CN108570223A - A kind of carbon-fiber-reinforced polyester composite material and preparation method thereof - Google Patents
A kind of carbon-fiber-reinforced polyester composite material and preparation method thereof Download PDFInfo
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- CN108570223A CN108570223A CN201810435929.5A CN201810435929A CN108570223A CN 108570223 A CN108570223 A CN 108570223A CN 201810435929 A CN201810435929 A CN 201810435929A CN 108570223 A CN108570223 A CN 108570223A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/20—Carboxylic acid amides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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Abstract
The present invention relates to a kind of carbon-fiber-reinforced polyester composite materials and preparation method thereof, the carbon fiber that surface is first coated to thermosetting resin sizing agent keeps the temperature 0.5~15min at 250~350 DEG C, fine mouth is added to be added by double screw extruder on the carbon fiber of Low Temperature Heat Treatment again, the mixture of thermoplastic polyester, antioxidant and lubricant is added from double screw extruder hopper, it is 160~220MPa to squeeze out and tensile strength is made, and bending strength is the carbon-fiber-reinforced polyester composite material of 240~290MPa；The mass ratio that surface coats the carbon fiber of thermosetting resin sizing agent, thermoplastic polyester, antioxidant and lubricant is 20~40:60~80:0.1~0.3:0.1~0.5.The preparation method of the present invention, heat treatment temperature is low, energy consumption is small, and carbon fiber surface is rich in the carboxyl that can be reacted with thermoplastic polyester after processing, is conducive to the chemical bonding with thermoplastic polyester, great application prospect.
Description
Technical field
The invention belongs to carbon fibre composite preparation field, it is related to a kind of carbon-fiber-reinforced polyester composite material and its system
Preparation Method.
Background technology
Polyester be by polyalcohol and polyacid polycondensation and polymer general name, refer mainly to polyethylene terephthalate
(PET) and linear thermoplastics' resin such as polybutylene terephthalate (PBT).It is with high-melting-point, high tenacity, outstanding heat-resisting
Performance, electric durability energy and dimensional stability are widely used in the fields such as weaving, automobile and electronic apparatus.
Carbon fiber (CF) has high intensity, high-modulus, good heat conductivity, thermal stability, fatigue durability and creep resistant
The features such as property, thus be commonly used as the reinforcing agent of polymer, be other glass fibre reinforced composions incomparable, quilt
It is widely used in the new high-tech industries such as aerospace, new energy, rail traffic, auto industry and sports goods field.It will
Carbon fiber with polyester is compound prepares carbon-fiber-reinforced polyester composite material, the excellent mechanical property of carbon fiber can be utilized to improve
The performance of composite material entirety.
It is commercialized the big multi-surface coated epoxy resin sizing agent of carbon fiber on the market at present, is to be directed to thermoset epoxy tree
The exploitation of aliphatic radical composite material.But surface coats carbon fiber and the nylon resin poor compatibility or incompatible of thermosetting resin
(tec fiber and application, 2014,39,1-6).This is because with thermoplastic polymer chemistry does not occur for epoxy resin sizing agent
Reaction, causes its composite material interlayer shear strength low；In addition, the forming temperature of thermosetting epoxy resin sizing agent is less than 250
DEG C, more than 250 DEG C epoxy resin sizing agents, which can degrade, generates gas, forms tiny micropore in composite material surface, causes compound
Material molding failure.
At present carbon fiber is carried out thermoplastic resin to enhance feasible method being to the carbon fiber coated with thermosetting resin
Destarch.The method of destarch has solvent method and ablation, the former needs a large amount of solvents, the latter to will produce a large amount of tar, not only pollute
Environment, and carbon fiber after starching is gone to will produce a large amount of lousiness, fracture of wire, to reduce the quality of carbon fiber.In addition, desizing
Pyroprocess can make to remove by the oxygen-containing functional group that anodic oxidation means obtain on carbon fiber, be unfavorable for carbon fiber and resin base
The infiltration of body and interface cohesion.The fundamental solution for solving carbon fiber for thermoplastic resin is the compatible of change carbon fiber sizing agent
Property, keep it compatible with thermoplastic resin.
《Composites:Part A》(2016,87,212-219) proposes to make using modified thermoplasticity phenol oxygroup resin
For sizing agent, secondary starching is carried out on commercialization carbon fiber, treated, and 6 composite material interlayer of carbon fiber reinforced nylon is cut
Shearing stress improves 20.4%, it is indicated that transesterification has occurred with thermoplastic matrix in the ester group contained in sizing agent, forms new
Chemical bonding acts on, to improve the interface performance of carbon fiber and thermoplastic resin.But this method carries out two to carbon fiber
Secondary starching, starching amount are up to 5.2~7.5%, considerably increase the convergence of carbon fiber wire interfascicular, are unfavorable for and thermoplastic resin
Wellability between matrix；Secondly thermoplasticity sizing agent itself can reactive group activity it is low, the interface binding power between carbon fiber
It is weak, it is smaller to the raising of fibre reinforced thermoplastic resin interface performance to result in the thermoplasticity sizing agent.
《Applied surface science》Surface is coated thermosetting epoxy resin by (2016,379,199-205)
Carbon fiber is vacuum-treated 2h at 200 DEG C, and reinforced epoxy composite material interface performance declines, this is because at Vacuum Heat
Carbon fiber to be managed, promotes carbon fiber before being molded with resin matrix, cross-linking reaction has occurred for itself in the sizing agent on carbon fiber, to
Reduce carbon fiber and the chemical reaction group in thermosetting resin matrix molding.This illustrates that vacuum heating treatment can promote carbon fiber
In dimension can reactive group reduction, be less useful for the thermoplastic resin matrix interface cohesion low with reactivity.
Therefore, a kind of carbon fiber coating thermosetting epoxy resin sizing agent to surface of exploitation carries out surface modification to improve
The great realistic meaning of method of itself and the mechanical property of thermoplastic resin compatibility, that is, composite material.
Invention content
The purpose of the present invention is to solve problems of the prior art, provide a kind of to surface cladding thermosetting property ring
The carbon fiber of oxygen resin sizing agent carries out surface and is modified to improve itself and the thermoplastic resin compatibility i.e. mechanical property of composite material
The surface of the carbon fiber of the method for energy, specifically surface cladding thermosetting resin sizing agent is modified, i.e., coats thermosetting property to surface
The carbon fiber of resin sizing agent carries out low-temperature oxidation processing, its surface is made to be rich in carboxyl, improves carbon fiber and surface coated heat
Interface binding power between thermosetting resin sizing agent improves the compatibility of carbon fiber and thermoplastic resin matrix.It then again will processing
Carbon fiber afterwards is compound with thermoplastic polyester, and treated, and carbon fiber surface is rich in carboxyl, with thermoplastic polyester matrix presenceization
Bonding action is learned, it can effective strengthened thermoplastic polyester interface performance.
The carbon fiber that the present invention coats surface thermosetting resin sizing agent carries out low-temperature oxidation processing, by the methylene on surface
Base and hydroxyl are oxidized to the carboxyl that can be reacted with the thermoplastic polyester matrix of subsequent processing, carbon fiber and follow-up place after improvement processing
Interface cohesion effect between the thermoplastic polyester matrix of reason, the carboxyl that this thermoset sizing agent surface oxidation generates can also be with carbon
The original oxygen-containing group dehydrogenation of fiber surface forms crosslinking, enhances the interface interaction between carbon fiber and thermosetting property sizing agent, to
Enhance interface and the mechanical property of integral composite.
In order to achieve the above object, the technical solution adopted by the present invention is：
Surface is first coated the carbon of thermosetting resin sizing agent by a kind of preparation method of carbon-fiber-reinforced polyester composite material
Fiber carries out Low Temperature Heat Treatment, then adds fine mouth to be added by double screw extruder on the carbon fiber of Low Temperature Heat Treatment, thermoplastic polyester,
The mixture of antioxidant and lubricant is added from double screw extruder hopper, squeezes out and carbon fiber reinforced polyester composite wood is made
Material；
The carbon fiber of the surface cladding thermosetting resin sizing agent, the matter of thermoplastic polyester, antioxidant and lubricant
Amount is than being 20~40:60~80:0.1~0.3:0.1~0.5.
The content of carbon fiber has a significant impact to the mechanical property of carbon-fiber-reinforced polyester composite material.By carbon fiber and gather
Ester resin uniformly mixes, and evenly dispersed carbon fiber can be formed by force with matrix resin in the interface of the two by the group on surface
Active force, load can be effectively transmitted to from matrix on reinforcement carbon fiber, so that reinforcement carbon fiber is carried main
Load, and carbon fiber has very high intensity, so the mechanical property for showing carbon-fiber-reinforced polyester composite material increases.Carbon
When the content of fiber is less than 20%, there are not enough carbon fibers to carry out the load of bearing composites, to affect reinforced polyester
The mechanical property of composite material.When carbon fiber content is more than 20%, pass through interface interaction strong between carbon fiber and matrix resin
Power can be such that the load of matrix is effectively transferred on carbon fiber so that the mechanical property of integral composite is significantly improved.
But when carbon fiber content is more than 40%, the composite materials property of the reinforced polyester resin of carbon fiber starts to reduce, this
It is because when carbon fiber fills too high amount, dispersion of the carbon fiber in polyester matrix is bad, can occur mutually in a small range
It tangles and agglomeration, the polyester matrix around the carbon fiber of reunion is few, or even forms pore defect, makes it by external action
Become stress weak spot when power, is more easy to cause the local failure of material, the mechanical performance of composite material is caused to decline.
Antioxidant play in the composite inhibit matrix high-temperature molding in thermal oxidative degradation and use in material because
The effect of the aging of product caused by heat, light etc..Therefore, oxidation resistant amount needs to add a certain amount of, and generally 0.1% adds to meet
The performance requirement of resistance to oxidation degradation in work and use, antioxidant such as hindered amines are converted to nitryl certainly after photooxidation
By base, this nitroxyl radicals are considered as really stable component, it can capture free radical, the product of generation again with peroxide
Compound free radical regenerates nitroxyl radicals.When additive amount reaches 0.3%, antioxidant can decompose under external influence
The number of free radical for generating and being consumed reaches balance so that the antioxygenic property of composite material reaches best, therefore chooses anti-
A concentration of the 0.1~0.3% of oxidation.
Play critically important effect in the processing and molding of lubricant in the composite, in forming process, lubricant is logical
It crosses between insertion polymer chain, weakens intermolecular active force, promote to generate sliding and rotation between macromolecule, or be coated on
The surface of fluoropolymer resin primary fine particles, to reduce the viscosity of thermoplastic melt, this method can in lower temperature and
The reduction that melt viscosity is realized under shear rate avoids the raising because of processing temperature from leading to melt fracture, energy consumption increase and heat
Excessive degradation occurs for plasticity polyester.Also, lubricant is mostly polar compound, they are with resin limited compatibility, Neng Goucong
Melt migration has certain compatibility, the shape in this way between melt and metal to surface, polar group and Mold Metal surface
The molecular layer stablize relatively at one layer, being isolated each other, therefore inhibit the adhesion between polyester fondant and processing equipment surface.In addition
Lubricant can also form self-lubricating layer in product surface, generate permanent lubricating action.To realize said effect, compound
Additive amount in material needs to be more than 0.1%, but to control 0.5%, because excessive lubricant can be in machine-shaping
Because the Partial digestion of itself generates excessive cracked gas, gap is generated in the composite, reduces the close of composite material entirety
Degree and mechanical property.
The Low Temperature Heat Treatment refers to 0.5~15min of heat preservation at 250~350 DEG C.
As preferred technical solution：
A kind of preparation method of carbon-fiber-reinforced polyester composite material as described above, the carbon fiber are polyacrylonitrile-radical
Carbon fiber, petroleum pitch-based carbon fiber, coal tar pitch base carbon fibre, viscose-based carbon fiber, phenolic aldehyde base carbon fibre, vapor phase growth carbon fiber
One or more of dimension, bacteria cellulose base carbon fibre, cellulose base carbon fiber and lignin-base carbon fiber；Its average length is
10 μm~3mm.
A kind of preparation method of carbon-fiber-reinforced polyester composite material as described above, the thermosetting resin sizing agent
Ingredient be epoxy resin and its derivative, unsaturated polyester resin, polyurethane resin, phenolic resin, melamine resin,
One or more of furane resins, polybutadiene and organic siliconresin；Protection scope of the present invention is not limited to that,
Its kin sizing agent is equally applicable to the present invention；The thermoplastic polyester is polybutylene terephthalate and poly- pair
Polyethylene terephthalate more than one, thermoplastic polyester of the invention is not limited to that, other kin polymer
It is equally applicable to the present invention；The antioxidant be four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters,
N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine or three [2,4- di-tert-butyl-phenyls] phosphorous acid
One or more of ester；The lubricant is zinc stearate, the double fatty acid amides of ethylene, ethylene-acrylic acid copolymer or silicone powder
One or more of.
A kind of preparation method of carbon-fiber-reinforced polyester composite material as described above, the Low Temperature Heat Treatment is to aoxidize
It is carried out in property atmosphere；The oxidizing atmosphere is the mixed gas ring of oxidizing gas environment or oxidizing gas and inert gas
Border, the volume ratio of oxidizing gas is more than or equal to 5% in mixed-gas environment.
A kind of preparation method of carbon-fiber-reinforced polyester composite material as described above, the oxidizing gas are titanium dioxide
One or more of nitrogen, chlorine, sulfur dioxide, sulfur trioxide, air and oxygen；The inert gas is nitrogen, argon gas, helium
Gas, neon, Krypton, xenon or radon gas, inert gas of the invention are not limited to that other kin gases can also fit
For the present invention.
A kind of preparation method of carbon-fiber-reinforced polyester composite material as described above, the surface coat thermosetting resin
Processing is pre-dried in the carbon fiber and thermoplastic polyester of sizing agent, and temperature is 100~150 DEG C, and the time is 2~6h, is pre-dried
Water content is less than 0.02wt% after processing.
There are ester groups on polyester macromolecule chain, and back reaction-hydrolysis of esterification easily occurs at high temperature, draws
Material mechanical performance and the deterioration of other performances are played, some researches show that：Under hot dry conditions, the anti-hydrolytic performance of polyester is splendid,
Stablize 5000 times than the oxidative degradation at same temperature, stablize 1000 times than the thermal degradation at same temperature, 100 DEG C with
On, under conditions of relative humidity is 100%, the hydrolysis rate of polyester is faster by 10 than the thermal degradation at identical temperature4Times, than in air
Fast 500 times of oxidative degradation.It therefore, must in order to obtain undegradable polyester in carbon fiber polyester high temperature process forming process
Must processing first be dried to sample, its moisture is made to be less than 0.02wt%.
In addition, the moisture in raw material has a certain impact for the final mechanical property tool of composite material, the water in raw material
Branch gasifies in composite material high-temperature molding, and since the viscosity of polymer melt is big, portion gas is difficult to overflow in time
To surface of material, remained in composite products in the form of stomata, causes the defect of product, during product use,
These defects will become stress concentration point, and material is made to be destroyed under lower mechanical strength.
A kind of preparation method of carbon-fiber-reinforced polyester composite material as described above, the double screw extruder is from feeding
Mouthful to extruder die head seven areas temperature settings be respectively 220~230 DEG C, 235~240 DEG C, 245~260 DEG C, 260~280
DEG C, 240~260 DEG C, 230~255 DEG C, 250~260 DEG C, engine speed be 300~400rpm.
A kind of preparation method of carbon-fiber-reinforced polyester composite material as described above, the carbon fiber reinforced polyester are compound
Material dry 2~6h at 100~150 DEG C, then it is injection moulded sample preparation, the injection molding mould temperature is 80~100 DEG C, note
It is 240~280 DEG C to mould forming temperature.
The present invention also provides a kind of using a kind of preparation method system of carbon-fiber-reinforced polyester composite material as described above
Carbon-fiber-reinforced polyester composite material, the tensile strength of the carbon-fiber-reinforced polyester composite material is 160~
220MPa, bending strength are 240~290MPa.The tensile strength of prior art carbon fiber polyester composite material be 110~
130MPa, bending strength are 180~200MPa, and properties of product of the invention are promoted greatly compared with the prior art.
Invention mechanism：
Different from the aerial heat ageing of single hot set property resin, the present invention coats thermosetting resin sizing agent to surface
Carbon fiber thermal treatment temperature be 250~350 DEG C.The thermal oxide of the carbon fiber of surface cladding thermosetting resin sizing agent has
Following characteristics：
(1) it is to meet the requirement for improving strengthened thermoplastic polyester interface performance, carbon fiber surface needs to be enriched with enough carboxylics
Base group carries out hot oxygen to enhance its binding ability with thermoplastic polyester, to surface cladding thermosetting resin sizing agent carbon fiber
Change handle, on the one hand can because promoting the unstable group of thermosetting resin sizing agent such as methylene and hydroxyl etc. to be oxidized to carboxyl,
On the other hand the de- conjunction of shrink or oxidative dehydrogenation of original oxygen-containing functional group and thermosetting property sizing agent on carbon fiber can be promoted to act on,
To consume the carbon fiber carboxylic group newly-generated because of thermal oxidation.Temperature is less than 250 DEG C, thermosetting resin surface
Methylene or hydroxyl oxidation activation energy it is high, cause oxidation rate low, thus the rate of newly-generated carboxyl be less than carbon fiber with
The rate that carboxyl caused by being reacted between sizing agent consumes so that carbon fiber surface can not be enriched with enough carboxylic groups.Therefore this hair
Bright heat treatment temperature is more than 250 DEG C, could meet the carbon fiber after thermal oxidation, a large amount of carboxyls of surface enrichment are wanted
It asks, is conducive to the raising of strengthened thermoplastic polyester interface performance.
(2) by coating the thermal oxidation of thermosetting resin sizing agent carbon fiber to surface, the heat of the carbon fiber is improved
Stability is avoided when subsequently carrying out 250 DEG C or more high temperature process moldings to thermoplastic polyester, the interface of the carbon fiber and polyester
Tiny micropore is formed in composite material surface because unstable group or carbochain degradation will produce a large amount of gas, reduces composite material
Interface and overall mechanical properties.If the heat treatment temperature of the present invention is less than 250 DEG C, then can not be made by thermal oxidation processes
Some groups or carbochain unstable in thermoplastic polyester matrix forming temperature decompose vapor away in advance, follow-up to be unfavorable for
The combination of composite material interface.
(3) process for treating surface of carbon fiber will match the production line of existing carbon fiber, therefore need in the short time (not surpass
A large amount of carboxyl is generated in half an hour).If heat treatment temperature is less than 250 DEG C, surface coats thermosetting resin sizing agent carbon fiber
On methylene or hydroxyl oxidation activation energy it is high, cause oxidation rate low, the online production to cannot be satisfied carbon fiber is wanted
It asks.
(4) when heat treatment temperature reaches 350 DEG C, carboxyl rhermal decomposition rate has been reached with the new rate for generating carboxyl of oxidation
It it is more than 350 DEG C to balance, such as heat treatment temperature, surface coats the methylene and hydroxyl oxygen on thermosetting resin sizing agent carbon fiber
The degradation rate for turning to carboxyl greatly improves, and carboxyl rhermal decomposition rate is more than the generating rate of carboxyl, the carboxyl amount for consumption of degrading
More than the carboxyl amount that thermal oxide generates, the amount of carbon fiber surface carboxyl can be reduced, and be unfavorable for follow-up strengthened thermoplastic polyester
Interface performance improve.
Advantageous effect：
(1) preparation method of a kind of carbon-fiber-reinforced polyester composite material of the invention, avoids secondary starching and makes carbon
The problem of pulp layer is greatly thickened on fiber surface, is conducive to the raising of carbon fiber and thermoplastic polyester wellability, and improves carbon fiber
The interface binding power of dimension and thermoplastic polyester；
(2) a kind of preparation method of carbon-fiber-reinforced polyester composite material of the invention, carbon fiber surface are coated with heat
Thermosetting resin sizing agent, compared to thermoplastic resin sizing agent, thermosetting resin sizing agent surface can reactive group it is more and living
Property it is high so that the interface cohesion between carbon fiber and thermosetting resin sizing agent is higher than thermoplastic resin sizing agent；
(3) preparation method of a kind of carbon-fiber-reinforced polyester composite material of the invention, heat treatment temperature is low, energy consumption is small,
Surface is coated thermosetting resin sizing agent carbon fiber carry out oxidation processes after, can reach with the high-temperature process reported not
The same effect of starching carbon fiber, surface are obtained rich in the carboxylic group that can be reacted with thermoplastic polyester matrix, subsequently by carbon fiber
Dimension is compound with thermoplastic polyester matrix, and chemical bonding effect is stronger, and the interface performance of composite material is greatly improved, great
Application prospect.
Description of the drawings
Fig. 1 is the surfaces XPS for the carbon fiber that low-temperature oxidation handles rear surface coated epoxy resin sizing agent in embodiment 1
Chemical composition and structure collection of illustrative plates；
Fig. 2 is the XPS surface chemistries composition and knot of the carbon fiber for the surface coated epoxy resin sizing agent being not handled by
Composition is composed.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) average length is the polyacrylonitrile-based carbon fibre of 10 μm of surface coated epoxy resin resin sizing agent and poly- pair
Terephtha-late dry 2h at 100 DEG C so that its water content is 0.019wt%；
(2) polyacrylonitrile-based carbon fibre of surface coated epoxy resin resin sizing agent is under 280 DEG C of oxidizing atmosphere
10min is kept the temperature, oxidizing atmosphere is air environment；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid fourth two
The mixture of ester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and zinc stearate is squeezed from twin-screw
Go out the addition of machine hopper, squeezes out and carbon-fiber-reinforced polyester composite material, wherein surface coated epoxy resin resin sizing agent is made
Polyacrylonitrile-based carbon fibre, polybutylene terephthalate, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] seasons penta
The mass ratio of four alcohol esters and zinc stearate is 20:80:0.1:0.1, double screw extruder from spout to extruder die head seven
Respectively 220 DEG C, 235 DEG C, 245 DEG C, 260 DEG C, 240 DEG C of area's temperature setting, 230 DEG C, 250 DEG C, engine speed 300rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 2h at 100 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 80 DEG C, and injection molding temperature is 240 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 160MPa, bending strength 240MPa, this reality
The XPS surface chemistry the Nomenclature Composition and Structure of Complexes collection of illustrative plates for applying the carbon fiber obtained after a step (2) processing is as shown in Figure 1.
Comparative example
A kind of preparation method of carbon fiber composite polyester material, basic step is same as Example 1, and difference is surface
The polyacrylonitrile-based carbon fibre of coated epoxy resin resin sizing agent is handled without step (2), final carbon fiber obtained
The tensile strength of composite polyester material is 110MPa, bending strength 180MPa, in this example carbon fiber XPS surface chemistries composition and
Structure collection of illustrative plates is as shown in Figure 2.
Complex chart 1 and 2 is analyzed it can be found that the peak of 284.7 and 285.6ev represents sp in figure2And sp3C-C keys,
What the peak of 286.5~286.7ev represented be hydroxyl or ehter bond C-OH＆C-O-C, 287.5ev peak represents is carbonyl or quinone knot
C=O keys on structure, what the peak of 288.8-289.2ev represented is the peak generation of carboxyl or ester group COOH＆COO, 291.2-291.4ev
Table is π-π * keys.Above-mentioned each figure is analyzed it can be found that the surface being not handled by coats the carbon fiber of thermosetting resin sizing agent
There are a large amount of hydroxyl and extremely a small amount of carboxyl in dimension table face, and the ratio that wherein hydroxyl accounts for C-C keys is 70.8%, and carboxyl is only
1.85%；Low-temperature oxidation treated carbon fiber (carbon fiber in Fig. 1), the carboxylic group ratio on surface greatly improve, reach
8.62%, it is possible thereby to find that the present invention changes the functional group of carbon fiber surface, its surface is made to be rich in carboxyl.By this example and reality
The comparison of example 1 is applied, (2) i.e. Low Temperature Heat Treatment significantly enhances the interlaminar shear strength of composite material the step of the application, that is, carries
The high interface binding power of carbon fiber and thermoplastic matrix.
Embodiment 2
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) average length is that the surface of 3mm coats the petroleum pitch-based carbon fiber of lactones modified epoxy sizing agent
6h is dried at 150 DEG C with polyethylene terephthalate so that its water content is 0.01wt%；
(2) surface is coated into oxidation of the petroleum pitch-based carbon fiber of lactones modified epoxy sizing agent at 250 DEG C
0.5min is kept the temperature under property atmosphere, oxidizing atmosphere is nitrogen dioxide environment；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid second two
Ester, N, N '-is bis--mixtures of (3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and the double fatty acid amides of ethylene
It is added from double screw extruder hopper, squeezes out and carbon-fiber-reinforced polyester composite material is made, wherein lactones is modified surface cladding
The petroleum pitch-based carbon fiber of epoxy resin sizing agent, polyethylene terephthalate, N, N '-is bis--(3- (3,5- di-t-butyls-
4- hydroxy phenyls) propiono) mass ratioes of the double fatty acid amides of hexamethylene diamine and ethylene is 40:60:0.2:0.3, double screw extruder
Respectively 230 DEG C, 240 DEG C, 260 DEG C, 280 DEG C, 260 DEG C of the 7th area temperature setting from spout to extruder die head, 255 DEG C,
260 DEG C, engine speed 400rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 6h at 150 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 100 DEG C, and injection molding temperature is 280 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 220MPa, bending strength 290MPa.
Embodiment 3
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 100 μm coats the coal tar pitch base carbon fiber of vinyl unsaturated polyester resin sizing agent
Peacekeeping polybutylene terephthalate dry 4h at 125 DEG C so that its water content is 0.015wt%；
(2) surface is coated into oxidation of the coal tar pitch base carbon fibre of vinyl unsaturated polyester resin sizing agent at 350 DEG C
15min is kept the temperature under property atmosphere, oxidizing atmosphere is chlorine gas environment；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid fourth two
The mixture of ester, three [2,4- di-tert-butyl-phenyls] phosphite esters and ethylene-acrylic acid copolymer is from double screw extruder hopper
It is added, squeezes out and carbon-fiber-reinforced polyester composite material is made, wherein surface coats vinyl unsaturated polyester resin sizing agent
Coal tar pitch base carbon fibre, polybutylene terephthalate, three [2,4- di-tert-butyl-phenyls] phosphite esters and ethylene-acrylic acid are total
The mass ratio of polymers is 30:70:0.2:0.3, seven area temperature setting point of the double screw extruder from spout to extruder die head
Wei not be 225 DEG C, 238 DEG C, 250 DEG C, 270 DEG C, 250 DEG C, 245 DEG C, 255 DEG C, engine speed 350rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 4h at 125 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 90 DEG C, and injection molding temperature is 260 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 180MPa, bending strength 260MPa.
Embodiment 4
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 1.5mm coats the viscose-based carbon fiber of phenolic resin sizing agent and poly- terephthaldehyde
Sour second diester dry 3h at 130 DEG C so that its water content is 0.015wt%；
(2) viscose-based carbon fiber that surface is coated to phenolic resin sizing agent is kept the temperature under 300 DEG C of oxidizing atmosphere
5min, oxidizing atmosphere are sulfur dioxide environment；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid second two
The mixture of ester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and silicone powder is from twin-screw extrusion
Machine hopper is added, and squeezes out and carbon-fiber-reinforced polyester composite material is made, wherein the viscose glue base of surface cladding phenolic resin sizing agent
The matter of carbon fiber, thermoplastic polyester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and silicone powder
Amount is than being 30:70:0.2:0.3, seven area temperature settings of the double screw extruder from spout to extruder die head are respectively 220
DEG C, 235 DEG C, 260 DEG C, 280 DEG C, 240 DEG C, 255 DEG C, 250 DEG C, engine speed 320rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 2h at 130 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 100 DEG C, and injection molding temperature is 240 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 175MPa, bending strength 245MPa.
Embodiment 5
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) average length is the phenolic aldehyde base carbon fibre of 50 μm of surface cladding melamine resin sizing agent and poly- pair
Terephtha-late/polyethylene terephthalate (mass ratio 1:1) the dry 6h at 150 DEG C so that its water content is
0.01wt%；
(2) surface is coated into oxidizing atmosphere of the phenolic aldehyde base carbon fibre of melamine resin sizing agent at 280 DEG C
Lower heat preservation 1min, oxidizing atmosphere are sulfur trioxide environment；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid fourth two
Ester/polyethylene terephthalate, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters/N, N '-is bis--
(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine (mass ratio 1:1) and zinc stearate/ethylene is double fatty
Amide (mass ratio 1:2) mixture is added from double screw extruder hopper, squeezes out and carbon fiber reinforced polyester composite wood is made
Phenolic aldehyde base carbon fibre, the polybutylene terephthalate/poly- to benzene of material, wherein surface cladding melamine resin sizing agent
Dioctyl phthalate second diester, four [β-(3,5- di-t-butyl -4- hydroxy phenyls) propionic acid] pentaerythritol esters/N, N '-is bis--(3- (3,5-
Di-tert-butyl-hydroxy phenyl) propiono) mass ratioes of the double fatty acid amides of hexamethylene diamine and zinc stearate/ethylene is 25:75:
0.3:0.5, seven areas temperature settings of the double screw extruder from spout to extruder die head are respectively 225 DEG C, 239 DEG C, 250
DEG C, 265 DEG C, 240~260 DEG C, 235 DEG C, 252 DEG C, engine speed 380rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 5h at 130 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 85 DEG C, and injection molding temperature is 250 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 168MPa, bending strength 241MPa.
Embodiment 6
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 300 μm coats the gas-phase growth of carbon fibre of furane resins sizing agent and gathers to benzene two
Formic acid fourth diester dry 2~6h at 100~150 DEG C so that its water content is less than 0.02wt%；
(2) gas-phase growth of carbon fibre that surface is coated to furane resins sizing agent is kept the temperature under 320 DEG C of oxidizing atmosphere
8min, oxidizing atmosphere are oxygen atmosphere；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid fourth two
Ester, N, N '-is bis--and the mixture of (3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and zinc stearate is from double spiral shells
Bar extruder hopper is added, and squeezes out and carbon-fiber-reinforced polyester composite material is made, and wherein surface coats furane resins sizing agent
Gas-phase growth of carbon fibre, polybutylene terephthalate, N, N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propionyl
Base) mass ratio of hexamethylene diamine and zinc stearate is 35:65:0.2:0.3, double screw extruder is from spout to extruder die head
Seven areas temperature settings are respectively 220 DEG C, 240 DEG C, 250 DEG C, 265 DEG C, 250 DEG C, 250 DEG C, 255 DEG C, and engine speed is
400rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 3h at 120 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 80 DEG C, and injection molding temperature is 265 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 200MPa, bending strength 272MPa.
Embodiment 7
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) average length be 200 μm surface coat polybutadiene sizing agent bacteria cellulose base carbon fibre and
Polyethylene terephthalate dry 2h at 150 DEG C so that its water content is 0.018wt%；
(2) surface is coated into oxidisability gas of the bacteria cellulose base carbon fibre of polybutadiene sizing agent at 310 DEG C
Keep the temperature 3min under atmosphere, oxidizing atmosphere is the mixed-gas environment of nitrogen dioxide and nitrogen, nitrogen dioxide in mixed-gas environment
Volume ratio be 5%；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid second two
Ester, N, N '-is bis--mixtures of (3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and the double fatty acid amides of ethylene
It is added from double screw extruder hopper, squeezes out and carbon-fiber-reinforced polyester composite material is made, wherein surface coats polybutadiene tree
Bacteria cellulose base carbon fibre, polyethylene terephthalate, the N of fat sizing agent, N '-be bis--(3- (3,5- di-t-butyl -4- hydroxyls
Base phenyl) propiono) mass ratioes of the double fatty acid amides of hexamethylene diamine and ethylene is 20:80:0.1:0.5, double screw extruder is fed certainly
Seven areas temperature settings of material mouth to extruder die head are respectively 225 DEG C, 240 DEG C, 245 DEG C, 260 DEG C, 260 DEG C, 255 DEG C, and 250
DEG C, engine speed 300rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 2h at 120 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 100 DEG C, and injection molding temperature is 260 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 165MPa, bending strength 240MPa.
Embodiment 8
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 1mm coats the cellulose base carbon fiber of organic siliconresin sizing agent and gathers to benzene two
Formic acid fourth diester/polyethylene terephthalate (mass ratio 2:1) the dry 2h at 150 DEG C so that its water content is
0.013wt%；
(2) the cellulose base carbon fiber that surface is coated to organic siliconresin sizing agent is protected under 340 DEG C of oxidizing atmosphere
Warm 9min, oxidizing atmosphere are the mixed-gas environment of chlorine and argon gas, and the volume ratio of chlorine is 10% in mixed-gas environment；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid fourth two
The mixture of ester/polyethylene terephthalate, three [2,4- di-tert-butyl-phenyls] phosphite esters and zinc stearate is from twin-screw
Extruder hopper is added, and squeezes out and carbon-fiber-reinforced polyester composite material is made, and wherein surface coats organic siliconresin sizing agent
Cellulose base carbon fiber, polybutylene terephthalate/polyethylene terephthalate, three [2,4- di-tert-butyl-phenyls] phosphorous
The mass ratio of acid esters and zinc stearate is 40:60:0.2:0.2, seven area of the double screw extruder from spout to extruder die head
Respectively 230 DEG C, 235 DEG C, 245 DEG C, 265 DEG C, 250 DEG C of temperature setting, 245 DEG C, 250 DEG C, engine speed 300rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 2h at 100 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 90 DEG C, and injection molding temperature is 260 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 213MPa, bending strength 285MPa.
Embodiment 9
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 1mm coats the lignin-base carbon fiber of polyurethane resin sizing agent and gathers to benzene two
Formic acid fourth diester dry 2h at 130 DEG C so that its water content is 0.018wt%；
(2) the lignin-base carbon fiber that surface is coated to polyurethane resin sizing agent is protected under 290 DEG C of oxidizing atmosphere
Warm 6min, oxidizing atmosphere are the mixed-gas environment of sulfur trioxide and nitrogen, the volume of sulfur trioxide in mixed-gas environment
Than being 20%；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid fourth two
Ester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester/tri- [2,4- di-tert-butyl-phenyls] phosphite esters
(mass ratio 2:1) and the mixture of silicone powder is added from double screw extruder hopper, and it is multiple to squeeze out obtained carbon fiber reinforced polyester
Condensation material, wherein surface coat lignin-base carbon fiber, polybutylene terephthalate, the four [β-of polyurethane resin sizing agent
(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester/tri- [2,4- di-tert-butyl-phenyls] phosphite ester and silicone powder
Mass ratio be 25:75:0.1:0.5, seven area temperature of the double screw extruder from spout to extruder die head, which are set, is respectively
230 DEG C, 235 DEG C, 260 DEG C, 280 DEG C, 260 DEG C, 255 DEG C, 250 DEG C, engine speed 330rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 3h at 120 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 100 DEG C, and injection molding temperature is 250 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 178MPa, bending strength 250MPa.
Embodiment 10
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface coated epoxy resin/unsaturated polyester resin sizing agent (mass ratio 1 that average length is 500 μm:
1) lignin-base carbon fiber and polybutylene terephthalate/polyethylene terephthalate (mass ratio 1:1) at 100 DEG C
Lower dry 2h so that its water content is 0.019wt%；
(2) by surface coated epoxy resin/unsaturated polyester resin sizing agent (mass ratio 1:1) lignin-base carbon fiber
Dimension keeps the temperature 0.8min under 260 DEG C of oxidizing atmosphere, and oxidizing atmosphere is the mixed-gas environment of sulfur dioxide and neon, is mixed
The volume ratio for closing gaseous environment sulfur dioxide is 50%；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid fourth two
Ester/polyethylene terephthalate, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and zinc stearate
Mixture from double screw extruder hopper be added, squeeze out be made carbon-fiber-reinforced polyester composite material, wherein surface coat ring
Lignin-base carbon fiber, the polybutylene terephthalate/poly terephthalic acid second of oxygen resin/unsaturated polyester resin sizing agent
The mass ratio of diester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and zinc stearate is 30:70:
0.2:0.3, seven areas temperature settings of the double screw extruder from spout to extruder die head are respectively 230 DEG C, 240 DEG C, 248
DEG C, 265 DEG C, 245 DEG C, 230 DEG C, 250 DEG C, engine speed 300rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 3h at 150 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 80 DEG C, and injection molding temperature is 250 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 176MPa, bending strength 258MPa.
Embodiment 11
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 10 μm coats melamine resin/furane resins sizing agent (mass ratio 1:
2) polyacrylonitrile-based carbon fibre and the polyethylene terephthalate dry 2.5h at 150 DEG C so that its water content is
0.019wt%；
(2) surface is coated into the polyacrylonitrile-based carbon fibre of melamine resin/furane resins sizing agent 270
DEG C oxidizing atmosphere under keep the temperature 5min, oxidizing atmosphere is nitrogen dioxide/chlorine gas environment (volume ratio 1:1)；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid second two
Double fatty acid amide/the ethylene-acrylic acids of ester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and ethylene
Copolymer (mass ratio 1:1) mixture is added from double screw extruder hopper, and it is compound to squeeze out obtained carbon fiber reinforced polyester
Material, wherein surface coat the polyacrylonitrile-based carbon fibre of melamine resin/furane resins sizing agent, poly- terephthaldehyde
Double fatty acid amide/the ethylene-of sour second diester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and ethylene
The mass ratio of acrylic copolymer is 30:70:0.1:0.1, seven area temperature of the double screw extruder from spout to extruder die head
Respectively 230 DEG C, 235 DEG C, 250 DEG C, 270 DEG C, 250 DEG C of degree setting, 250 DEG C, 255 DEG C, engine speed 350rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 2h at 110 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 95 DEG C, and injection molding temperature is 250 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 157MPa, bending strength 246MPa.
Embodiment 12
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 2mm coats polybutadiene/organic siliconresin sizing agent (mass ratio 2:9)
Gas-phase growth of carbon fibre and the polyethylene terephthalate dry 3h at 110 DEG C so that its water content is 0.016wt%；
(2) surface is coated into the gas-phase growth of carbon fibre of polybutadiene/organic siliconresin sizing agent at 290 DEG C
12min is kept the temperature under oxidizing atmosphere, oxidizing atmosphere is the mixed-gas environment of nitrogen dioxide, chlorine and helium, mixed gas
The volume ratio of chlorine is 5% in environment, and the volume ratio of nitrogen dioxide is 15%；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid second two
Ester, N, N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and zinc stearate/silicone powder (mass ratio
It is 2:1) mixture is added from double screw extruder hopper, squeezes out and carbon-fiber-reinforced polyester composite material, wherein surface is made
Gas-phase growth of carbon fibre, polyethylene terephthalate, the N of polybutadiene/organic siliconresin sizing agent are coated, N '-is bis--
(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and the mass ratio of zinc stearate/silicone powder are 35:65:
0.1:0.3, seven areas temperature settings of the double screw extruder from spout to extruder die head are respectively 225 DEG C, 240 DEG C, 245
DEG C, 265 DEG C, 250 DEG C, 255 DEG C, 260 DEG C, engine speed 400rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 2h at 150 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 100 DEG C, and injection molding temperature is 280 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 212MPa, bending strength 280MPa.
Embodiment 13
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 400 μm coats unsaturated polyester resin/organic siliconresin sizing agent (mass ratio 1:
1) polyacrylonitrile-based carbon fibre and the polyethylene terephthalate dry 2h at 130 DEG C so that its water content is
0.016wt%；
(2) surface is coated into the polyacrylonitrile-based carbon fibre of unsaturated polyester resin/organic siliconresin sizing agent 255
DEG C oxidizing atmosphere under keep the temperature 1min, oxidizing atmosphere is the mixed-gas environment of chlorine and Krypton, in mixed-gas environment
The volume ratio of chlorine is 6%；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid second two
The mixture of the double fatty acid amides of ester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and ethylene is certainly double
Screw extruder hopper is added, and the obtained carbon-fiber-reinforced polyester composite material of extrusion, wherein surface cladding unsaturated polyester resin/
Polyacrylonitrile-based carbon fibre, polyethylene terephthalate, the four [β-(3,5- di-t-butyl -4- hydroxyls of organic siliconresin sizing agent
Base phenyl) propionic acid] mass ratioes of the double fatty acid amides of pentaerythritol ester and ethylene is 32:68:0.3:0.1, double screw extruder is certainly
Seven areas temperature settings of spout to extruder die head are respectively 225 DEG C, 240 DEG C, 255 DEG C, 265 DEG C, 250 DEG C, 255 DEG C, and 260
DEG C, engine speed 400rpm.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 216MPa, bending strength 287MPa.
Embodiment 14
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 0.5mm coats phenolic resin/melamine resin sizing agent (mass ratio 2:
3) viscose-based carbon fiber and polybutylene terephthalate dry 2h at 150 DEG C so that its water content is 0.015wt%；
(2) surface is coated into oxygen of the viscose-based carbon fiber of phenolic resin/melamine resin sizing agent at 345 DEG C
14min is kept the temperature under the property changed atmosphere, and oxidizing atmosphere is the mixed-gas environment of nitrogen dioxide and xenon, two in mixed-gas environment
The volume ratio of nitrogen oxide is 70%；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid fourth two
The mixture of the double fatty acid amides of ester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and ethylene is certainly double
Screw extruder hopper is added, and squeezes out and carbon-fiber-reinforced polyester composite material is made, and wherein surface coats phenolic resin/melamine
Viscose-based carbon fiber, polybutylene terephthalate, the four [β-(3,5- di-t-butyl -4- hydroxy benzenes of amine-formaldehyde resins sizing agent
Base) propionic acid] mass ratioes of the double fatty acid amides of pentaerythritol ester and ethylene is 20:80:0.2:0.1, double screw extruder is from feeding
Mouthful to seven areas temperature settings of extruder die head be respectively 220 DEG C, 240 DEG C, 250 DEG C, 270 DEG C, 250 DEG C, 250 DEG C, 255 DEG C,
Engine speed is 350rpm.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 165MPa, bending strength 240MPa.
Embodiment 15
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 2mm coats furane resins/organic siliconresin sizing agent (mass ratio 1:3) phenolic aldehyde
Base carbon fibre and the polybutylene terephthalate dry 5h at 140 DEG C so that its water content is 0.016wt%；
(2) surface is coated into oxidisability gas of the phenolic aldehyde base carbon fibre of furane resins/organic siliconresin sizing agent at 305 DEG C
Keep the temperature 7min under atmosphere, oxidizing atmosphere is the mixed-gas environment of sulfur dioxide, chlorine and radon gas, chlorine in mixed-gas environment
Volume ratio be 15%, the volume ratio of sulfur dioxide is 25%；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid fourth two
The mixture of ester, three [2,4- di-tert-butyl-phenyls] phosphite esters and ethylene-acrylic acid copolymer is from double screw extruder hopper
It is added, squeezes out and carbon-fiber-reinforced polyester composite material is made, wherein surface coats furane resins/organic siliconresin sizing agent
Phenolic aldehyde base carbon fibre, polybutylene terephthalate, three [2,4- di-tert-butyl-phenyls] phosphite esters and ethylene-acrylic acid copolymer
The mass ratio of object is 30:70:0.2:0.4, seven area temperature setting difference of the double screw extruder from spout to extruder die head
It is 225 DEG C, 238 DEG C, 245 DEG C, 280 DEG C, 240 DEG C, 230 DEG C, 255 DEG C, engine speed 320rpm.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 172MPa, bending strength 250MPa.
Embodiment 16
A kind of preparation method of carbon-fiber-reinforced polyester composite material, its step are as follows：
(1) surface that average length is 10 μm coats polybutadiene/phenolic resin sizing agent (mass ratio 3:1)
Bacteria cellulose base carbon fibre and the polyethylene terephthalate dry 2h at 150 DEG C so that its water content is
0.018wt%；
(2) surface is coated into the bacteria cellulose base carbon fibre of polybutadiene/phenolic resin sizing agent at 255 DEG C
Oxidizing atmosphere under keep the temperature 4min, oxidizing atmosphere is the mixed-gas environment of sulfur trioxide, oxygen and radon gas, mixed gas
The volume ratio of sulfur trioxide is 2% in environment, and the volume ratio of oxygen is 4%；
(3) fine mouth is added to be added by double screw extruder on step (1) treated carbon fiber, poly terephthalic acid second two
The mixture of ester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and zinc stearate is squeezed from twin-screw
Go out the addition of machine hopper, squeeze out and carbon-fiber-reinforced polyester composite material is made, wherein surface coats polybutadiene/phenolic resin
Bacteria cellulose base carbon fibre, polyethylene terephthalate, the four [β-(3,5- di-tert-butyl-hydroxy phenyls) of sizing agent
Propionic acid] mass ratio of pentaerythritol ester and zinc stearate is 40:60:0.3:0.5, double screw extruder is from spout to extrusion
Respectively 230 DEG C, 240 DEG C, 260 DEG C, 270 DEG C, 250 DEG C of the 7th area temperature setting of machine die head, 235 DEG C, 255 DEG C, engine speed
For 300rpm；
(4) carbon-fiber-reinforced polyester composite material is dried to 2h at 140 DEG C, then is injection moulded sample preparation, it is injection molding
Mould temperature is 80 DEG C, and injection molding temperature is 260 DEG C.
The tensile strength of carbon-fiber-reinforced polyester composite material obtained is 217MPa, bending strength 288MPa.
Claims (9)
1. a kind of preparation method of carbon-fiber-reinforced polyester composite material, it is characterized in that：First surface is coated on thermosetting resin
The carbon fiber for starching agent carries out Low Temperature Heat Treatment, then adds fine mouth to be added by double screw extruder on the carbon fiber of Low Temperature Heat Treatment, heat
The mixture of plasticity polyester, antioxidant and lubricant is added from double screw extruder hopper, and it is poly- to squeeze out obtained fibre reinforced
Ester composite material；
The carbon fiber of the surface cladding thermosetting resin sizing agent, the mass ratio of thermoplastic polyester, antioxidant and lubricant
It is 20~40:60~80:0.1~0.3:0.1~0.5；
The Low Temperature Heat Treatment refers to 0.5~15min of heat preservation at 250~350 DEG C.
2. a kind of preparation method of carbon-fiber-reinforced polyester composite material according to claim 1, which is characterized in that described
Carbon fiber is polyacrylonitrile-based carbon fibre, petroleum pitch-based carbon fiber, coal tar pitch base carbon fibre, viscose-based carbon fiber, phenolic aldehyde base
One in carbon fiber, gas-phase growth of carbon fibre, bacteria cellulose base carbon fibre, cellulose base carbon fiber and lignin-base carbon fiber
Kind or more；Its average length is 10 μm~3mm.
3. a kind of preparation method of carbon-fiber-reinforced polyester composite material according to claim 1, which is characterized in that described
The ingredient of thermosetting resin sizing agent is epoxy resin and its derivative, unsaturated polyester resin, polyurethane resin, phenolic aldehyde tree
One or more of fat, melamine resin, furane resins, polybutadiene and organic siliconresin；The thermoplasticity
Polyester is more than one of polybutylene terephthalate and polyethylene terephthalate；The antioxidant be four [β-(3,
5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, N, N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) third
Acyl group) one or more of hexamethylene diamine or three [2,4- di-tert-butyl-phenyls] phosphite esters；The lubricant is zinc stearate, second
One or more of the double fatty acid amides of support, ethylene-acrylic acid copolymer or silicone powder.
4. a kind of preparation method of carbon-fiber-reinforced polyester composite material according to claim 1, which is characterized in that described
Low Temperature Heat Treatment is carried out in oxidizing atmosphere；The oxidizing atmosphere be oxidizing gas environment or oxidizing gas with it is lazy
Property gas mixed-gas environment, the volume ratio of oxidizing gas is more than or equal to 5% in mixed-gas environment.
5. a kind of preparation method of carbon-fiber-reinforced polyester composite material according to claim 4, which is characterized in that described
Oxidizing gas is one or more of nitrogen dioxide, chlorine, sulfur dioxide, sulfur trioxide, air and oxygen；The indifferent gas
Body is nitrogen, argon gas, helium, neon, Krypton, xenon or radon gas.
6. a kind of preparation method of carbon-fiber-reinforced polyester composite material according to claim 1, which is characterized in that described
Processing is pre-dried in the carbon fiber and thermoplastic polyester of surface cladding thermosetting resin sizing agent, and temperature is 100~150 DEG C, when
Between be 2~6h, be pre-dried processing after water content be less than 0.02wt%.
7. a kind of preparation method of carbon-fiber-reinforced polyester composite material according to claim 1, which is characterized in that described
Seven areas temperature settings of the double screw extruder from spout to extruder die head are respectively 220~230 DEG C, 235~240 DEG C, 245
~260 DEG C, 260~280 DEG C, 240~260 DEG C, 230~255 DEG C, 250~260 DEG C, engine speed is 300~400rpm.
8. a kind of preparation method of carbon-fiber-reinforced polyester composite material according to claim 1, which is characterized in that described
Carbon-fiber-reinforced polyester composite material dry 2~6h at 100~150 DEG C, then it is injection moulded sample preparation, the injection molding mould
Temperature is 80~100 DEG C, and injection molding temperature is 240~280 DEG C.
9. being made using a kind of such as preparation method of carbon-fiber-reinforced polyester composite material of claim 1~8 any one of them
Carbon-fiber-reinforced polyester composite material, it is characterized in that：The tensile strength of the carbon-fiber-reinforced polyester composite material be 160~
220MPa, bending strength are 240~290MPa.
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| WO2022144159A1 (en) * | 2020-12-28 | 2022-07-07 | Basf Se | Polybutylene terephthalate composition and article |
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