CN106883559A - A kind of preparation method of high rigidity carbon fibre composite resin matrix - Google Patents
A kind of preparation method of high rigidity carbon fibre composite resin matrix Download PDFInfo
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
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Abstract
The present invention is main body by from high-performance epoxy resin, fluorine-containing epoxy resin compounding is added to introduce the strong and unyielding degree that the strong fluorine element for inhaling electrical characteristics carrys out regulatory molecule chain structure with the diverse location of backbone structure simultaneously, resin system modulus and adhesive property with carbon fiber interface are further improved by adding functionalized carbon nano-tube, by adjusting matrix resin, fluorine resin, curing agent, accelerator, proportioning between CNT prepares a kind of low viscosity, it is good with carbon fiber wellability, working life is long, and composite product has high rigidity, the resin dedicated system of winding of high-modulus, efficiently solve the matching problem with high-modules carbon fibre, the transversely deforming of composite is regulated and controled, there is great directive significance to preparing high rigidity composite and its correlated product.
Description
Technical field
The invention belongs to fiber resin matrix field of compound material, a kind of high rigidity carbon fibre composite tree is related generally to
Aliphatic radical body and preparation method thereof.
Background technology
The carbon fiber resin matrix composite excellent performance such as have intensity high, light weight, fatigue durability good, in aviation boat
The civilian aspects such as its field, the research of lightweight automotive field low energy consumption new-energy automobile and petrochemical industry physical culture building materials have
Important application.In recent years, the development of carbon fibre composite rises year by year with usage trend, wherein industrial carbon fiber is compound
Material cylinder progressively develops into full carbon fiber composite structure by all-metal construction cylinder, relative to conventional metal frames cylinder
Body, with light weight, that intensity is high, fatigue resistance is good, long service life, production technology are easy, structure designability is strong etc. is many
Advantage.Prepare high rigidity carbon fibre composite cylinder and need to improve its axial modulus and modulus of shearing simultaneously, it is necessary to using
The high modulus carbon fiber material of demand is met in intensity.
The mechanical properties such as the excellent intensity of carbon fiber and modulus are given full play to, it is necessary to select to match and set with carbon fiber
Aliphatic radical body.The performances such as elastic modelling quantity, elongation at break due to resin and fiber are mismatched, and failure mode is often multi-stag
Progressive failure, in general, the elongation at break of resin matrix is higher than carbon fiber, and the modulus of resin matrix and intensity etc. are remote low
In carbon fiber.Actually intensity of compatibility of deformation of the matrix with fiber under outer stress than matrix in itself is even more important,
The strong and unyielding property matching between fiber and resin matrix need to be paid the utmost attention to.Even if the intensity of resin is very high (but compared with reinforcing fiber
It is always very low), and extension at break very little, when fiber is also in compared with low stress level, fiber strain has been more than the matrix limit
Strain, now matrix will ftracture, and cause composite gradually to lose globality and destroy, and fibre strength cannot fully be sent out
Wave.Elongation at break resin matrix higher, before can guarantee that fibrous fracture matrix keep integrality, therefore composite by because
Fibrous fracture and destroy.But to ensure the rigidity and heat resistance of resin matrix, its elongation at break is also unsuitable excessive.Use height
Composite prepared by modules carbon fibre, fiber and resin matrix will simultaneously bear larger load under relatively low deformation, therefore
The rigidity and intensity of resin matrix need further to improve.(Chen Ping, not smoothgoing tin is high, Chen Hui, giant dragon high, Han Bing, Zhu Xing for Chen Ping et al.
The loose carbon fibre composites motor body research composite journals of tough epoxy resin matrix, 2002,02:24-
27) with TDE-85 and E51 as matrix resin, by adding through toughening agent modified aromatic amine curing agent DDM, can be with T700 carbon
Fiber matched well, but when being applied to high-modules carbon fibre, resin modulus is not enough and heat resistance is poor, it is difficult to meet high rigidity and be combined
The use demand of material.
Meanwhile, good fiber-resin basal body interface performance is also the necessary condition for playing carbon fiber strength and modulus, carbon
Fiber is the graphite-structure with skin-core shape, and the graphite crystallization degree on its top layer is very high and into relative inertness, and surface tension is very
Greatly, bonded with resin matrix poor.To improve the interface performance of composite, do not require nothing more than to surface treatment of carbon fibers to improve
Surface-active, also requires that resin matrix has good interface wellability and cementability.To meet leaching of the resin matrix to fiber
Lubricant nature, typically requires that the viscosity of resin matrix is low, so that when composite processing is molded, resin can more be sufficiently wet
Fiber, improves the interface performance of composite.(Huang Yeqing, Zhang Kang are helped yellow industry green grass or young crops et al., and the clean carbon fiber wet windings of Wang Xiao are used
Epoxy resin-base studies [J], thermosetting resin, 2007,01:27-29) with three-functionality-degree epoxy as matrix resin, mixing virtue
Fragrant amine is curing agent, have studied the epoxy resin-base of suitable T700 carbon fibre composites wet winding technology, the resin base
Body is applied to high-strength carbon fiber composite.But the research report on high-modules carbon fibre resin matrix is then less.
High rigidity carbon fibre composite field is prepared, needing exploitation one kind badly can be provided simultaneously with height with high-modules carbon fibre matched well
The resin dedicated system of intensity, high-modulus and good process, wellability and long pot life.
The content of the invention
The present invention is matrix resin by from high-performance epoxy resin, while adding fluorine-containing epoxy resin organic to change
Compound backbone structure, regulates and controls its strong and unyielding degree；Suitable curing agent and accelerator and its proportioning are selected, resinite is effectively controlled
The working life of system and activity of curing reaction；Add the interface between treated functionalized carbon nano-tube increase fiber-resin
Performance.Prepared by adjusting the proportioning of matrix resin, fluorine-containing epoxy resin, curing agent, accelerator and functionalized carbon nano-tube
A kind of low-viscosity, high rigidity, long pot life matched with high-strength carbon fibre well, the excellent winding epoxy of comprehensive mechanical property
Resin system, can be applied to the preparation of high rigidity carbon fibre composite, solve that resin matrix modulus is low and high strength carbon fine
The problem of dimension matching difference, has filled up the blank of the epoxy resin research for being matched with high-strength carbon fibre at this stage.
To achieve the above object, the present invention provides a kind of preparation side of high rigidity carbon fibre composite resin matrix
Method, its particular technique content is as follows：
A kind of carbon fibre composite resin matrix in the present invention, the resin matrix is 100 by mass fraction proportioning:
(10-40):(20-50):(1-4):The matrix resin of (0.1-2), fluorine resin, curing agent, accelerator and functionalized carbon nanometer
Pipe is constituted.
Wherein, matrix resin be selected from polyfunctionality diglycidyl ether type epoxy resin in it is several, or polyfunctionality shrink
It is several in glycerine ester type epoxy resin, or polyfunctionality diglycidyl ether type and polyfunctionality glycidyl ester type epoxy resin
In several compound；Fluorine resin be 2,2- bis-phenol base HFC-236fas diglycidyl ether, octafluorobiphenyl diglycidyl ether,
One kind in double (base in hexafluoro antelope) the benzene diglycidyl ethers of 1,3- (double light propyl group of hexafluoro) benzene diglycidyl ethers and 1,4- or
Several compounds.
Specific preparation method the present invention also aims to provide above-mentioned composite resin matrix.
The preparation method of above-mentioned composite resin matrix, comprises the following steps：First by selected matrix resin
Mixing 20-60min is stirred at 60-100 DEG C by proportioning with fluorine resin；Then by selected curing agent and accelerator and
Functionalized carbon nano-tube is stirred mixing 40-80min by proportioning at 80-150 DEG C, is cooled to ultrasonic agitation 30min at 60 DEG C.
Further, by well mixed matrix resin, fluorine resin blending ingredients and curing agent, accelerator, CNT mixing group
Point mixing 20-40min is stirred at 30-60 DEG C by proportioning, finally deaeration obtains described winding resin matrix under vacuo.
Effect of the invention is：1) it is used as matrix resin, fluorine-containing epoxy by from high-performance, multiple functionality epoxide resin
Resin changes molecular backbone structure, the composite resin matrix is had excellent mechanical strength and modulus, fluorine-containing epoxy
The strong and unyielding degree of Effective Regulation resin system is capable of in the change of resin content.2) imidazoles accelerator is used, resinite is ensure that
System has working life more long and relatively low viscosity, composite can in the curing process solidified homogeneous, to obtain structure
The good product of regular, apparent mass.3) fiber-resin interface performance, good fibre are improved from functionalized carbon nano-tube
Dimension-resin boundary surface can not only improve the intensity in vertical fibers direction, can also improve along the intensity and modulus of machine direction.
Below in conjunction with form, present disclosure is described in detail with specific embodiment.Table 1 is in each embodiment
The mass fraction of used each concrete component, table 2 is the mechanical strength performance pair of each embodiment and each group sample in comparative example
Than table 3 is the mechanical moduli performance comparison of each embodiment and each group sample in comparative example.
Specific implementation method
The method of testing provided according to GB/T2567-2008 in embodiment is cast on SUNS universal testing machines
The stretching of body and crooked test；The winding method provided according to GB/T4550-2005 prepares carbon fibre composite flat board, according to
The method of testing that GB/T3354-2014 and GB/T3354-2014 is provided prepares test sample, on SUNS universal testing machines
Unidirectionally answer stretching and the crooked test of material, the method for testing provided according to GB/T1458-2008 is tried in SUNS universal materials
Shearing test between the NOL rings extension test, the NOL circular layers that carry out annular composite material sample is tested on machine.
Wherein, because pour mass is prepared using high rigidity resin system, therefore it is prepared by consistent with sample state dimensioning
Mould directly prepare, with avoid the flat band method later stage cut sample when cause machining destroy；Similarly, prepared by NOL rings sample
Using monocyclic winding method prepare, with avoid cylinder cut it is around-France cut ring process in cause machining destroy.
Embodiment of the present invention is further illustrated with embodiment below, but the invention is not restricted to following examples.Under
Experimental technique described in embodiment is stated, unless otherwise specified, conventional method is；The reagent and material, unless otherwise specified,
Commercially obtain.
Embodiment 1
By the mass fraction of matrix resin, fluorine resin, curing agent, accelerator and functionalized carbon nano-tube according to 100:
20:40:2:It is prepared by 1 proportioning.Main body epoxy resin uses hexahydrophthalic acid 2-glycidyl fat, diglycidyl ether type ring
The compound of oxygen tree fat AG80 and butyl glycidyl ether, fluorine-containing epoxy resin uses 2,2- bis-phenol bases HFC-236fa two to shrink sweet
Oily ether is a kind of, and curing agent uses trien, the compound of IPD IPD, and accelerator uses 2- ethyl -4- first
Base imidazoles, CNT uses aminated carbon nano tube, carbon fiber to use the T700S-12K of toray company.Preparation process
It is as follows：Matrix resin and fluorine resin are stirred into mixing 30min by proportioning at 70 DEG C；By selected curing agent and accelerator
And functionalized carbon nano-tube is stirred mixing 50min by proportioning at 120 DEG C, is cooled to ultrasonic agitation 30min at 60 DEG C.Will
Well mixed matrix resin, fluorine resin blending ingredients and curing agent, accelerator, CNT blending ingredients are by proportioning 45
Mixing 20min is stirred at DEG C, finally deaeration obtains described winding resin matrix under vacuo.Resin adhesive liquid is poured to advance
With resin-cast body sample in ready mould, unidirectional carbon fiber reinforced plasticses flat board and carbon are prepared by winding shaping process
Fibrous composite NOL rings.Sample condition of cure is 90 DEG C/1h+120 DEG C/2h+150 DEG C/2h, after solidifying and being cooled to room temperature,
Taking out sample carries out demoulding treatment, carries out the size grinding process of correlation according to corresponding Standard and tests.
Ju Ti Pei Fang design is as shown in table 1 in embodiment, resin-cast body, unidirectional composite material, the stretching of NOL rings and layer
As shown in table 2, Moduli data is as shown in table 3 for the intensity data of the Mechanics Performance Testing cut.
Comparative example 1
Without fluorine-containing epoxy resin, other conditions are consistent with step and embodiment 1.Resin-cast body, unidirectional composite wood
As shown in table 2, Moduli data is as shown in table 3 for the intensity data of the Mechanics Performance Testing that material, the stretching of NOL rings and layer are cut.By
As can be seen that not having larger without the intensity that resin-cast body, unidirectional composite material, NOL rings after fluorine resin are stretched in table 3
Change, but modulus decline is obvious, i.e., and fluorine resin can be effectively increased resin system modulus.
Embodiment 2
By the mass fraction of matrix resin, fluorine resin, curing agent, accelerator and functionalized carbon nano-tube according to 100:
10:30:2:It is prepared by 1 proportioning.Main body epoxy resin shrinks sweet using hexahydrophthalic acid 2-glycidyl fat, bisphenol-A two
The compound of oily ether E51 and butyl glycidyl ether, fluorine-containing epoxy resin uses 1,3- (double light propyl group of hexafluoro) benzene two to shrink sweet
Oily ether is a kind of, and curing agent uses trien, the compound of diaminodiphenyl-methane (DDM), and accelerator uses 2- second
Base -4-methylimidazole, CNT uses carboxylic carbon nano-tube, carbon fiber to use the T700S-12K of toray company.System
Standby process is as follows：Matrix resin and fluorine resin are stirred into mixing 30min by proportioning at 70 DEG C；By selected curing agent and
Accelerator and functionalized carbon nano-tube are stirred mixing 50min by proportioning at 120 DEG C, are cooled to ultrasonic agitation at 60 DEG C
30min.Well mixed matrix resin, fluorine resin blending ingredients and curing agent, accelerator, CNT blending ingredients are pressed
Proportioning stirs mixing 20min at 45 DEG C, and finally deaeration obtains described winding resin matrix under vacuo.Resin adhesive liquid is poured
Build into preprepared mould with resin-cast body sample, unidirectional carbon fiber reinforced plasticses are prepared by winding shaping process
Flat board and carbon fibre composite NOL rings.Sample condition of cure is 90 DEG C/1h+120 DEG C/2h+150 DEG C/2h, solidification and cooling
To room temperature, taking out sample carries out demoulding treatment, carries out the size grinding process of correlation according to corresponding Standard and surveys
Examination.
Ju Ti Pei Fang design is as shown in table 1 in embodiment, resin-cast body, unidirectional composite material, the stretching of NOL rings and layer
As shown in table 2, Moduli data is as shown in table 3 for the intensity data of the Mechanics Performance Testing cut.
Comparative example 2
Without functionalized carbon nano-tube, other conditions are consistent with step and embodiment 2.It is resin-cast body, unidirectional compound
As shown in table 2, Moduli data is as shown in table 3 for the intensity data of the Mechanics Performance Testing that material, the stretching of NOL rings and layer are cut.
When without functionalized carbon nano-tube, NOL rings interlaminar shear strength declines substantially, and functionalized carbon nano-tube can be effectively increased
The interface performance of carbon fiber-resin.
Embodiment 3
By the mass fraction of matrix resin, fluorine resin, curing agent, accelerator and functionalized carbon nano-tube according to 100:
10:30:2:It is prepared by 1 proportioning.Main body epoxy resin is using contracting hexahydrophthalic acid 2-glycidyl fat, diglycidyl ether type
The compound of epoxy resin AG80, bisphenol A diglycidyl ether E51 and butyl glycidyl ether, fluorine-containing epoxy resin uses 2,
2- bis-phenol base HFC-236fas diglycidyl ether is a kind of, and curing agent uses trien, diaminodiphenyl-methane (DDM)
Compound, accelerator uses 1- amino-ethyls -2-methylimidazole (AMZ), CNT to use carboxylic carbon nano-tube, and carbon is fine
Dimension uses the T700S-12K of toray company.Preparation process is as follows：Matrix resin and fluorine resin are pressed and is matched at 70 DEG C
Stirring mixing 30min；Selected curing agent and accelerator and functionalized carbon nano-tube are stirred mixed by proportioning at 120 DEG C
50min is closed, ultrasonic agitation 30min at 60 DEG C is cooled to.Matrix resin that will be well mixed, fluorine resin blending ingredients and solid
Agent, accelerator, CNT blending ingredients are stirred mixing 20min by proportioning at 45 DEG C, and finally deaeration is obtained under vacuo
Described winding resin matrix.Resin adhesive liquid is poured into preprepared mould with resin-cast body sample, by twining
Unidirectional carbon fiber reinforced plasticses flat board and carbon fibre composite NOL rings are prepared around moulding process.Sample condition of cure be 90 DEG C/
1h+120 DEG C/2h+150 DEG C/2h, after solidifying and being cooled to room temperature, taking out sample carries out demoulding treatment, according to corresponding GB
It is required that carrying out the size grinding process of correlation and testing.
Ju Ti Pei Fang design is as shown in table 1 in embodiment, resin-cast body, unidirectional composite material, the stretching of NOL rings and layer
As shown in table 2, Moduli data is as shown in table 3 for the intensity data of the Mechanics Performance Testing cut.
Comparative example 3
The functionalized carbon nano-tube that will be added replaces with the carbon Guan Yuanguan for not carrying out functionalization, other conditions and step
It is rapid consistent with embodiment 3.The intensity number of the Mechanics Performance Testing that resin-cast body, unidirectional composite material, the stretching of NOL rings and layer are cut
According to as shown in table 2, Moduli data is as shown in table 3.Resin-cast body, unidirectional composite material mechanical strength performance in comparative example
It has been declined that, thus it is more excellent using functionalized carbon nano-tube personality.
Embodiment 4
By the mass fraction of matrix resin, fluorine resin, curing agent, accelerator and functionalized carbon nano-tube according to 100:
20:40:2:It is prepared by 1 proportioning.Main body epoxy resin uses hexahydrophthalic acid 2-glycidyl fat, diglycidyl ether type ring
The compound of oxygen tree fat DER353 and butyl glycidyl ether, fluorine-containing epoxy resin is contracted using Isosorbide-5-Nitrae-bis- (base in hexafluoro antelope) benzene two
Water glycerin ether is a kind of, and curing agent uses trien, diaminodiphenyl-methane (DDM) compound, and accelerator uses 1-
Amino-ethyl -2-methylimidazole (AMZ), CNT uses aminated carbon nano tube, and carbon fiber is using toray company
T700S-12K.Preparation process is as follows：Matrix resin and fluorine resin are stirred into mixing 30min by proportioning at 70 DEG C；Will be selected
Curing agent and accelerator and functionalized carbon nano-tube are stirred mixing 50min by proportioning at 120 DEG C, are cooled to 60 DEG C
When ultrasonic agitation 30min.By well mixed matrix resin, fluorine resin blending ingredients and curing agent, accelerator, CNT
Blending ingredients are stirred mixing 20min by proportioning at 45 DEG C, and finally deaeration obtains described winding resin matrix under vacuo.Will
Resin adhesive liquid is poured into preprepared mould with resin-cast body sample, and unidirectional carbon fiber is prepared by winding shaping process
Dimension composite material flat plate and carbon fibre composite NOL rings.Sample condition of cure is 90 DEG C/1h+120 DEG C/2h+150 DEG C/2h,
After solidifying and being cooled to room temperature, taking out sample carries out demoulding treatment, and the size for carrying out correlation according to corresponding Standard is beaten
Mill is processed and tested.
Ju Ti Pei Fang design is as shown in table 1 in embodiment, resin-cast body, unidirectional composite material, the stretching of NOL rings and layer
As shown in table 2, Moduli data is as shown in table 3 for the intensity data of the Mechanics Performance Testing cut.
Comparative example 4
Curing agent uses triethyl group toluenediamine, and the addition of curing agent is still total matter of curing agent in embodiment 4
Amount number, i.e. curing agent are the amine substance of single component, and other conditions are consistent with step and embodiment 4.Resin-cast body, list
The intensity data of the Mechanics Performance Testing cut to composite, the stretching of NOL rings and layer is as shown in table 2, in Moduli data such as table 3
It is shown.It is by the table 3 of table 2 as can be seen that addition one pack system curing agent mechanical strength and modulus properties can decline therefore solid with compounding
The resin system combination property of agent is more excellent.
Embodiment 5
By the mass fraction of matrix resin, fluorine resin, curing agent, accelerator and functionalized carbon nano-tube according to 100:
20:40:1:It is prepared by 1 proportioning.Main body epoxy resin uses hexahydrophthalic acid 2-glycidyl fat, diglycidyl ether type ring
The compound of oxygen tree fat DER353 and butyl glycidyl ether, fluorine-containing epoxy resin uses 2,2- bis-phenol bases HFC-236fa two to shrink
Glycerin ether is a kind of, and curing agent uses trien, the compound of IPD IPD, and accelerator uses 2- ethyls -4-
Methylimidazole, CNT uses aminated carbon nano tube, carbon fiber to use the T700S-12K of toray company.Prepared
Journey is as follows：Matrix resin and fluorine resin are stirred into mixing 30min by proportioning at 70 DEG C；By selected curing agent and promotion
Agent and functionalized carbon nano-tube are stirred mixing 50min by proportioning at 120 DEG C, are cooled to ultrasonic agitation 30min at 60 DEG C.
Well mixed matrix resin, fluorine resin blending ingredients and curing agent, accelerator, CNT blending ingredients are existed by proportioning
Mixing 20min is stirred at 45 DEG C, finally deaeration obtains described winding resin matrix under vacuo.Resin adhesive liquid is poured to pre-
First in ready mould with resin-cast body sample, by winding shaping process prepare unidirectional carbon fiber reinforced plasticses flat board and
Carbon fibre composite NOL rings.Sample condition of cure is 90 DEG C/1h+120 DEG C/2h+150 DEG C/2h, solidifies and be cooled to room temperature
Afterwards, taking out sample carries out demoulding treatment, carries out the size grinding process of correlation according to corresponding Standard and tests.
Ju Ti Pei Fang design is as shown in table 1 in embodiment, resin-cast body, unidirectional composite material, the stretching of NOL rings and layer
As shown in table 2, Moduli data is as shown in table 3 for the intensity data of the Mechanics Performance Testing cut.
Comparative example 5
In curing agent and accelerator and functionalized carbon nano-tube blend step, ultrasonic agitation treatment is not carried out, other
Condition is consistent with step and embodiment 5.The Mechanics Performance Testing that resin-cast body, unidirectional composite material, the stretching of NOL rings and layer are cut
Intensity data as shown in table 2, Moduli data is as shown in table 3.From table 2 and table 3, after not carrying out ultrasonic agitation treatment
The test result discreteness of mechanical strength and modulus is larger, and ultrasonic agitation can make functionalized carbon nano-tube steady in resin system
It is fixed dispersed therefore more excellent using the resin system performance of ultrasonic agitation PROCESS FOR TREATMENT.
The mass fraction of each component in the embodiment of table 1
The mechanical strength performance of each group sample in the embodiment of table 2 and comparative example
The mechanical moduli performance of each group sample in the embodiment of table 3 and comparative example
Claims (5)
1. a kind of preparation method of high rigidity carbon fibre composite resin matrix, it is characterised in that：Matched by mass fraction
It is 100:(10-40):(20-50):(1-4):The matrix resin of (0.1-2), fluorine resin, curing agent, accelerator and functionalization
CNT is constituted.
2. the preparation method of a kind of high rigidity carbon fibre composite resin matrix according to claims 1, it is special
Levy and be：Described matrix resin be selected from polyfunctionality diglycidyl ether type epoxy resin in it is several, or polyfunctionality shrink
It is several in glycerine ester type epoxy resin, or polyfunctionality diglycidyl ether type and polyfunctionality glycidyl ester type epoxy resin
In several compound；Fluorine resin be 2,2- bis-phenol base HFC-236fas diglycidyl ether, octafluorobiphenyl diglycidyl ether,
One kind in double (base in hexafluoro antelope) the benzene diglycidyl ethers of 1,3- (double light propyl group of hexafluoro) benzene diglycidyl ethers and 1,4- or
It is several.
3. the preparation method of a kind of high rigidity carbon fibre composite cylinder resin matrix according to claims 1, its
It is characterised by：Curing agent is selected from the compound of aliphatic amine, aliphatic cyclic amine, polyetheramine or fluorine-containing aromatic amine；Accelerator is selected from imidazoles
One or more in analog derivative；Functionalized carbon nano-tube is amido carbon nano tube, the CNT of silanization, epoxidation
One kind in CNT or the silanization CNT jointly modified with Nano particles of silicon dioxide.
4. the preparation method of a kind of high rigidity carbon fibre composite resin matrix according to claims 1, it is special
Levy and be：Matrix resin and fluorine resin are stirred into mixing 20-60min by proportioning at 60-100 DEG C；By selected solidification
Mixing 40-80min is stirred in agent and accelerator and functionalized carbon nano-tube by proportioning at 80-150 DEG C, when being cooled to 60 DEG C
Ultrasonic agitation 30min.
5. the preparation method of a kind of high rigidity carbon fibre composite resin matrix according to claims 1, it is special
Levy and be：By well mixed matrix resin, fluorine resin blending ingredients and curing agent, accelerator, CNT blending ingredients
Mixing 20-40min is stirred at 30-60 DEG C by proportioning, finally deaeration obtains described winding resin matrix under vacuo.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710259181.3A CN106883559B (en) | 2017-04-20 | 2017-04-20 | A kind of preparation method of high rigidity carbon fibre composite resin matrix |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253712A (en) * | 2020-01-22 | 2020-06-09 | 核工业第八研究所 | Matrix resin material for wet winding of carbon fiber composite high-pressure container |
| CN113278339A (en) * | 2021-05-11 | 2021-08-20 | 宁波市镇海兴强磁性材料有限公司 | Anti-cracking rare earth permanent magnet organic composite coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122125A (en) * | 2012-11-16 | 2013-05-29 | 北京化工大学 | Resin mixture containing carbon nano tube for carbon fiber wet process winding and preparation method thereof |
| CN103396656A (en) * | 2013-08-27 | 2013-11-20 | 连云港神鹰碳纤维自行车有限责任公司 | Preparation method of epoxy resin system for nanometer modified carbon fiber prepreg |
| CN105907042A (en) * | 2016-06-17 | 2016-08-31 | 华南理工大学 | Functionalized carbon nano-tube epoxy resin nano-composite and preparation method thereof |
-
2017
- 2017-04-20 CN CN201710259181.3A patent/CN106883559B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122125A (en) * | 2012-11-16 | 2013-05-29 | 北京化工大学 | Resin mixture containing carbon nano tube for carbon fiber wet process winding and preparation method thereof |
| CN103396656A (en) * | 2013-08-27 | 2013-11-20 | 连云港神鹰碳纤维自行车有限责任公司 | Preparation method of epoxy resin system for nanometer modified carbon fiber prepreg |
| CN105907042A (en) * | 2016-06-17 | 2016-08-31 | 华南理工大学 | Functionalized carbon nano-tube epoxy resin nano-composite and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| FAN-LONG JIN ET AL.: ""Effect of fluorine functional groups on surface and mechanical interfacial properties of epoxy resins"", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253712A (en) * | 2020-01-22 | 2020-06-09 | 核工业第八研究所 | Matrix resin material for wet winding of carbon fiber composite high-pressure container |
| CN113278339A (en) * | 2021-05-11 | 2021-08-20 | 宁波市镇海兴强磁性材料有限公司 | Anti-cracking rare earth permanent magnet organic composite coating and preparation method thereof |
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