CN103483816A - Carbon fiber reinforced polyimide composite material and preparation method thereof - Google Patents
Carbon fiber reinforced polyimide composite material and preparation method thereof Download PDFInfo
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- CN103483816A CN103483816A CN201310362352.7A CN201310362352A CN103483816A CN 103483816 A CN103483816 A CN 103483816A CN 201310362352 A CN201310362352 A CN 201310362352A CN 103483816 A CN103483816 A CN 103483816A
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- C—CHEMISTRY; METALLURGY
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a carbon fiber reinforced polyimide composite material. The carbon fiber reinforced polyimide composite material is characterized by comprising the following components in percentage by weight: 10-60% of thermoplastic polyimide, 5-50% of carbon fiber, 5-20% of compatibilizer, 0.2-1.5% of coupling agent, 0-1% of antioxidant, 0-1% of light stabilizer and 0-10% of processing aid. The preparation method of the polyimide composite material comprises the steps of firstly preparing various raw materials; then sequentially adding the thermoplastic polyimide, the compatibilizer, the coupling agent, the antioxidant, the light stabilizer and the processing aid into a high-speed mixing machine for dispersing and mixing; placing the materials after mixing into an extruding machine after the completion of mixing, and independently introducing the carbon fiber through a carbon fiber port of the extruding machine during extrusion for mixing, extruding and granulating the materials so as to obtain granules of the polyimide composite material. The polyimide composite material provided by the invention has the advantages of relatively high rigidity, strength and toughness, and can be widely applied to aerospace, automobiles, electronic and electrical appliances, industrial machinery and other fields.
Description
Technical field
The invention belongs to the thermoplastic macromolecule material technical field, be specifically related to the fine composite polyimide material and preparation method thereof that strengthens of a kind of carbon.
Background technology
Polyimide (PI) is that a class be take the polymkeric substance that imide ring is feature structure, has outstanding resistance to elevated temperatures, good mechanical property, electric property, wear resistance and stability.The polyimide goods generally are applied to the fields such as Aeronautics and Astronautics, electrical equipment, machinery, chemical industry, microelectronics.But goods are crisp, machine-shaping is difficult because its cyclized structure easily causes, limited polyimide more being widely used at numerous areas.Thermoplastic polyimide (TPI) is one of special engineering plastics with good thermoplastic processability grown up on the basis of traditional Thermocurable polyimide (PI), it not only can adopt all processing mode moulding of thermoset PI, also can adopt the method moulding with injection moulding of extruding that is suitable for thermoplastics, therefore be particularly suitable for the baroque goods of once shaped, without secondary processing, the problems such as traditional thermoset PI forming process is difficult, product form is single have been solved.TPI introduces flexible chain or linear chain segment structure often in the monomer molecule structure of synthetic PI, thus the thermoplastic processability who improves PI.But the introducing of soft segment must cause the decline of the strength of materials and high-temperature behavior, limited to a certain extent its application in high-end fields such as Aeronautics and Astronautics.Therefore, be necessary to adopt other modes to carry out modification to polyimide, when improving the thermoplastic processability, guarantee that the performances such as its intensity, rigidity and toughness meet the demands.
Summary of the invention
Technical problem to be solved by this invention is, for the deficiencies in the prior art, to provide a kind of fine composite polyimide material and simple preparation method of step thereof of strengthening of carbon with high stiffness, intensity and toughness.
The present invention solves the problems of the technologies described above adopted technical scheme: the fine composite polyimide material that strengthens of a kind of carbon, its weight percent forms and comprises: thermoplastic polyimide 10～60%, carbon fiber 5～50%, compatilizer 5～20%, coupling agent 0.2～1.5%, oxidation inhibitor 0～1%, the steady agent 0～1% of light, processing aid 0～10%;
Described compatilizer is one or more in ethylene-methyl acrylate-glyceryl methacrylate multipolymer, ternary isopropyl grafting rubbers maleic anhydride and ethylene-vinyl acetate copolymer;
Described coupling agent is one or more in silane coupling agent, titanate coupling agent and aluminate coupling agent;
Described oxidation inhibitor is one or more in phenolic antioxidant, amine antioxidants, phosphite ester kind antioxidant, monothioester kind antioxidant and metal passivator;
The steady agent of described light is one or both in the steady agent of diformazan ketone light and the steady agent of hindered amines light;
Described processing aid is one or more in silicone powder, vinyl bis-stearamides, dimethyl silicone oil, PEI-Sulfone multipolymer.
Preferably, described silane coupling agent is one or more in 3-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane and γ-(methacryloxypropyl) propyl trimethoxy silicane; Described titanate coupling agent is one or more in sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, monoalkoxy unsaturated fatty acids titanic acid ester and Di(dioctylpyrophosphato) ethylene titanate; Described aluminate coupling agent is aluminic acid three isopropyl esters.
Preferably, described phenolic antioxidant is N, N '-bis--(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] one or more in pentaerythritol ester and β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid; Described amine antioxidants is 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline) and N, one or both in N '-diphenyl-para-phenylene diamine; Described phosphite ester kind antioxidant is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester; Described monothioester kind antioxidant is one or both in the two stearyl alcohol esters of thio-2 acid and the two lauryl alcohol esters of thio-2 acid; Described metal passivator is N, N '-bis-salicylidene propylene diamine.
Preferably, the steady agent of described diformazan ketone light is 2-[4-[2-hydroxyl-3-tridecane oxygen base propyl group] the oxygen base]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines and 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] the oxygen base]-the 2-hydroxy phenyl]-4,6-two (2, the mixture of the 4-3,5-dimethylphenyl)-1,3,5-triazines; The steady agent of described hindered amines light is poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines ethanol) ester.
Preferably, the product that the marque that described PEI-Sulfone multipolymer provides for husky the primary radical innovations plastics (China) company limited is Extem XH1005 or Ultem VH1003.
The fine preparation method who strengthens composite polyimide material of a kind of carbon, comprise the following steps: at first by thermoplastic polyimide 10～60%, carbon fiber 5～50%, compatilizer 5～20%, coupling agent 0.2～1.5%, oxidation inhibitor 0～1%, the steady agent 0～1% of light, the weight percent composition of processing aid 0～10% is ready to various raw materials; Then other raw materials except carbon fiber are joined to dispersing and mixing in the high-speed mixer that rotating speed is 600～900rpm successively, mixing time is 5～10min, and mixing temperature is 50～70 ℃; After having mixed, mixed material is put into to forcing machine, forcing machine Ge district temperature is controlled to 220 ℃, 260 ℃, 290 ℃, 295 ℃, 295 ℃, 300 ℃, 300 ℃, 305 ℃, 305 ℃, 300 ℃ successively from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 38～42, the extrusion screw rod rotating speed is 300～400rpm, rate of feeding is 15～30rpm, glass fiber opening by forcing machine when extruding is introduced separately into carbon fiber to be mixed material to extrude and granulation, obtains the pellet of composite polyimide material.
Compared with prior art, the invention has the advantages that: the present invention, by the suitable selection to matrix resin, filler, processing aid etc., obtains both having high stiffness and intensity, has again the thermoplastic polyimide composite material of higher toughness.The carbon fiber that plays enhancement is mineral filler, the specific tenacity of carbon fiber (CF) is high, wear-resistant, antifatigue, thermal expansivity are little, and there are the characteristics of self-lubricating, add carbon fiber in matrix material of the present invention after, the performances such as mechanical property, resistance to elevated temperatures and frictional behaviour of composite polyimide material of the present invention have greatly been improved.Composite polyimide material of the present invention can be widely used in the fields such as aviation, automobile, electronic apparatus, industrial machinery, and concrete purposes comprises: engine is for combustion systematic part, jet engine element, compressor and generator part, fastener, spline joint and electronics contact device; Automotive engine component, bearing, piston bush, timing gear; Printed-wiring board (PWB) on electronic industry, insulating material, thermotolerance cable, terminal stud, socket; High temp resistance self-lubricating bearing on mechanical industry, compression blade and piston machine, sealing-ring, insulating equipment cover, thrust washer, axle bush etc.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The weight percent of each embodiment composite polyimide material forms in Table 1.Weight percent by table 1 forms the raw material that is ready to each embodiment.The raw material of take english abbreviation or be called for short meaning is thermoplastic polyimide---TPI, carbon fiber---CF, ethylene-methyl acrylate-glyceryl methacrylate multipolymer---EMAG, ternary isopropyl grafting rubbers maleic anhydride---EPDM-g-MAH, 3-aminopropyl triethoxysilane---KH-550, γ-(2, the 3-glycidoxy) propyl trimethoxy silicane---KH-560, γ-(methacryloxypropyl) propyl trimethoxy silicane---KH-570, Di(dioctylpyrophosphato) ethylene titanate---TMC-311, N, N '-bis--(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine---1098, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester---1010, β-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid---1076, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester---168, two stearyl alcohol ester---the DSTP of thio-2 acid, two lauryl alcohol ester---the DLTDP of thio-2 acid, N, N '-bis-salicylidene propylene diamine---T1201, poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidines ethanol) ester---UV-622, 2-[4-[2-hydroxyl-3-tridecane oxygen base propyl group] the oxygen base]-the 2-hydroxy phenyl]-4, 6-two (2, the 4-3,5-dimethylphenyl)-1, 3, 5-triazine and 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] the oxygen base]-the 2-hydroxy phenyl]-4, 6-two (2, the 4-3,5-dimethylphenyl)-1, 3, 5-triazine mixture---UV-400, vinyl bis-stearamides---EBS.
The weight percent proportioning (%) of table 1 embodiment 1～embodiment 5 composite polyimide materials
Embodiment 1: at first by 66.65% thermoplastic polyimide (TPI), 25% carbon fiber (CF), 5% ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), 0.25% 3-aminopropyl triethoxysilane (KH-550), 0.25% Di(dioctylpyrophosphato) ethylene titanate (TMC-311), 0.1% β-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid (1076), the two lauryl alcohol esters (anti-DLTDP) of 0.25% thio-2 acid, 0.1% N, N '-bis-salicylidene propylene diamine (T1201), 0.2% poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidines ethanol) ester (622), 0.2% EBS, the weight percent composition of 2% Extem XH1005 is ready to various raw materials, then other raw materials except carbon fiber are joined to dispersing and mixing in the high-speed mixer that rotating speed is 600rpm successively, mixing time is 5min, and mixing temperature is 60 ℃, after having mixed, mixed material is put into to forcing machine, forcing machine Ge district temperature is controlled to 220 ℃, 260 ℃, 290 ℃, 295 ℃, 295 ℃, 300 ℃, 300 ℃, 305 ℃, 305 ℃, 300 ℃ successively from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 40, the extrusion screw rod rotating speed is 300rpm, rate of feeding is 15rpm, glass fiber opening by forcing machine when extruding is introduced separately into carbon fiber to be mixed material to extrude and granulation, obtains the pellet of composite polyimide material.
Embodiment 2: at first by 61.65% thermoplastic polyimide (TPI), 30% carbon fiber (CF), 5% ternary isopropyl grafting rubbers maleic anhydride EPDM-g-MAH, 0.25% γ-(2, the 3-glycidoxy) propyl trimethoxy silicane (KH-560), 0.25% Di(dioctylpyrophosphato) ethylene titanate (TMC-311), 0.1% four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester---1010, two stearyl alcohol ester---the DSTP of 0.25% thio-2 acid, 0.1% N, N '-bis-salicylidene propylene diamine (T1201), 0.2% N, N '-bis-salicylidene propylene diamine (T1201), poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidines ethanol) ester (UV-622), 2-[4-[2-hydroxyl-3-tridecane oxygen base propyl group] the oxygen base]-the 2-hydroxy phenyl]-4, 6-two (2, the 4-3,5-dimethylphenyl)-1, 3, 5-triazine and 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] the oxygen base]-the 2-hydroxy phenyl]-4, 6-two (2, the 4-3,5-dimethylphenyl)-1, 3, 5-triazine mixture (UV-400), 0.2% dimethyl silicone oil, the weight percent composition of 2% ExtemXH1005 is ready to various raw materials, then other raw materials except carbon fiber are joined to dispersing and mixing in the high-speed mixer that rotating speed is 800rpm successively, mixing time is 7min, and mixing temperature is 50 ℃, after having mixed, mixed material is put into to forcing machine, forcing machine Ge district temperature is controlled to 220 ℃, 260 ℃, 290 ℃, 295 ℃, 295 ℃, 300 ℃, 300 ℃, 305 ℃, 305 ℃, 300 ℃ successively from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 39, the extrusion screw rod rotating speed is 380rpm, rate of feeding is 20rpm, glass fiber opening by forcing machine when extruding is introduced separately into carbon fiber to be mixed material to extrude and granulation, obtains the pellet of composite polyimide material.
Embodiment 3: at first by 56.65% thermoplastic polyimide (TPI), 35% carbon fiber (CF), 2.5% ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EGMA), 2.5% ternary isopropyl grafting rubbers maleic anhydride EPDM-g-MAH, 0.25% γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570), 0.25% Di(dioctylpyrophosphato) ethylene titanate (TMC-311), 0.1% three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (168), the two lauryl alcohol esters (anti-DLTDP) of 0.25% thio-2 acid, 0.1% N, N '-bis-salicylidene propylene diamine (T1201), 0.2% poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidines ethanol) ester (UV-622), 0.2% EBS, the weight percent composition of 2% ExtemXH1005 is ready to various raw materials, then other raw materials except carbon fiber are joined to dispersing and mixing in the high-speed mixer that rotating speed is 650rpm successively, mixing time is 10min, and mixing temperature is 65 ℃, after having mixed, mixed material is put into to forcing machine, forcing machine Ge district temperature is controlled to 220 ℃, 260 ℃, 290 ℃, 295 ℃, 295 ℃, 300 ℃, 300 ℃, 305 ℃, 305 ℃, 300 ℃ successively from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 42, the extrusion screw rod rotating speed is 400rpm, rate of feeding is 30rpm, glass fiber opening by forcing machine when extruding is introduced separately into carbon fiber to be mixed material to extrude and granulation, obtains the pellet of composite polyimide material.
Embodiment 4: at first by 51.55% thermoplastic polyimide (TPI), 40% carbon fiber (CF), 1% ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EGMA), 4% ternary isopropyl grafting rubbers maleic anhydride EPDM-g-MAH, 0.25% 3-aminopropyl triethoxysilane (KH-550), 0.25% Di(dioctylpyrophosphato) ethylene titanate (TMC-311), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 1010 of 0.1%, two stearyl alcohol ester---the DSTP of 0.25% thio-2 acid, 0.1% N, N '-bis-salicylidene propylene diamine (T1201), 0.1% N, the 2-[4-[2-hydroxyl of N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine 1098,0.2%-3-tridecane oxygen base propyl group] the oxygen base]-the 2-hydroxy phenyl]-4, 6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines and 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] the oxygen base]-the 2-hydroxy phenyl]-4, 6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines mixture UV-400, 0.2% dimethyl silicone oil, 0.1% EBS, the weight percent composition of 2% Extem XH1005 is ready to various raw materials, then other raw materials except carbon fiber are joined to dispersing and mixing in the high-speed mixer that rotating speed is 900rpm successively, mixing time is 6min, and mixing temperature is 55 ℃, after having mixed, mixed material is put into to forcing machine, forcing machine Ge district temperature is controlled to 220 ℃, 260 ℃, 290 ℃, 295 ℃, 295 ℃, 300 ℃, 300 ℃, 305 ℃, 305 ℃, 300 ℃ successively from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 38, the extrusion screw rod rotating speed is 320rpm, rate of feeding is 18rpm, glass fiber opening by forcing machine when extruding is introduced separately into carbon fiber to be mixed material to extrude and granulation, obtains the pellet of composite polyimide material.
Embodiment 5: at first by 46.55% thermoplastic polyimide (TPI), 50% carbon fiber (CF), 2% ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EGMA), 3% ternary isopropyl grafting rubbers maleic anhydride EPDM-g-MAH, 0.25% 3-aminopropyl triethoxysilane (KH-550), 0.25% Di(dioctylpyrophosphato) ethylene titanate (TMC-311), 0.1% N, N '-bis--(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine 1098, 0.1% three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (anti-168), the two lauryl alcohol esters (anti-DLTDP) of 0.25% thio-2 acid, 0.2% poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidines ethanol) ester (UV-622), 0.1% dimethyl silicone oil, 0.2% EBS, the weight percent composition of 2% Extem XH1005 is ready to various raw materials, then other raw materials except carbon fiber are joined to dispersing and mixing in the high-speed mixer that rotating speed is 620rpm successively, mixing time is 7min, and mixing temperature is 70 ℃, after having mixed, mixed material is put into to forcing machine, forcing machine Ge district temperature is controlled to 220 ℃, 260 ℃, 290 ℃, 295 ℃, 295 ℃, 300 ℃, 300 ℃, 305 ℃, 305 ℃, 300 ℃ successively from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 41, the extrusion screw rod rotating speed is 350rpm, rate of feeding is 25rpm, glass fiber opening by forcing machine when extruding is introduced separately into carbon fiber to be mixed material to extrude and granulation, obtains the pellet of composite polyimide material.
Pellet for the composite polyimide material obtained in above embodiment 1～embodiment 5, adopt GB GB/T1843-2008 " plastics izodtest method " to test socle girder notched Izod impact strength performance, adopt GB GB/T1634-2004 " plastics bending load heat-drawn wire test method " test heat-drawn wire performance, adopt GB GB/T 1040-2006 " plastic tensile test method " to test tensile strength, elongation at break properties, adopt GB/T9341-2008 " Plastics-Oetermination of flexural properties method " to test flexural strength and modulus in flexure, its performance test results is in Table 2.Visible, composite polyimide material provided by the invention has higher rigidity, intensity and toughness.
The performance test results of table 2 embodiment 1～embodiment 6 composite polyimide materials
Claims (6)
1. the fine composite polyimide material that strengthens of carbon, is characterized in that, its weight percent forms and comprises: thermoplastic polyimide 10 ~ 60%, carbon fiber 5 ~ 50%, compatilizer 5 ~ 20%, coupling agent 0.2 ~ 1.5%, oxidation inhibitor 0 ~ 1%, the steady agent 0 ~ 1% of light, processing aid 0 ~ 10%;
Described compatilizer is one or more in ethylene-methyl acrylate-glyceryl methacrylate multipolymer, ternary isopropyl grafting rubbers maleic anhydride and ethylene-vinyl acetate copolymer;
Described coupling agent is one or more in silane coupling agent, titanate coupling agent and aluminate coupling agent;
Described oxidation inhibitor is one or more in phenolic antioxidant, amine antioxidants, phosphite ester kind antioxidant, monothioester kind antioxidant and metal passivator;
The steady agent of described light is one or both in the steady agent of diformazan ketone light and the steady agent of hindered amines light;
Described processing aid is one or more in silicone powder, vinyl bis-stearamides, dimethyl silicone oil, PEI-Sulfone multipolymer.
2. a kind of carbon fibre according to claim 1 strengthens composite polyimide material, it is characterized in that: described silane coupling agent is one or more in 3-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane and γ-(methacryloxypropyl) propyl trimethoxy silicane; Described titanate coupling agent is one or more in sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, monoalkoxy unsaturated fatty acids titanic acid ester and Di(dioctylpyrophosphato) ethylene titanate; Described aluminate coupling agent is aluminic acid three isopropyl esters.
3. a kind of carbon fibre according to claim 1 strengthens composite polyimide material, it is characterized in that: described phenolic antioxidant is N, N '-bis--(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] one or more in pentaerythritol ester and β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid; Described amine antioxidants is 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline) and N, one or both in N '-diphenyl-para-phenylene diamine; Described phosphite ester kind antioxidant is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester; Described monothioester kind antioxidant is one or both in the two stearyl alcohol esters of thio-2 acid and the two lauryl alcohol esters of thio-2 acid; Described metal passivator is N, N '-bis-salicylidene propylene diamine.
4. a kind of carbon fibre according to claim 1 strengthens composite polyimide material, it is characterized in that: the steady agent of described diformazan ketone light is 2-[4-[2-hydroxyl-3-tridecane oxygen base propyl group] the oxygen base]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines and 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] the oxygen base]-the 2-hydroxy phenyl]-4,6-two (2, the mixture of the 4-3,5-dimethylphenyl)-1,3,5-triazines; The steady agent of described hindered amines light is poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines ethanol) ester.
5. the fine composite polyimide material that strengthens of a kind of carbon according to claim 1, is characterized in that: the product that the marque that described PEI-Sulfone multipolymer provides for husky the primary radical innovations plastics (China) company limited is Extem XH1005 or Ultem VH1003.
6. the fine preparation method who strengthens composite polyimide material of a carbon, it is characterized in that comprising the following steps: at first by thermoplastic polyimide 10 ~ 60%, carbon fiber 5 ~ 50%, compatilizer 5 ~ 20%, coupling agent 0.2 ~ 1.5%, oxidation inhibitor 0 ~ 1%, the steady agent 0 ~ 1% of light, the weight percent composition of processing aid 0 ~ 10% is ready to various raw materials; Then other raw materials except carbon fiber are joined to dispersing and mixing in the high-speed mixer that rotating speed is 600 ~ 900rpm successively, mixing time is 5 ~ 10min, and mixing temperature is 50 ~ 70 ℃; After having mixed, mixed material is put into to forcing machine, forcing machine Ge district temperature is controlled to 220 ℃, 260 ℃, 290 ℃, 295 ℃, 295 ℃, 300 ℃, 300 ℃, 305 ℃, 305 ℃, 300 ℃ successively from the feeding section to head temperature, the extrusion screw rod length-to-diameter ratio is 38 ~ 42, the extrusion screw rod rotating speed is 300 ~ 400rpm, rate of feeding is 15 ~ 30rpm, glass fiber opening by forcing machine when extruding is introduced separately into carbon fiber to be mixed material to extrude and granulation, obtains the pellet of composite polyimide material.
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| CN105647182A (en) * | 2016-04-05 | 2016-06-08 | 吴江市林旺纺织厂 | Thermal insulation material for textiles and preparation method of thermal insulation material |
| CN105713385A (en) * | 2014-11-30 | 2016-06-29 | 黑龙江鑫达企业集团有限公司 | Surface treatment carbon fiber-reinforced thermoplastic polyimide composite material |
| CN105713386A (en) * | 2014-11-30 | 2016-06-29 | 黑龙江鑫达企业集团有限公司 | Carbon fiber-reinforced thermoplastic polyimide composite material |
| CN105838069A (en) * | 2016-04-15 | 2016-08-10 | 湖州新奥克化工有限公司 | Carbon fiber/polyimide resin composite material and preparation method thereof |
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| CN104031387B (en) * | 2014-06-27 | 2016-09-07 | 自贡中天胜新材料科技有限公司 | A kind of self-lubricating polyimides elastic wear-resisting composite and preparation method |
| CN106795644A (en) * | 2014-09-09 | 2017-05-31 | 古河电气工业株式会社 | Copper foil for printed wiring board and copper clad laminate |
| CN106795644B (en) * | 2014-09-09 | 2019-10-01 | 古河电气工业株式会社 | Copper foil for printed wiring board and copper clad laminate |
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| CN105838069A (en) * | 2016-04-15 | 2016-08-10 | 湖州新奥克化工有限公司 | Carbon fiber/polyimide resin composite material and preparation method thereof |
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| CN109181232A (en) * | 2018-09-28 | 2019-01-11 | 陈琪峰 | A kind of preparation method of low temperature resistant electrical insulating material |
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