CN106432691A - Curing agent special for pultrusion, and application thereof - Google Patents
Curing agent special for pultrusion, and application thereof Download PDFInfo
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- CN106432691A CN106432691A CN201610576111.6A CN201610576111A CN106432691A CN 106432691 A CN106432691 A CN 106432691A CN 201610576111 A CN201610576111 A CN 201610576111A CN 106432691 A CN106432691 A CN 106432691A
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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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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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
- C08G59/20—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 epoxy compounds used
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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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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- Epoxy Resins (AREA)
Abstract
The invention provides a curing agent special for pultrusion, and the application thereof, and belongs to the synthesis technical field of curing agents. The curing agent special for pultrusion is obtained through mixing up acid anhydride, a promoting agent, a toughening agent, a coupling agent and a lubricant. The curing agent and the epoxy resin are mixed to obtain an epoxy resin curing system. According to the technical scheme of the invention, a compound accelerant system, based on the coordination of a high-temperature accelerant and a low-temperature accelerant, is adopted. In this way, the gelation time of the mixture of the curing agent and the epoxy resin is reduced. Meanwhile, the viscosity of a mixed adhesive is lowered, so that the impregnation of glass fibers is more thorough. The viscosity is prevented from going up. Through adding the toughening agent, an obtained product is excellent in low-temperature impact strength and crack resistance. Through adding the coupling agent, the interface state of the mixed adhesive and glass fibers is improved and the bonding force of a composite interface is enhanced. The production efficiency and the product quality of the pultrusion industry are comprehensively improved. moreover, the problem in the prior art that products obtained through the speed-up excess production based on conventional curing agent and epoxy resin mixed adhesives cannot meet the requirements on mechanical properties and are too high in brittleness so as to easily crack in most occasions can be solved.
Description
Technical field
The invention belongs to pultrusion curing agent technical field, be specifically related to a kind of based on methyl tetrahydro phthalic anhydride, pass through
Add various auxiliary agent, adjust curing agent performance, prepare the pultrusion solidifying that can improve pultrusion speed and pultrusion material property
Agent and application thereof.
Background technology
Methyl tetrahydro phthalic anhydride and Application comparison in pultrusion industry for the methyl hexahydrophthalic anhydride curing agent are extensive.The pultrusion of China
Industry in development in recent years quickly, due to the little upper detective of investment, presents universal Flowering Phenomenon, but scale is not very big.So
Situation formed and mostly count at present pultrusion producer and be all absorbed in a market, a kind of product, a kind of technique, even only to a use
Family.They to control oneself grasp technology and user maintain strict secrecy, its result is not have enough personnel or time to test green wood
The exploitation of material, let alone the exploitation in market.
To in the investigation of pultrusion industry and practice process, the inventors found that：Major part producer scale is universal
Smaller, without technical professional, curing agent used uses methyl tetrahydro phthalic anhydride, altax P-30 or benzyl diformazan mostly
Amine, is optimized without other auxiliary agents.The category of accelerator is few and addition does not has standard, and a lot of producer is in order to improve yield
Blindly speed-raising, arbitrarily increases the amount of accelerator, although pultrusion mandrel surface have cured, but the mechanical property of product can not meet and wants
Asking, therefore index each factory gap is relatively big, causes inconvenience in design and use for the user, is more easy to make the product of inferior quality be mixed into
Market, produces quality accident, the problem such as has undesirable effect.Curing agent used by current pultrude process is commonly methyl tetrahydrochysene benzene
Acid anhydride, selecting by the requirement to product colour of accelerator, it is desirable to low employing DMP-30, it is desirable to the employing benzyl diformazan of lighter color
Amine, the input amount of normal process is 1.2%-1.5%, blindly adds accelerator for speed-raising and does not includes, and the gel time of epoxy glue is
5-6 min/130℃.Pultrude process condition is temperature 130 DEG C before mould, temperature 180 DEG C after mould, post-curing oven temperature 150 DEG C,
The glass plug of a diameter of 24mm, pultrusion speed is typically at 6-7cm/min.Pultrusion plug carries out dye absorption test, assay
15min minute is without infiltration.Water-diffusion test, the Leakage Current value under 12kV is less than 1.0.Hot beam test, is 280-
350MPa.
Determine that the factor of resin curing rate mainly has the activity of accelerator, concentration and forming temperature.At forming temperature one
In the case of determining, the activity of optional accelerator（The species of accelerator）Meet certain solidification with the concentration adjusting accelerator
Speed, but the concentration of accelerator can not be increased simply, because reduction Average Segment Length is made by too high promoter concentration
Goods become fragile, and affect product properties, and rate of polymerization is directly proportional to the square root of promoter concentration, economically considers also
It is non-remunerative.Therefore, in order to meet certain curing rate, accelerator activity just plays a decisive role.So pressing current technique
Promoting that dosage raises speed to 10cm/min by blindly increasing, the mechanical property of pultrusion plug will be unable to meet requirement, and hot bending resistance tries
Test result and only have 128MPa.Data above is all the workshop actual production situation recognized from producer, is situated between without document so far
Continue.
Use two or more accelerator to be the effective ways improving moulding process, improving production efficiency simultaneously,
It can be effectively improved the curing rate of resin curing system, can reduce again forming temperature simultaneously.Selecting compound promotion system
When should consider that its cooperative effect considers the combination of high/low temperature accelerator again.Selecting method is：First the reaction according to resin
Characteristic is by the selected high temperature accelerator of experiment, such as benzoyl peroxide or TBPB tertiary butyl perbenzoate etc.；Select in unison again
Middle low temperature accelerator, such as benzyl dimethylamine, adjacent hydroxybenzyl dimethylamine etc..Both ratios to consider following several
Point：First be low temperature accelerator addition often substantially shorten epoxy glue can validity period, and with amount increase and aggravate；
Secondly more common at present middle low temperature accelerator price is high.Therefore, the addition of low temperature accelerator must be come by experiment
Determine to reach to improve the purpose of moulding process and product quality, raising production efficiency under same cure cycle.
Content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of pultrusion special curing agent and
Its application, it is a kind of to be specifically designed for the LCM that pultrusion industry is combined preparation, solves in pultrusion industry because accelerating to produce
The pultrusion bar product matter difference, the valency that cause are low, and mechanical performance index each factory gap is bigger etc. is unfavorable for pultrusion industrial development
Problem.
Described a kind of pultrusion special curing agent, it is characterised in that by curing agent base-material, accelerator, toughener and coupling agent
Obtaining by evenly mixing, curing agent base-material, accelerator, toughener and coupling agent charged material weight ratio are 100：2-5：1-3：1-3, institute
Stating curing agent base-material is methyl tetrahydro phthalic anhydride or methyl tetrahydro phthalic anhydride and methyl hexahydrophthalic anhydride, HHPA, the acid of sodium methide Dick
Acid anhydride, hydrogenating methyl sodium Dick acid anhydrides, 4-methyl hexahydrophthalic anhydride, any one or more in methylcyclohexene tetracarboxylic dianhydride are mixed
Compound.
Described a kind of pultrusion special curing agent, it is characterised in that methyl tetrahydro phthalic anhydride includes methyl tetrahydro phthalic anhydride JHY910
With methyl tetrahydro phthalic anhydride JHY906.
Described a kind of pultrusion special curing agent, it is characterised in that curing agent base-material, accelerator, toughener and coupling agent are thrown
Material weight ratio is 100：3：2：1.
Described a kind of pultrusion special curing agent, it is characterised in that accelerator is selected from triethanolamine, adjacent hydroxybenzyl diformazan
Amine, tetraethylammonium bromide, benzyl dimethylamine, triethylamine, adjacent hydroxybenzyl dimethylamine, trien, dicyandiamide, 1,8-bis-
Aza-bicyclo (5,4,0)-7-endecatylene, 2-ethyl-4-methylimidazole, 1-benzyl-2-ethyl imidazol(e), 1-amino-ethyl-2-
The two or more mixture worked in coordination with mutually in methylimidazole, modified imidazole, benzoyl peroxide, TBPB tertiary butyl perbenzoate.
Described a kind of pultrusion special curing agent, it is characterised in that toughener selected from cardanol epoxy compound, poly-the third two
Alcohol diglycidyl ether, bisphenol-A-alkylene oxide addition product diglycidyl ether, linoleic acid dimer diglycidyl ether, poly-
Any one in propane diols, trihydroxylic alcohol, caprolactone polyalcohols, polytetramethylene glycol or terminal carboxyl polyester.
Described a kind of pultrusion special curing agent, it is characterised in that coupling agent is selected from r-chloropropyl trimethoxyl silane, ethene
Base trichlorosilane, VTES, vinyl three (2-methoxy ethoxy) silane, γ-(methacryloxypropyl)
Propyl trimethoxy silicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyl trimethoxy
Silane, γ-mercaptopropyl trimethoxy silane, gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl) γ-aminopropyl front three
Any one in TMOS, γ-ureidopropyltriethoxysilane or anilino-methylene tri Ethoxysilane.
Application in epoxy resin solidifying system for the described a kind of pultrusion special curing agent.
Described application, it is characterised in that curing agent and epoxy resin are mixed to get epoxy glue in proportion, coagulating of epoxy glue
The glue time is 3-4min/130 DEG C, can validity period be more than 8 hours, and pultrusion speed is more than 95mm/min, curing agent and epoxy
The mass ratio that feeds intake of resin is 80-90：100；Described epoxy resin is bisphenol A type epoxy resin, including E-51, E-52D, E-
54th, any one in E-55, E-56D, E-39D, E-39 or two kinds of mixtures.
Described application, it is characterised in that curing agent is 85 with the mass ratio that feeds intake of epoxy resin：100；Described asphalt mixtures modified by epoxy resin
Fat is E-51.
Described application, it is characterised in that during pultrusion speed test, can add lubricant, described lubricant is selected from polyethylene
Any one in wax, OPE, paraffin, montanin wax, silicone oil, methyl-silicone oil, synthesizing polyester wax or lignite wax, lubrication
Agent is 0.5-1.0 with the mass ratio that feeds intake of curing agent base-material：100, preferably 0.7：100.
The preparation of described a kind of pultrusion special curing agent and application process, it is characterised in that this pultrusion special curing agent
It is with necessarily by auxiliary agents such as the acid anhydrides such as methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride and accelerator, toughener, coupling agent, lubricants
Ratio composition, by selecting suitable epoxy resin species and consumption, obtain pultrusion special epoxy resin curing system, with this
Method prepares the gel time that 1. pultrusion material can reduce curing agent and mixture of epoxy resins；2. the viscous of epoxy glue is reduced
Degree, makes glass fiber impregnation more thorough, slows down viscosity and rise, and growth can validity period；3. adding toughener makes product low-temperature impact strong
Degree, crack resistance are excellent；4. increase the interface state that coupling agent improves epoxy glue and glass fiber more, improve composite material interface
Cohesive force；5. the pipe of diameter 24mm, pultrusion speed is promoted to 10-11cm/min from the 6-7cm/min of current technique.
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention is as follows：
1）The present invention, by using above-mentioned technology, the curing agent obtaining, is mixed to get pultrusion special epoxy resin with epoxy resin
Curing system, effectively reduces the gel time of curing agent and mixture of epoxy resins, from the 5-6 min/130 DEG C fall of current technique
Low to 3-4 min/130 DEG C；Reduce the viscosity of epoxy glue, make glass fiber impregnation more thorough, slow down viscosity and rise, can validity period from
5h originally rises to more than 8h；Ensure the performance of pultrusion material while improve its pultrusion speed, pultrusion can be improved comprehensively
Industry production efficiency and product quality, make pultrusion speed be more than 95mm/min, solves with conventional curing agent and asphalt mixtures modified by epoxy resin
Fat epoxy glue carries out speed-raising and exceeds the quata to produce, and causes the product producing necessarily cannot meet mechanical property, past in many use occasions
Toward encountering, fragility is too high, be easy to problems of crack；
2）The present invention makes product low temperature impact strength, crack resistance excellent by adding toughener；
3）The present invention is limited the coupling agent of number by adding, and improves the interface state of epoxy glue and glass fiber, improves composite wood
The cohesive force at material interface.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, all other embodiment that those of ordinary skill in the art are obtained under the premise of not making creative work, all
Belong to the scope of protection of the invention.
The embodiment of the present invention provides preparation and the application process of a kind of pultrusion special curing agent, can improve pultrusion row comprehensively
Industry production efficiency and product quality.It is described in detail individually below.
The preparation of a kind of pultrusion special curing agent that the present invention provides and application process：Be specially by methyl tetrahydro phthalic anhydride,
The auxiliary agents such as the acid anhydrides such as methyl hexahydrophthalic anhydride and accelerator, toughener, coupling agent, lubricant form with certain proportion, by choosing
Select suitable epoxy resin species and consumption, obtain pultrusion special epoxy resin curing system.Pultrusion special curing agent is carried out
Quality index is tested, and glue made after mixing in proportion with epoxy resin after the assay was approved does gel test again, can make
With phase test and module test.Carrying out pultrude process application test after test passes, prepared pultrusion plug does mechanical property again
Test.
Comparative example
Methyl tetrahydro phthalic anhydride JHY910 70 g, methyl tetrahydro phthalic anhydride JHY906 30g, add benzyl dimethylamine 1.5g, and stirring is all
Even.Weigh FD-128 epoxy resin 125g again, after stirring, pour into test tube is tested respectively 90 DEG C, 100 DEG C, 110 DEG C, 120
DEG C, 130 DEG C, gel time 27'32 " the 60th, 17'42 " the 38th, 12'20 " the 19th, 8'30 " the 52nd, the 5'10 " the 87th, 3'50 " 45 at 140 DEG C.
The epoxy glue having configured being put into each hour tested viscosity in the baking oven of 40 degrees Celsius, initial viscosity is 265mPa/s, 40 DEG C,
Within 1 hour, being 370 mPa/s, within 2 hours, being 680 mPa/s, 40 DEG C, 3 hours 1050 mPa/s, 40 DEG C, 4 hours be 1670 mPa/
S, 40 DEG C, 5 hours be 2270 mPa/s, within 6 hours, is 4950 mPa/s, can validity period up to 6 hours.Pultrusion special curing agent
With FD-128 epoxy resin 80：After 100 mix, add 0.7% montanin wax and carry out pultrusion application test, diameter of mandrel 24mm, mould
Temperature 130 DEG C before tool, rear temperature 180 DEG C, post-curing oven temperature 150 DEG C, pultrusion speed is 60mm/min.Pultrusion plug carries out inhaling red
Test, assay 15min minute is without infiltration.Water-diffusion test, the Leakage Current value under 12kV is 0.8.Hot beam test,
For 282MPa.
Embodiment 1
Taking methyl tetrahydro phthalic anhydride JHY910 70g, methyl tetrahydro phthalic anhydride JHY906 25g, HHPA 5g add stirring in beaker
Uniformly, triethanolamine 2g, 1-benzyl-2-ethyl imidazol(e) 2g, polypropylene glycol diglycidyl ether 2g, γ-glycidol oxygen are added
Propyl trimethoxy silicane 1g, stirs respectively, then weighs FD-128 epoxy resin 119g, after stirring, pours test tube into
Middle test 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, gel time 13'37 " the 80th, 7'53 " the 16th, the 5' at 140 DEG C respectively
49"11、3'28"46、2'32"17、2'01"15.The epoxy glue having configured is put in the baking oven of 40 degrees Celsius each hour and survey
Examination viscosity, initial viscosity is 250mPa/s, 40 DEG C, within 1 hour, is 350 mPa/s, within 2 hours, is 620 mPa/s, 40 DEG C, 3 hours
930 mPa/s, 40 DEG C, 4 hours be 1450 mPa/s, 40 DEG C, within 5 hours, is 1970 mPa/s, within 6 hours, is 2520 mPa/s, 7
Hour be 2920 mPa/s, within 8 hours, be 5350 mPa/s, can validity period up to 8 hours.Pultrusion special curing agent and FD-128 ring
Epoxy resins 90：After 100 mix, add 0.7% montanin wax and carry out pultrusion application test, diameter of mandrel 24mm, temperature 130 before mould
DEG C, rear temperature 180 DEG C, post-curing oven temperature 150 DEG C, pultrusion speed is 95mm/min.Pultrusion plug carries out dye absorption test, inspection
Result 15min minute is without infiltration.Water-diffusion test, the Leakage Current value under 12kV is 0.9.Hot beam test, be
280MPa.
Embodiment 2
Taking methyl tetrahydro phthalic anhydride JHY910 70g, methyl tetrahydro phthalic anhydride JHY906 25g, sodium methide Dick acid anhydrides 5g add beaker
In stir, add triethanolamine 1.5g, modified imidazole 2g, adjacent hydroxybenzyl dimethylamine 0.5, polypropylene glycol diglycidyl
Ether 2g, γ-glycidoxypropyl trimethoxy silane 1g, stirs respectively, then weighs FD-128 epoxy resin 119g, stirs
Mix after uniformly, pour into and test tube is tested 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, the gel time 15' at 140 DEG C respectively
54"00、8'55"87、6'03"45、3'53"80、2'46"20、2'02"28.The epoxy glue having configured is put into 40 degrees Celsius
Each hour tested viscosity in baking oven, initial viscosity is 460mPa/s, 40 DEG C, within 1 hour, is 540 mPa/s, 40 DEG C, 2 hours 720
MPa/s, 40 DEG C, 3 hours be 980 mPa/s, and 40 DEG C, 4 hours is 1250, within 5 hours, is 1600 mPa/s, 40 DEG C, within 6 hours, is
2250 mPa/s, 40 DEG C, 7 hours be 2900 mPa/s, 40 DEG C, within 8 hours, is 5100 mPa/s, 40 DEG C, can validity period substantially may be used
To reach 8 hours.Pultrusion special curing agent and FD-128 epoxy resin 90：After 100 mix, add 0.7% montanin wax and draw
Squeeze application test, diameter of mandrel 24mm, temperature 130 DEG C before mould, rear temperature 180 DEG C, post-curing oven temperature 150 DEG C, pultrusion speed
For 100mm/min.Pultrusion plug carries out dye absorption test, and assay 15min minute is without infiltration.Water-diffusion test, under 12kV
Leakage Current value is 0.9.Hot beam test, is 285MPa.
Embodiment 3
Taking methyl tetrahydro phthalic anhydride JHY910 70g, methyl tetrahydro phthalic anhydride JHY906 25g, methyl hexahydrophthalic anhydride 5g add in beaker
Stir, add triethanolamine 1.0g, modified imidazole 1.5g, adjacent hydroxybenzyl dimethylamine 0.5, polypropylene glycol diglycidyl
Ether 2g, γ-glycidoxypropyl trimethoxy silane 1g, stirs respectively, then weighs FD-128 epoxy resin 119g, stirs
Mix after uniformly, pour into and test tube is tested 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, the gel time 19' at 140 DEG C respectively
37"63、9'55"99、6'18"35、3'58"90、3'03"87、2'08"23.The epoxy glue having configured is put into 40 degrees Celsius
Each hour tested viscosity in baking oven, initial viscosity is 310mPa/s, 40 DEG C, within 1 hour, is 480 mPa/s, 40 DEG C, 2 hours 670
MPa/s, 40 DEG C, 3 hours be 890 mPa/s, and 40 DEG C, 4 hours is 1100, within 5 hours, is 1500 mPa/s, 40 DEG C, within 6 hours, is
2150 mPa/s, 40 DEG C, 7 hours be 2750 mPa/s, 40 DEG C, within 8 hours, is 4700 mPa/s, 40 DEG C, can validity period can reach
By 8 hours.Pultrusion special curing agent and FD-128 epoxy resin 90：After 100 mix, add 0.7% montanin wax carry out pultrusion should
By test, diameter of mandrel 24mm, temperature 130 DEG C before mould, rear temperature 180 DEG C, post-curing oven temperature 150 DEG C, pultrusion speed is
110mm/min.Pultrusion plug carries out dye absorption test, and assay 15min minute is without infiltration.Water-diffusion test, letting out under 12kV
Dew current value is 0.9.Hot beam test, is 305MPa.
Embodiment 4
Taking methyl tetrahydro phthalic anhydride JHY910 70g, methyl tetrahydro phthalic anhydride JHY906 25g, methyl hexahydrophthalic anhydride 5g add in beaker
Stir, add triethanolamine 1.0g, modified imidazole 1.5g, adjacent hydroxybenzyl dimethylamine 0.5, polypropylene glycol diglycidyl
Ether 2g, γ-glycidoxypropyl trimethoxy silane 1g, stirs respectively, then weighs FD-128 epoxy resin 125g, stirs
Mix after uniformly, pour into and test tube is tested 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, the gel time 15' at 140 DEG C respectively
28"79、9'30"77、5'54"61、4'13"20、3'30"98、2'49"69.The epoxy glue having configured is put into 40 degrees Celsius
Each hour tested viscosity in baking oven, initial viscosity is 320mPa/s, 40 DEG C, within 1 hour, is 510 mPa/s, 40 DEG C, 2 hours 690
MPa/s, 40 DEG C, 3 hours be 910 mPa/s, and 40 DEG C, 4 hours is 1150, and 5 hours is 1450mPa/s, 40 DEG C, within 6 hours, is
1780 mPa/s, 40 DEG C, 7 hours be 2150 mPa/s, 40 DEG C, within 8 hours, is 2500 mPa/s, and 40 DEG C, 9 hours is 5150
MPa/s, can validity period can reach 9 hours substantially by 40 DEG C.Pultrusion special curing agent and 128 epoxy resin 85：100 mixing are all
After even, add 0.7% montanin wax and carry out pultrusion application test, diameter of mandrel 24mm, temperature 130 DEG C before mould, rear temperature 180 DEG C, solidify afterwards
Oven temperature 150 DEG C, pultrusion speed is 110mm/min.Pultrusion plug carries out dye absorption test, and assay 15min minute is without oozing
Thoroughly.Water-diffusion test, the Leakage Current value under 12kV is 0.8.Hot beam test, is 298MPa.
Embodiment 5
Taking methyl tetrahydro phthalic anhydride JHY910 70g, methyl tetrahydro phthalic anhydride JHY906 25g, methyl hexahydrophthalic anhydride 5g add in beaker
Stir, add triethanolamine 1.0g, modified imidazole 1.5g, tetraethylammonium bromide 0.5, polypropylene glycol diglycidyl ether
2g, γ-glycidoxypropyl trimethoxy silane 1g, stirs respectively, then weighs FD-128 epoxy resin 125g, stirring
After Jun Yun, pour into and test tube is tested 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, gel time 16'18 at 140 DEG C respectively "
49、9'34"57、5'48"85、4'15"25、3'11"88、2'24"65.The epoxy glue having configured is put into the baking oven of 40 degrees Celsius
In each hour tested viscosity, initial viscosity is 260mPa/s, 40 DEG C, within 1 hour, is 450 mPa/s, 40 DEG C, 2 hours 640
MPa/s, 40 DEG C, 3 hours be 880 mPa/s, and 40 DEG C, 4 hours is 1070, and 5 hours is 1400mPa/s, 40 DEG C, within 6 hours, is
1680 mPa/s, 40 DEG C, 7 hours be 2250 mPa/s, 40 DEG C, within 8 hours, is 2750 mPa/s, and 40 DEG C, 9 hours is 5300
MPa/s, can validity period can reach 9 hours substantially by 40 DEG C.Pultrusion special curing agent and 128 epoxy resin 85：100 mixing are all
After even, add 0.7% montanin wax and carry out pultrusion application test, diameter of mandrel 24mm, temperature 140 DEG C before mould, rear temperature 180 DEG C, solidify afterwards
Oven temperature 150 DEG C, pultrusion speed is 110mm/min.Pultrusion plug carries out dye absorption test, and assay 15min minute is without oozing
Thoroughly.Water-diffusion test, the Leakage Current value under 12kV is 0.8.Hot beam test, is 310MPa.
The extraordinary curing agent complex configuration of the pulling being provided the embodiment of the present invention above, is described in detail, herein
In apply principle and embodiment to the present invention for the specific case and be set forth, the explanation of above example is only intended to side
Assistant solves method and the core concept thereof of the present invention；Simultaneously for one of ordinary skill in the art, according to the think of of the present invention
Thinking, all will change in specific embodiments and applications, in sum, it is right that this specification content should not be construed as
The restriction of the present invention.
Claims (10)
1. a pultrusion special curing agent, it is characterised in that blended all by curing agent base-material, accelerator, toughener and coupling agent
Even obtaining, curing agent base-material, accelerator, toughener and coupling agent charged material weight ratio are 100：2-5：1-3：1-3, described curing agent
Base-material is methyl tetrahydro phthalic anhydride or methyl tetrahydro phthalic anhydride and methyl hexahydrophthalic anhydride, HHPA, sodium methide Dick acid anhydrides, hydrogenation
Sodium methide Dick acid anhydrides, 4-methyl hexahydrophthalic anhydride, any one or more mixture in methylcyclohexene tetracarboxylic dianhydride.
2. a kind of pultrusion special curing agent according to claim 1, it is characterised in that methyl tetrahydro phthalic anhydride includes methyl four
Hydrogen phthalic anhydride JHY910 and methyl tetrahydro phthalic anhydride JHY906 Jiaxing Zhengda Chemical Co., Ltd. produce.
3. a kind of pultrusion special curing agent according to claim 1 and 2, it is characterised in that curing agent base-material, accelerator, increasing
Tough dose and coupling agent charged material weight ratio are 100：3：2：1.
4. a kind of pultrusion special curing agent according to claim 1 and 2, it is characterised in that accelerator is selected from triethanolamine,
Adjacent hydroxybenzyl dimethylamine, tetraethylammonium bromide, benzyl dimethylamine, triethylamine, adjacent hydroxybenzyl dimethylamine, triethylene four
Amine, dicyandiamide, 1,8-diaza-bicyclic (5,4,0)-7-endecatylene, 2-ethyl-4-methylimidazole, 1-benzyl-2-ethyl miaow
Two kinds working in coordination with mutually in azoles, 1-amino-ethyl-2-methylimidazole, modified imidazole, benzoyl peroxide, TBPB tertiary butyl perbenzoate
Or multiple mixture.
5. a kind of pultrusion special curing agent according to claim 1 and 2, it is characterised in that toughener is selected from cardanol epoxy
Compound, polypropylene glycol diglycidyl ether, bisphenol-A-alkylene oxide addition product diglycidyl ether, linoleic acid dimer two
Any one in glycidol ether, polypropylene glycol, trihydroxylic alcohol, caprolactone polyalcohols, polytetramethylene glycol or terminal carboxyl polyester.
6. a kind of pultrusion special curing agent according to claim 1 and 2, it is characterised in that coupling agent is selected from chloropropyl front three
TMOS, vinyl trichlorosilane, VTES, vinyl three (2-methoxy ethoxy) silane, γ-
(methacryloxypropyl) propyl trimethoxy silicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidol
Oxygen propyl trimethoxy silicane, γ-mercaptopropyl trimethoxy silane, gamma-aminopropyl-triethoxy-silane, N-β (ammonia second
Base) γ-aminopropyltrimethoxysilane, in γ-ureidopropyltriethoxysilane or anilino-methylene tri Ethoxysilane
Any one.
7. an a kind of pultrusion special curing agent according to claim 1 application in epoxy resin solidifying system.
8. application according to claim 7, it is characterised in that curing agent and epoxy resin are mixed to get epoxy glue in proportion,
The gel time of epoxy glue is 3-4min/130 DEG C, can validity period be more than 8 hours, and pultrusion speed is more than 95mm/min, Gu
Agent is 80-90 with the mass ratio that feeds intake of epoxy resin：100；Described epoxy resin is bisphenol A type epoxy resin, including E-51,
Any one or two kinds of mixtures in E-52D, E-54, E-55, E-56D, E-39D, E-39.
9. application according to claim 7, it is characterised in that curing agent is 85 with the mass ratio that feeds intake of epoxy resin：100；
Described epoxy resin is E-51.
10. application according to claim 8, it is characterised in that during pultrusion speed test, needs to add lubricant, described profit
Lubrication prescription is in Tissuemat E, OPE, paraffin, montanin wax, silicone oil, methyl-silicone oil, synthesizing polyester wax or lignite wax
Any one, the mass ratio that feeds intake of lubricant and curing agent base-material is 0.5-1.0：100, preferably 0.7：100.
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| CN201610576111.6A CN106432691A (en) | 2016-07-21 | 2016-07-21 | Curing agent special for pultrusion, and application thereof |
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| CN114907548A (en) * | 2022-05-16 | 2022-08-16 | 南京海拓复合材料有限责任公司 | Epoxy resin batch for pultrusion of composite material and preparation method thereof |
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| CN103665758A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Modified epoxy resin system for carbon fiber boards for pultrusion structure reinforcement |
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Application publication date: 20170222 |