CN105542458B - A kind of high-strength and high ductility polyimide resin based composites and preparation method thereof - Google Patents

A kind of high-strength and high ductility polyimide resin based composites and preparation method thereof Download PDF

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CN105542458B
CN105542458B CN201610035838.3A CN201610035838A CN105542458B CN 105542458 B CN105542458 B CN 105542458B CN 201610035838 A CN201610035838 A CN 201610035838A CN 105542458 B CN105542458 B CN 105542458B
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polyimide resin
polyimides
fiber
based composites
strength
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CN105542458A (en
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田国峰
曾勇要
韩恩林
齐胜利
牛鸿庆
武德珍
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
    • F16D69/02—Composition of linings ; Methods of manufacturing
    • F16D69/025—Compositions based on an organic binder
    • F16D69/026—Compositions based on an organic binder containing fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2279/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain not provided for in groups B29K2261/00 - B29K2277/00, as reinforcement
    • B29K2279/08—PI, i.e. polyimides or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2879/00—Use of polymers having nitrogen, with or without oxygen, or carbon only, in the main chain not provided for in groups B29K2861/00 - B29K2877/00, as mould material
    • B29K2879/08—PI, i.e. polyimides or derivatives thereof
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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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    • C08J2479/00—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 C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
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Abstract

A kind of high-strength and high ductility polyimide resin based composites and preparation method thereof, belong to polyimide resin technical field.This method includes：(1) polyimide resin solution is prepared；(2) polyimides fiber is surface-treated；(3) product that step (2) obtains is dispersed in the polyimide resin solution that step (1) obtains under agitation；(4) mixed slurry for obtaining step (3) carries out heating treatment；(5) product for obtaining step (4) carries out hot-forming processing；The polyimides fiber is at least one of polyimide fiber pulp, polyimides chopped strand and polyimides fibrid.Additionally provide high-strength and high ductility polyimide resin based composites made from the above method.Polyimide resin based composites made from the method for the present invention have higher toughness, more excellent temperature tolerance, mechanics and processing characteristics.

Description

A kind of high-strength and high ductility polyimide resin based composites and preparation method thereof
Technical field
The present invention relates to high temperature resistant, high intensity, high toughness polyimide composite field, in particular it relates to a kind of high High-strength and high ductility polyimide resin base prepared by the preparation method and this method of strong high-ductility polyimide resin based composites Composite, belong to polyimide resin technical field.
Background technology
Polyimide material has excellent resistance to elevated temperatures, mechanical property, absolutely with its unique heteroaromatic rigid structure The performance characteristics such as edge performance and corrosion-resistant, resistance to irradiation, obtained resin, film, fiber, composite is produced using it as raw material It is widely applied Deng in each field such as electron and electrician, machine-building, Aero-Space.Wherein, polyimide resin conduct Temperature resistant grade highest matrix material in organic material, it is the structures such as high temperature gear, brake block, aircraft tail, rocket covering, housing The preferred material considered in part preparation process.The limit that its property indices directly affects prepared product uses bar Part, so as to limit the development of the technology in corresponding field and lifting.By taking supersonic plane shell material as an example, from polymer Material can be very good to meet needs of the aircraft for loss of weight, but surface temperature caused by high-speed flight is to the resistance to height of material Warm nature can propose strict requirements.Therefore, polyimide resin material successively experienced the first generation resistance to 316 DEG C of materials, second For the resistance to 426 DEG C of materials of resistance to 371 DEG C of materials and the present third generation.
To obtain the polyimide resin material of more high-temperature resistant grade, maximally efficient method is to adjust the chemistry of strand Structure, introduce rigid radical.In order to improve the processing characteristics of polyimide resin material, it is necessary to reduce molecular weight, so as to reduce Melt viscosity.However, the introducing of rigid radical can reduce molecule chain flexibility, the reduction of molecular weight will cause the crosslinking after solidifying Density improves, and two kinds of factors can reduce the impact strength and toughness of product.There is research using addition TPI tree The method of fat, although can effectively improve the toughness of product, the heat resistance of material can be influenceed to a certain extent.
Therefore, how above-mentioned relation is balanced, higher heatproof is pursued while toughness of material and processing characteristics is not influenceed Performance and mechanical property, it is the important topic that existing high-performance polyimide resin material research field is faced.
The content of the invention
The invention aims to overcome polyimide resin material toughness, processing characteristics and heatproof in the prior art The defects of performance and excellent mechanical property can not have concurrently, there is provided a kind of that there is higher toughness, more excellent temperature tolerance, mechanical property Energy and the polyimide resin based composites of processing characteristics and preparation method thereof.
Therefore, to achieve these goals, the invention provides a kind of high-strength and high ductility polyimide resin based composites Preparation method, this method includes：
(1) polyimide resin solution is prepared；
(2) polyimides fiber is surface-treated；
(3) the polyimides fiber for the surface treatment under agitation obtaining step (2) is dispersed in step (1) and obtained To polyimide resin solution in；
(4) mixed slurry for obtaining step (3) carries out heating treatment；
(5) product for obtaining step (4) carries out hot-forming processing.
In step (1), the solid content of the polyimide resin solution is 5-40wt%；Polyimide resin is strand Hold the polyimide resin containing unsaturated bond, it is preferable that the weight average molecular weight of polyimide resin is 2000-20000.
The polyimides fiber is that polyimide fiber pulp, polyimides chopped strand and polyimides precipitating are fine At least one of dimension.
When polyimides fiber is polyimide fiber pulp, it is preferable that the polyimide fiber pulp is averaged Length is 0.1-10mm, more preferably 0.5-2mm, specific surface area 5-20m2/g；
The method of the surface treatment is soda solution grouting or low temperature plasma method.The soda solution grouting includes：It is molten using NaOH Liquid etches fiber 1-10min, and the concentration of NaOH solution is 5-10wt%, it is preferable that per the pending fibers of 1g, corresponding NaOH solution Dosage be 20-100ml；The low temperature plasma method includes：Using oxygen plasma to fiber under power 200-250W Carry out surface treatment 1-10min.
Step (3), the polyimide resin solution of 100 parts by weight, the dosage of the corresponding polyimides fiber is 5- 40 parts by weight, preferably 5-15 parts by weight.
In step (3), scattered temperature is 25-80 DEG C, preferably 25 DEG C -50 DEG C；Stirring condition includes：Mixing speed is 100-2000r/min, preferably 200-1000r/min.
The mode of step (4) described heating treatment includes：150-300 DEG C is risen to 2-10 DEG C/min heating rate, is protected Warm 0.5-2h, it is preferable that rise to 150-250 DEG C with 5-10 DEG C/min heating rate, be incubated 1-1.5h.
The condition of step (5) hot-forming processing includes：Temperature is 320-400 DEG C, pressure 1-8MPa, time 0.5- 2h。
The preparation method of above-mentioned polyimides fibrid includes：
(1) amine monomers and anhydrides monomer are reacted into generation polyamic acid product in polar solvent；
(2) by the product dilution that step (1) obtains to polyamic acid concentration is 1-14wt% and viscosity is less than at room temperature 500cp, then the solution after dilution is injected in precipitating reagent under agitation；
(3) product for obtaining step (2) carries out hot imidization.
On the other hand, the invention provides high-strength and high ductility polyimide resin based composites prepared by the above method.Institute Obtain application of the high-strength and high ductility polyimide resin based composites in brake block.
In the present invention, using polyimides fiber (be specially polyimide fiber pulp, polyimides chopped strand and Polyimides fibrid) modified have the advantage that and innovative is filled to polyimide resin.First, above-mentioned polyamides Imines fiber surface contains a large amount of active groups (carboxyl-COOH and amino-NH-) after processing, when being mixed with resin solution Complete resin bed can be coated in fiber surface by the hydrogen bond action between active group, realize the close knot of fiber and resin Close；Secondly, in the product after forming and hardening, fiber can form the network of 3 D stereo, play skeletal support effect, not only may be used To improve the mechanical strength of product, the toughness of product can also be increased substantially；3rd, it is most important that the toughness reinforcing, enhancing are filled out The chemical constitution of material is all polyimides, has been effectively maintained the excellent resistance to elevated temperatures of polyimide material and resistance to ultraviolet irradiation And the performance characteristics such as low water absorption, the temperature resistant grade of resin matrix is not interfered with not only, additionally it is possible to is improved to a certain extent The applied at elevated temperature performance of product.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of preparation method of high-strength and high ductility polyimide resin based composites, the party Method includes：
(1) polyimide resin solution is prepared；
(2) polyimides fiber is surface-treated；
(3) product that step (2) obtains is dispersed in the polyimide resin solution that step (1) obtains under agitation In；
(4) mixed slurry for obtaining step (3) carries out heating treatment；
(5) product for obtaining step (4) carries out hot-forming processing；
The polyimides fiber is that polyimide fiber pulp, polyimides chopped strand and polyimides precipitating are fine At least one of dimension.
According to method of the present invention, in step (1), it is preferable that the solid content of the polyimide resin solution is 5-40 weight %, solvent for use are ethanol.
It is highly preferred that polyimide resin is the polyimide resin that molecular chain-end contains unsaturated bond, so as to enter Intensity, toughness and the heat-resisting quantity of polyimide resin based composites made from the raising of one step.
It is further preferred that the weight average molecular weight of polyimide resin is 2000-20000, so as to further improve Intensity, toughness and the heat-resisting quantity of obtained polyimide resin based composites.
In the present invention, polyimide resin commercially available can also can be made by oneself, wherein homemade method can be that this area is each The conventional method of kind, such as may be referred to " Chen Jiansheng, left Red Army, high different mountain, He Guanjun, Fan Lin, Yang Shiyong, phenylacetylene base envelope Hold preparation and the performance study of PMR polyimide type resins, aeronautical material journal, the preparation method in 27 (5) 66-70 " documents.
According to method of the present invention, in step (2), it is preferable that the polyimides fiber is that polyimides is fine Pulp is tieed up, so as to further improve intensity, toughness and the heat-resisting quantity of obtained polyimide resin based composites.More Preferably, the average length of the polyimide fiber pulp is 0.1-10mm, most preferably 0.5-2mm, specific surface area 5- 20m2/ g, so as to further improve intensity, toughness and the heat-resisting quantity of obtained polyimide resin based composites.
In the present invention, it is preferable that the preparation method of polyimides fibrid includes：(1) by amine monomers and anhydrides Monomer reacts generation polyamic acid product in polar solvent；(2) by the product dilution that step (1) obtains to polyamic acid concentration Viscosity is less than 500cp for 1-14wt% and at room temperature, and the solution after dilution is then injected into precipitating reagent under agitation and (such as gone Ionized water, acetone etc.) in；(3) product for obtaining step (2) carries out hot imidization.
In a kind of most preferably embodiment, the preparation method of polyimides fibrid includes：(1) by benzidine It is 5 by volume to be dissolved in N, N- dimethyl acetamide and dimethylbenzene:1 in the mixed solvent, then add anhydrides monomer (acid The composition of anhydride monomer is preferably：2,3,3 ', 4 '-BPDA, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride and 3,3 ', 4, 4 '-oxydiphthalic, weight ratio are 1：5：1) mol ratio for, controlling benzidine and anhydrides monomer is 1：1.05 and Every liter of in the mixed solvent solids content is 300g, and stirring reaction generates polyamic acid product；(2) what is obtained into step (1) is poly- The content that above-mentioned mixed solvent to polyamic acid are added in acid amides acid product is 10wt%, and solution viscosity is 300cp at room temperature, so It is injected under agitation in deionized water afterwards, is further continued for stirring, product is then washed with water, obtains polyamic acid precipitating fibre Dimension；(3) the polyamic acid fibrid that step (2) obtains is carried out hot imidization, obtained by fluidization hot imidization Polyimides fibrid.
In the present invention, when using polyimides fibrid, its average length can be with 0.1-10mm, when sub- using polyamides During amine chopped strand, its average length can be with 1-20mm.
According to method of the present invention, in step (2), the method for the surface treatment can be the various routines in this area Method, such as can be soda solution grouting or low temperature plasma method.Preferably, the soda solution grouting includes：Carved using NaOH solution Fiber 1-10min is lost, the concentration of NaOH solution is 5-10 weight %, it is preferable that relative to the pending fibers of 1g, NaOH solution Dosage is 20-100ml, so as to further improve the intensity of obtained polyimide resin based composites, toughness and resistance to It is high temperatures.
Preferably, the low temperature plasma method includes：Fiber is entered using oxygen plasma under power 200-250W Row surface treatment 1-10min, so as to further improve the intensity of obtained polyimide resin based composites, toughness and Heat-resisting quantity.
The method of the present invention can also include：The product that step (2) obtains is washed with water to after neutrality and is redispersed in step Suddenly in the polyimide resin solution that (1) obtains.
According to method of the present invention, in step (3), it is preferable that the polyimide resin relative to 100 parts by weight is molten Liquid, the dosage of the corresponding polyimides fiber is 5-40 parts by weight, more preferably 5-15 parts by weight, so as to further The intensity of polyimide resin based composites, toughness and heat-resisting quantity made from raising.
According to method of the present invention, in step (3), it is preferable that the scattered temperature is 25-80 DEG C, more preferably For 25 DEG C -50 DEG C, so as to further improve intensity, toughness and the high temperature resistant of obtained polyimide resin based composites Property.
According to method of the present invention, in step (3), it is preferable that the stirring condition includes：Mixing speed is 100- 2000r/min, more preferably 200-1000r/min, so as to further improve obtained polyimide resin base composite wood Intensity, toughness and the heat-resisting quantity of material.
According to method of the present invention, in step (4), it is preferable that the mode of the heating treatment includes：With 2-10 DEG C/min heating rate rises to 150-300 DEG C, it is incubated 0.5-2h, it is preferable that rise to 5-10 DEG C/min heating rate 150-250 DEG C, 1-1.5h is incubated, so as to further improve the intensity of obtained polyimide resin based composites, tough Property and heat-resisting quantity.
According to method of the present invention, in step (5), the condition of the hot-forming processing can be that this area is various Hot-forming treatment conditions, it is preferable that the condition of the hot-forming processing includes：Temperature is 320-400 DEG C, pressure 1- 8MPa, time 0.5-2h, so as to further improve the intensity of obtained polyimide resin based composites, toughness and Heat-resisting quantity.
On the other hand, the invention provides high-strength and high ductility polyimide resin based composites prepared by the above method.
5 weight % heat decomposition temperatures of the high-strength and high ductility polyimide resin based composites of the present invention are curved more than 550 DEG C Qu Qiangdu is more than 120MPa, and tensile strength is more than 90MPa, and elongation at break is more than 4%, and impact strength is more than 20Jcm-2。
Embodiment
Polyimide resin is according to document " Chen Jiansheng, left Red Army, high different mountain, He Guanjun, Fan Lin, Yang Shiyong, phenylacetylene base Preparation and the performance study of PMR polyimide type resins, aeronautical material journal are blocked, prepared by the method in 27 (5) 66-70 ".
Polyimide fiber pulp and polyimides chopped strand are purchased from Jiangsu Xian Nuo new materials Science and Technology Ltd..
The preparation method of polyimides fibrid is：Benzidine is dissolved in N, N- dimethyl acetamide and dimethylbenzene It is 5 by volume:1 in the mixed solvent, then adding anhydrides monomers, (composition of anhydrides monomer is：2,3,3 ', 4 '-connection Acid dianhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides and 3,3 ', 4,4 '-oxydiphthalic, weight ratio is 1：5：1), The mol ratio for controlling benzidine and anhydrides monomer is 1：1.05, and every liter of in the mixed solvent solids content is 300g, at 5 DEG C Lower stirring reaction 3h generates polyamic acid product；(2) to add above-mentioned mixing in the polyamic acid product obtained into step (1) molten Agent to the content of polyamic acid is 10 weight %, and solution viscosity is 300cp at room temperature, then in 50 DEG C, 1000r/min stirring speed It is injected under degree in deionized water, is further continued for stirring 15min, product is then washed with water, obtains polyamic acid fibrid； (3) by the polyamic acid fibrid that step (2) obtains by fluidization hot imidization, the hot imidization at 350 DEG C 5min, obtain polyimides fibrid.Application of the gained high-strength and high ductility polyimide resin based composites in brake block.
Embodiment 1
The present embodiment is used to illustrate high-strength and high ductility polyimide resin based composites of the present invention and preparation method thereof.
(1) use 1500ml 5wt%NaOH solution surfaces processing 15g polyimides pulp fibers (average length 2mm, Specific surface area is 7m2/g)5min；
(2) step (1) is obtained into product and is washed with water to neutrality；
(3) in the case where 40 DEG C of temperature, mixing speed are 600r/min, the polyimides pulp fibers that step (2) is obtained divide It is dispersed in polyimide resin solution made from 100g (solid content 40%, weight average molecular weight 2000)；
(4) heating rate of the mixed slurry through 5 DEG C/min that step (3) obtains is risen to 240 DEG C, and is incubated 1h；
(5) under conditions of temperature is 370 DEG C, pressure is 6MPa, the product that step (4) is obtained carries out hot-forming place 1h is managed, high-strength and high ductility polyimide resin based composites A1 is made.
Embodiment 2
The present embodiment is used to illustrate high-strength and high ductility polyimide resin based composites of the present invention and preparation method thereof.
(1) power be 200W under, use oxygen plasma to 5g polyimides pulp fibers (average length 1mm, than Surface area is 11m2/ g) carry out surface treatment 5min；
(2) step (1) is obtained into product and is washed with water to neutrality；
(3) in the case where 25 DEG C of temperature, mixing speed are 1000r/min, the polyimides pulp fibers that step (2) is obtained divide It is dispersed in polyimide resin solution made from 100g (solid content 30%, weight average molecular weight 10000)；
(4) heating rate of the mixed slurry through 10 DEG C/min that step (3) obtains is risen to 220 DEG C, and is incubated 1h；
(5) under conditions of temperature is 320 DEG C, pressure is 2MPa, the product that step (4) is obtained carries out hot-forming place 2h is managed, high-strength and high ductility polyimide resin based composites A2 is made.
Embodiment 3
The present embodiment is used to illustrate high-strength and high ductility polyimide resin based composites of the present invention and preparation method thereof.
(1) use 500ml 10wt%NaOH solution surfaces processing 10g polyimides pulp fibers (average length for 0.5mm, specific surface area 16m2/g)2min；
(2) step (1) is obtained into product and is washed with water to neutrality；
(3) in the case where temperature 50 C, mixing speed are 200r/min, the polyimides pulp fibers that step (2) is obtained divide It is dispersed in polyimide resin solution made from 100g (solid content 20%, weight average molecular weight 20000)；
(4) heating rate of the mixed slurry through 8 DEG C/min that step (3) obtains is risen to 150 DEG C, and is incubated 1.5h；
(5) under conditions of temperature is 370 DEG C, pressure is 1MPa, the product that step (4) is obtained carries out hot-forming place 0.5h is managed, high-strength and high ductility polyimide resin based composites A3 is made.
Embodiment 4
The present embodiment is used to illustrate high-strength and high ductility polyimide resin based composites of the present invention and preparation method thereof.
Method according to embodiment 1 prepares high-strength and high ductility polyimide resin based composites A4, unlike, it will implement Polyimides pulp fibers in example 1 replace with obtained polyimides fibrid.
Embodiment 5
The present embodiment is used to illustrate high-strength and high ductility polyimide resin based composites of the present invention and preparation method thereof.
Method according to embodiment 1 prepares high-strength and high ductility polyimide resin based composites A5, unlike, it will implement Polyimides pulp fibers in example 1 replace with the equal polyimides chopped strand of average length.
Embodiment 6
The present embodiment is used to illustrate high-strength and high ductility polyimide resin based composites of the present invention and preparation method thereof.
Method according to embodiment 1 prepares high-strength and high ductility polyimide resin based composites A6, unlike, polyamides is sub- The amount of amine pulp fibers is 3g, and the weight average molecular weight of polyimide resin is 1000, and the solid content of polyimide resin solution is 3wt%.
Embodiment 7
The present embodiment is used to illustrate high-strength and high ductility polyimide resin based composites of the present invention and preparation method thereof.
Method according to embodiment 1 prepares high-strength and high ductility polyimide resin based composites A7, unlike, relative to 100g polyimide resin solution, the dosage of polyimides pulp fibers is 40g.
Embodiment 8
The present embodiment is used to illustrate high-strength and high ductility polyimide resin based composites of the present invention and preparation method thereof.
Method according to embodiment 1 prepares high-strength and high ductility polyimide resin based composites A8, unlike, at heating The mode of reason is：280 DEG C are risen to 2 DEG C/min heating rate, is incubated 2h.
Test case
Using the heat decomposition temperature of thermal gravimetric analyzer determination sample, its 5wt% heat decomposition temperature result see the table below 1.
Using universal testing machine, according to the bending property of GB/T 9341-2000 determination samples, according to GB/T The tensile property of 1040.4-2006 determination samples, impact strength is determined using radial-boom impact tester, measurement result is seen below Table 1.
Table 1
By data above as can be seen that the polyimide resin based composites prepared using the method for the present invention are had Higher heat decomposition temperature and higher toughness and intensity.
When the polyimides fiber is polyimide fiber pulp, obtained polyimides tree can be further improved Intensity, toughness and the heat-resisting quantity of resin-based composite, embodiment 1 can be seen that compared with embodiment 4 and 5.
When the solid content of the polyimide resin solution is 5-40wt%, polyimide resin is that molecular chain-end contains not The polyimide resin of saturated bond, (above-described embodiment, polyamides are sub- when the weight average molecular weight of polyimide resin is 2000-20000 Polyimide resin is the polyimide resin that molecular chain-end contains unsaturated bond), it can further improve obtained polyimide resin Intensity, toughness and the heat-resisting quantity of based composites, embodiment 1 can be seen that compared with embodiment 6.
When the polyimide resin solution relative to 100 parts by weight, the dosage of the polyimides fiber is 5-15 weights When measuring part, intensity, toughness and the heat-resisting quantity of obtained polyimide resin based composites can be further improved, will be implemented Example 1 can be seen that compared with embodiment 7.
The mode of heating treatment includes：150-250 DEG C is risen to 5-10 DEG C/min heating rate, when being incubated 1-1.5h, Intensity, toughness and the heat-resisting quantity of obtained polyimide resin based composites can be further improved, by embodiment 1 and in fact Apply example 8 compare it can be seen that.
In the present invention, using polyimides fiber (be specially polyimide fiber pulp, polyimides chopped strand and Polyimides fibrid) modified have the advantage that and innovative is filled to polyimide resin.First, above-mentioned polyamides Imines fiber surface contains a large amount of active groups (carboxyl-COOH and amino-NH-) after processing, when being mixed with resin solution Complete resin bed can be coated in fiber surface by the hydrogen bond action between active group, realize the close knot of fiber and resin Close；Secondly, in the product after forming and hardening, fiber can form the network of 3 D stereo, play skeletal support effect, not only may be used To improve the mechanical strength of product, the toughness of product can also be increased substantially；3rd, it is most important that the toughness reinforcing, enhancing are filled out The chemical constitution of material is all polyimides, has been effectively maintained the excellent resistance to elevated temperatures of polyimide material and resistance to ultraviolet irradiation And the performance characteristics such as low water absorption, the temperature resistant grade of resin matrix is not interfered with not only, additionally it is possible to is improved to a certain extent The applied at elevated temperature performance of product.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.

Claims (8)

1. a kind of preparation method of high-strength and high ductility polyimide resin based composites, it is characterised in that this method includes following Step：
(1) polyimide resin solution is prepared；
(2) polyimides fiber is surface-treated；
(3) the polyimides fiber for the surface treatment under agitation obtaining step (2) is dispersed in what step (1) obtained In polyimide resin solution；
(4) mixed slurry for obtaining step (3) carries out heating treatment；
(5) product for obtaining step (4) carries out hot-forming processing；
The polyimides fiber is in polyimide fiber pulp, polyimides chopped strand and polyimides fibrid At least one；When polyimides fiber is polyimide fiber pulp, the average length of polyimide fiber pulp is 0.1-10mm；When polyimides fiber is polyimides fibrid, its average length is 0.1-10mm, and polyimide is fine Tie up for polyimides chopped strand when, its average length is 1-20mm；
Step (3), the polyimide resin solution of 100 parts by weight, the dosage of the corresponding polyimides fiber is 5-40 weights Measure part；Scattered temperature is 25-80 DEG C.
2. according to a kind of preparation method of high-strength and high ductility polyimide resin based composites described in claim 1, its feature It is, in step (1), polyimide resin is the polyimide resin that molecular chain-end contains unsaturated bond；Polyimide resin The solid content of solution is 5-40wt%；The weight average molecular weight of polyimide resin is 2000-20000.
3. according to a kind of preparation method of high-strength and high ductility polyimide resin based composites described in claim 1, its feature It is, the preparation method of polyimides fibrid includes：
(1) amine monomers and anhydrides monomer are reacted into generation polyamic acid product in polar solvent；
(2) it is 1-14wt% and viscosity is less than 500cp at room temperature by the product dilution that step (1) obtains to polyamic acid concentration, Then the solution after dilution is injected in precipitating reagent under agitation；
(3) product for obtaining step (2) carries out hot imidization.
4. according to a kind of preparation method of high-strength and high ductility polyimide resin based composites described in claim 1, its feature It is, the method for surface treatment is soda solution grouting or low temperature plasma method；The soda solution grouting includes：Etched using NaOH solution fine 1-10min is tieed up, the concentration of NaOH solution is 5-10wt%；The low temperature plasma method includes：Adopted under power 200-250W Surface treatment 1-10min is carried out to fiber with oxygen plasma.
5. according to a kind of preparation method of high-strength and high ductility polyimide resin based composites described in claim 1, its feature It is,
The mode of step (4) described heating treatment includes：150-300 DEG C is risen to 2-10 DEG C/min heating rate, insulation 0.5-2h；
The condition of step (5) hot-forming processing includes：Temperature is 320-400 DEG C, pressure 1-8MPa, time 0.5-2h.
6. according to a kind of preparation method of high-strength and high ductility polyimide resin based composites described in claim 5, its feature It is, the polyimide resin solution of 100 parts by weight, the dosage of the corresponding polyimides fiber is 5-15 parts by weight；
Scattered temperature is 25 DEG C -50 DEG C；
The mode of heating treatment：150-250 DEG C is risen to 5-10 DEG C/min heating rate, is incubated 1-1.5h.
7. according to a kind of preparation method of high-strength and high ductility polyimide resin based composites described in claim 1, its feature It is, when polyimides fiber is polyimide fiber pulp, the average length of polyimide fiber pulp is 0.5-2mm, Specific surface area is 5-20m2/g。
8. the high-strength and high ductility polyimide resin based composites that any one methods described according to claim 1-7 is prepared Application, the application in brake block.
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