyimide target product.
Get 500 parts of first kind of polyimide solutions and 100 parts of second kind of polyimide solutions,, mix in the N`-dimethyl formamide, obtain commixed type polyimide dipping glue at 200 parts of N.
Getting glass fibre cellular material or Nomex cellular material impregnated in the above-mentioned dipping glue, behind the uniformly penetrating, take out cellular material and after 2-4 hour, toasted 2-4 hour at 110-140 ℃ again in baking under 85-95 ℃, 160-180 ℃ was toasted 3-5 hour, and obtained resin enhanced cellular material.Glass fibre honeycomb behind the dipping: heat resisting temperature has surpassed 400 ℃, and after 450 ℃/20min test, the concora crush intensity of honeycomb is still greater than 1Mpa.Nomex honeycomb behind the dipping: heat resisting temperature surpasses 200 ℃, and after 200 ℃/120min test, concora crush intensity is still up to more than the 1MPa.The specific inductivity that records honeycomb under the room temperature is about 2.5.
Embodiment 2
Prepare first kind of polyimide polymer: with 50 part 4, two (4-amino-2-trifluoromethyl phenolic group) biphenyl of 4`-add in 850 parts of N-Methyl pyrrolidone under protection of inert gas is stirred.After dissolving finishes, under 0-25 ℃, add 48 part 3 in batches, 3`, 4, the 4`-benzophenone tetracarboxylic dianhydride reacted 1-24 hour, obtained the homogeneous phase thick liquid.The mixture of 50 parts of acetic anhydride and triethylamine (1: 1) is added under continuously stirring in the aforesaid liquid, and 0-25 ℃ was reacted 1-24 hour down, obtains clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Prepare second kind of polyimide polymer: under protection of inert gas is stirred, add 50 parts of pyromellitic acid anhydrides in 850 parts of N-Methyl pyrrolidone; after dissolving finishes; under 0-5 ℃; add 50 part 2 in batches; 4`-tolylene diisocyanate and 4, the mixture of 4`-'-diphenylmethane diisocyanate (1: 3) reacted 4-6 hour; 5 parts of aluminum isopropylates are added in the aforesaid liquid under continuously stirring, be warming up to 55-140 ℃ of reaction 4-11 hour.Be cooled to room temperature and obtain clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Get 800 parts of first kind of polyimide solutions and 100 parts of second kind of polyimide solutions,, mix in the N`-dimethyl formamide, obtain commixed type polyimide dipping glue at 200 parts of N.
Employing is with embodiment 1 identical method impregnated glass fiber cellular material or Nomex cellular material, and the effect that obtains is with embodiment 1.
Embodiment 3
Prepare first kind of polyimide polymer: with 56 part 4, two (3-amino-5-trifluoromethyl phenolic group) biphenyl of 4`-add in 850 parts of N-Methyl pyrrolidone under protection of inert gas is stirred.After dissolving finishes, under 0-25 ℃, add 46 part 3 in batches, 3`, 4, the 4`-diphenyl ether tetraformic dianhydride reacted 1-24 hour.Obtain the homogeneous phase thick liquid.The mixture of 50 parts of acetic anhydride and triethylamine (1: 1) is added under continuously stirring in the aforesaid liquid, and 0-25 ℃ was reacted 1-24 hour down, obtains clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Prepare second kind of polyimide polymer: 52 parts of dihydroxyphenyl propane dianhydrides are added in 850 parts of N-Methyl pyrrolidone under protection of inert gas is stirred.After dissolving finishes, under 0-5 ℃, add 49 part 2, the 4`-tolylene diisocyanate reacted 4-6 hour, and 5 parts of aluminum isopropylates are added in the aforesaid liquid under continuously stirring in batches, was warming up to 55-140 ℃ of reaction 4-11 hour.Be cooled to room temperature and obtain clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Get 300 parts of first kind of polyimide solutions and 100 parts of second kind of polyimide solutions,, mix in the N`-dimethyl formamide, obtain commixed type polyimide dipping glue at 100 parts of N.
Employing is with embodiment 1 identical method impregnated glass fiber cellular material or Nomex cellular material, and the effect that obtains is with embodiment 1.
Embodiment 4
Prepare first kind of polyimide polymer: with 46 part 1, two (4-amino-2-trifluoromethyl phenolic group) benzene of 4`-add 850 parts of N under protection of inert gas is stirred, in the N`-dimethyl formamide.After dissolving finishes, under 0-25 ℃, add 51 parts of pyromellitic acid anhydrides and 3 in batches, 3`, 4, the mixture of 4`-benzophenone tetracarboxylic dianhydride (1: 3) reacted 1-24 hour.Obtain the homogeneous phase thick liquid.The mixture of 50 parts of acetic anhydride and triethylamine (1: 1) is added under continuously stirring in the aforesaid liquid, and 0-25 ℃ was reacted 1-24 hour down, obtains clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Prepare second kind of polyimide polymer: 56 parts of pyromellitic acid anhydrides are added in 850 parts of N-Methyl pyrrolidone under protection of inert gas is stirred.After dissolving finishes, under 0-5 ℃, add 46 part 2 in batches, 4`-tolylene diisocyanate and 4, the mixture of 4`-'-diphenylmethane diisocyanate (1: 5) reacts and 5 parts of aluminum isopropylates was added in the aforesaid liquid under continuously stirring in 4-6 hour, is warming up to 55-140 ℃ of reaction 4-11 hour.Be cooled to room temperature and obtain clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Get 700 parts of first kind of polyimide solutions and 100 parts of second kind of polyimide solutions,, mix in the N`-dimethyl formamide, obtain commixed type polyimide dipping glue at 150 parts of N.
Employing is with embodiment 1 identical method impregnated glass fiber cellular material or Nomex cellular material, and the effect that obtains is with embodiment 1.
Embodiment 5
Prepare first kind of polyimide polymer: with 48 part 1; two (4-amino-2-trifluoromethyl phenolic group) benzene and 4 of 4`-; the mixture of two (3-amino-5-trifluoromethyl phenolic group) biphenyl (1: 2) of 4`-is under protection of inert gas is stirred; add 850 parts of N, in the mixed solvent of N`-dimethyl formamide and N-Methyl pyrrolidone (5: 2).After dissolving finishes, under 0-25 ℃, add 54 part 3 in batches, 3`, 4, the 4`-bibenzene tetracarboxylic dianhydride reacted 1-24 hour, obtained the homogeneous phase thick liquid.The mixture of 50 parts of acetic anhydride and triethylamine (1: 1) is added under continuously stirring in the aforesaid liquid, and 0-25 ℃ was reacted 1-24 hour down, obtains clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Prepare second kind of polyimide polymer: 54 parts of dihydroxyphenyl propane dianhydrides are added in 850 parts of N-Methyl pyrrolidone under protection of inert gas is stirred.After dissolving finishes, under 0-5 ℃, add 48 part 2 in batches, 4`-tolylene diisocyanate and 4, the mixture of 4`-'-diphenylmethane diisocyanate (4: 1) reacted 4-6 hour, 5 parts of aluminum isopropylates are added in the aforesaid liquid under continuously stirring, be warming up to 55-140 ℃ of reaction 4-11 hour.Be cooled to room temperature and obtain clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Get 400 parts of first kind of polyimide solutions and 100 parts of second kind of polyimide solutions,, mix in the N`-dimethyl formamide, obtain commixed type polyimide dipping glue at 200 parts of N.
Employing is with embodiment 1 identical method impregnated glass fiber cellular material or Nomex cellular material, and the effect of dipping glue is with embodiment 1.
Embodiment 6
Prepare first kind of polyimide polymer: with 44 part 1; two (4-amino-2-trifluoromethyl phenolic group) benzene, 4 of 4`-; the mixture of two (4-amino-2-trifluoromethyl phenolic group) biphenyl (1: 2) of 4`-is under protection of inert gas is stirred; add 850 parts of N, in the mixed solvent of N`-dimethyl formamide and N-Methyl pyrrolidone (4: 1).After dissolving finishes, under 0-25 ℃, add 52 part 3 in batches, dihydroxyphenyl propane dianhydride and 3,3`, 4, the mixture of 4`-benzophenone tetracarboxylic dianhydride (1: 4) reacted 1-24 hour.Obtain the homogeneous phase thick liquid.The mixture of 50 parts of acetic anhydride and triethylamine (1: 1) is added under continuously stirring in the aforesaid liquid, and 0-25 ℃ was reacted 1-24 hour down, obtains clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Prepare second kind of polyimide polymer: with 52 part 3,3`, 4,4`-bibenzene tetracarboxylic dianhydride and 3`, 4, the mixture of 4`-diphenyl ether tetraformic dianhydride (1: 2) under protection of inert gas is stirred, adds in 850 parts of N-Methyl pyrrolidone.After dissolving finishes, under 0-5 ℃, add 46 part 2 in batches, 4`-tolylene diisocyanate and 4, the mixture of 4`-'-diphenylmethane diisocyanate (1: 3) reacted 4-6 hour, 5 parts of aluminum isopropylates are added in the aforesaid liquid under continuously stirring, be warming up to 55-140 ℃ of reaction 4-11 hour.Be cooled to room temperature and obtain clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Get 600 parts of first kind of polyimide solutions and 100 parts of second kind of polyimide solutions,, mix in the N`-dimethyl formamide, obtain commixed type polyimide dipping glue at 100 parts of N.
Employing is with embodiment 1 identical method impregnated glass fiber cellular material or Nomex cellular material, and the effect that obtains is with embodiment 1.
Embodiment 7
Prepare first kind of polyimide polymer: with 47 part 4; two (4-amino-2-trifluoromethyl phenolic group) biphenyl, 4 of 4`-; the mixture of two (3-amino-5-trifluoromethyl phenolic group) biphenyl (1: 1) of 4`-is under protection of inert gas is stirred; add 850 parts of N, in the mixed solvent of N`-dimethyl formamide and N-Methyl pyrrolidone (3: 1).After dissolving finishes, under 0-25 ℃, add 53 parts of dihydroxyphenyl propane dianhydrides in batches, reacted 1-24 hour, obtain the homogeneous phase thick liquid.The mixture of 50 parts of acetic anhydride and triethylamine (1: 1) is added under continuously stirring in the aforesaid liquid, and 0-25 ℃ was reacted 1-24 hour down, obtains clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Prepare second kind of polyimide polymer: with 53 part 3,3`, 4, the mixture of 4`-benzophenone tetracarboxylic dianhydride and pyromellitic acid anhydride (3: 1) adds in 850 parts of N-Methyl pyrrolidone under protection of inert gas is stirred.After dissolving finishes, under 0-5 ℃, add 48 part 2 in batches, 4`-tolylene diisocyanate and 4, the mixture of 4`-'-diphenylmethane diisocyanate (1: 3) reacts and 5 parts of aluminum isopropylates was added in the aforesaid liquid under continuously stirring in 4-6 hour, is warming up to 55-140 ℃ of reaction 4-11 hour.Be cooled to room temperature and obtain clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Get 800 parts of first kind of polyimide solutions and 100 parts of second kind of polyimide solutions,, mix in the N`-dimethyl formamide, obtain commixed type polyimide dipping glue at 200 parts of N.
Employing is with embodiment 1 identical method impregnated glass fiber cellular material or Nomex cellular material, and the effect that obtains is with embodiment 1.
Embodiment 8
Prepare first kind of polyimide polymer: with 54 part 4, two (4-amino-2-trifluoromethyl phenolic group) biphenyl of 4`-add in 850 parts of N-Methyl pyrrolidone under protection of inert gas is stirred.After dissolving finishes, under 0-25 ℃, add 46 part 2, two (3, the 4-two carboxyphenyls) hexafluoropropane dianhydrides of 2`-reacted 1-24 hour, obtained the homogeneous phase thick liquid in batches.The mixture of 50 parts of acetic anhydride and triethylamine (1: 1) is added under continuously stirring in the aforesaid liquid, and 0-25 ℃ was reacted 1-24 hour down, obtains clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Prepare second kind of polyimide polymer: with 58 part 3,3`, 4,4`-benzophenone tetracarboxylic dianhydride and 3,3`, 4, the mixture of 4`-diphenyl ether tetraformic dianhydride (1: 1) adds in 850 parts of N-Methyl pyrrolidone under protection of inert gas is stirred.After dissolving finishes, under 0-5 ℃, add 44 part 2 in batches, 4`-tolylene diisocyanate and 4, the mixture of 4`-'-diphenylmethane diisocyanate (1: 1) reacted 4-6 hour, 5 parts of aluminum isopropylates are added in the aforesaid liquid under continuously stirring, be warming up to 55-140 ℃ of reaction 4-11 hour.Be cooled to room temperature and obtain clear solution.Imido grpup and carbonyl charateristic avsorption band occur with infrared absorption spectrometry, prove by building-up reactions to obtain corresponding polyimide target product.
Get 300 parts of first kind of polyimide solutions and 100 parts of second kind of polyimide solutions,, mix in the N`-dimethyl formamide, obtain commixed type polyimide dipping glue at 200 parts of N.
Employing is with embodiment 1 identical method impregnated glass fiber cellular material or Nomex cellular material, and the effect that obtains is with embodiment 1.
Claims (10)
1. the blend of two kinds of polyimide polymers is characterized in that:
First kind of polyimide polymer adopts following component synthetic:
(1) have the aromatic series tetracarboxylic dianhydride of following structure:
Wherein Ar is aromatic quaternary groups, comprises the non-condensed nucleus aromatic group that condensed nucleus aromatic group or other linking group are connected;
(2) the aromatic series fluorinated diamine has following general structure:
H
2N-R-NH
2
Wherein R is aromatic divalent group;
(3) organic solvent is N-Methyl pyrrolidone or N, and the N`-dimethyl formamide is chosen any one kind of them or two kinds of solvents that mixing is formed;
(4) catalyzer is the mixture of acetic anhydride and triethylamine, the perhaps mixture of acetic anhydride and pyridine, and consumption is the 0.1-2% weight percent of total charging capacity;
Described second kind of polyimide polymer adopts following component synthetic:
(1) have the aromatic series tetracarboxylic dianhydride of following structure:
Wherein Ar is aromatic quaternary groups, comprises the non-condensed nucleus aromatic group that condensed nucleus aromatic group or other linking group are connected;
The aromatic series tetracarboxylic dianhydride comprises pyromellitic acid anhydride, 3,3`, and 4,4`-bibenzene tetracarboxylic dianhydride, 3,3`, 4,4`-diphenyl ether tetraformic dianhydride, 3,3`, 4,4`-benzophenone tetracarboxylic dianhydride and dihydroxyphenyl propane dianhydride are chosen any one kind of them or several composition;
(2) aromatic diisocyanate has following general structure:
OCN-R-NCO
Wherein R is aromatic divalent group, comprises 2,4`-tolylene diisocyanate, 4, and the 4`-'-diphenylmethane diisocyanate is chosen any one kind of them or two kinds of mixing are formed;
(3) organic solvent is N-Methyl pyrrolidone or N, and the N`-dimethyl formamide is chosen any one kind of them or two kinds of solvents that mixing is formed;
(4) catalyzer is an aluminum isopropylate, and consumption is the 0.1-2% weight percent of total charging capacity.
2. according to the blend of the polyimide polymer of claim 1, it is characterized in that described first kind of polyimide polymer obtains by following method:
Under nitrogen or argon shield, fluorinated diamine of the present invention under agitation is dissolved in the organic solvent system, after dissolving finishes, under 0-25 ℃, add the aromatic series tetracarboxylic dianhydride in batches, obtained thick liquid in sustained reaction 1-24 hour.Add down catalyzer at 0-25 ℃, react again under the continuously stirring and continue 1-24 hour, obtain clear solution.
3. according to the blend of the polyimide polymer of claim 1, it is characterized in that described second kind of polyimide polymer obtains by following method:
Under nitrogen or argon shield; under agitation be dissolved in aromatic series tetracarboxylic dianhydride of the present invention in the organic solvent system; after dissolving finishes; under 0-25 ℃; add aromatic diisocyanate and catalyzer in batches; be reflected under the continuously stirring and continue 4-6 hour, be warming up to 55-140 ℃ of reaction 4-11 hour, be cooled to room temperature and obtain clear solution.
4. according to the blend of the polyimide polymer of claim 1, it is characterized in that described aromatic series tetracarboxylic dianhydride comprises: pyromellitic acid anhydride, 3,3`, 4,4`-bibenzene tetracarboxylic dianhydride, 3,3`, 4,4`-diphenyl ether tetraformic dianhydride, 3,3`, 4,4`-benzophenone tetracarboxylic dianhydride, dihydroxyphenyl propane dianhydride and 2,2`-two (3,4-two carboxyphenyls) hexafluoropropane dianhydride is chosen any one kind of them or several mixing is formed.
5. according to the blend of the polyimide polymer of claim 1, it is characterized in that, described aromatic series fluorinated diamine comprises: 1, two (4-amino-2-trifluoromethyl phenolic group) benzene, 4 of 4`-, two (4-amino-2-trifluoromethyl phenolic group) biphenyl, 4 of 4`-, two (3-amino-5-trifluoromethyl phenolic group) biphenyl of 4`-are chosen any one kind of them or several mixing is formed.
6. according to the blend of the polyimide polymer of claim 1, it is characterized in that described aromatic diisocyanate comprises: 2,4`-tolylene diisocyanate, 4, the 4`-'-diphenylmethane diisocyanate, choose any one kind of them or two kinds mix and form.
7. a commixed type polyimide high temperature-resistant floods glue, it is characterized in that, with the blend of two kinds of polyimide polymers of claim 1, blend obtains polyimide dipping glue as follows: first kind of polyimide polymer and second kind of polyimide polymer be 2-10 in proportion: 1 blend in organic solvent.
8. according to the commixed type polyimide high temperature-resistant dipping glue of claim 7, it is characterized in that described blend ratio is 3-8: 1, described organic solvent is N, the N`-dimethyl formamide.
9. the using method of commixed type polyimide high temperature-resistant dipping glue as claimed in claim 7 is characterized in that, glass fibre cellular material or Nomax cellular material be impregnated in uniformly penetrating in the glue.
10. enhanced cellular material, it is characterized in that, glass fibre cellular material or Nomax cellular material be impregnated in the commixed type polyimide high temperature-resistant dipping glue as claimed in claim 7, behind the uniformly penetrating, in 80-95 ℃ of baking 2-4 hour, 110-140 ℃ was toasted 2-4 hour, 160-180 ℃ of baking 3-5 hour, made resin enhanced cellular material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230196B (en) * | 2008-02-26 | 2010-06-02 | 东南大学 | In-situ polymerization PI modified nylon composite material |
| CN108485592A (en) * | 2018-03-23 | 2018-09-04 | 黑龙江省科学院石油化学研究院 | A kind of long-term resistance to 300 DEG C of paper honeycombs core bar adhesive and preparation method thereof |
| CN109852340A (en) * | 2018-12-21 | 2019-06-07 | 福建省海钛智能科技有限公司 | A kind of YASI-BDAPOFP type Organic fluoride silica gel and preparation method thereof |
| CN110028788A (en) * | 2018-01-11 | 2019-07-19 | 洛阳轴承研究所有限公司 | A kind of composite polyimide material, porous polyimide retainer and preparation method thereof, bearing |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082068C (en) * | 1998-04-01 | 2002-04-03 | 中国科学院化学研究所 | Short staple-containing composite polyimide material and its preparation and use |
| CN1117133C (en) * | 1999-09-21 | 2003-08-06 | 中国科学院化学研究所 | Soluble polyimide coating glue and its preparation and use |
| CN1117795C (en) * | 1999-10-22 | 2003-08-13 | 中国科学院化学研究所 | Polyimides coating adhesive with hydrolysis resistance and high solid content and its preparation method |
| JP2001262116A (en) * | 2000-03-16 | 2001-09-26 | Nippon Steel Chem Co Ltd | Adhesive polyimide resin for electronic component |
| CN1229421C (en) * | 2003-04-04 | 2005-11-30 | 中国科学院化学研究所 | Soluble fluorine-containing polyamidoimide resin, its preparation method and application |
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- 2006-07-24 CN CNB2006101036082A patent/CN100462403C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101230196B (en) * | 2008-02-26 | 2010-06-02 | 东南大学 | In-situ polymerization PI modified nylon composite material |
| CN110028788A (en) * | 2018-01-11 | 2019-07-19 | 洛阳轴承研究所有限公司 | A kind of composite polyimide material, porous polyimide retainer and preparation method thereof, bearing |
| CN108485592A (en) * | 2018-03-23 | 2018-09-04 | 黑龙江省科学院石油化学研究院 | A kind of long-term resistance to 300 DEG C of paper honeycombs core bar adhesive and preparation method thereof |
| CN109852340A (en) * | 2018-12-21 | 2019-06-07 | 福建省海钛智能科技有限公司 | A kind of YASI-BDAPOFP type Organic fluoride silica gel and preparation method thereof |
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| CN100462403C (en) | 2009-02-18 |
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