CN106751486A

CN106751486A - A kind of preparation method of crystal waste slag/BAHPFP type epoxy matrix resin composites

Info

Publication number: CN106751486A
Application number: CN201611101490.XA
Authority: CN
Inventors: 虞鑫海; 周志伟
Original assignee: Donghua University; Shanghai Ruitu Electronic Material Co Ltd
Current assignee: Donghua University; Shanghai Ruitu Electronic Material Co Ltd
Priority date: 2016-12-05
Filing date: 2016-12-05
Publication date: 2017-05-31
Anticipated expiration: 2036-12-05
Also published as: CN106751486B

Abstract

The present invention relates to a kind of preparation method of crystal waste slag/BAHPFP type epoxy matrix resin composites, including：By crystal waste slag drying, powdered, coupling agent surface treatment is carried out；Then crystal waste slag powder is well mixed with BAHPFP types epoxy matrix resin, chopped fiber, obtains BAHPFP type epoxy resin-base composite material systems, be packed into mould, heat-pressure curing shaping is obtained final product.The composite that the present invention is prepared not only can efficient process crystal waste slag, environmental pollution is eliminated, and can be turned waste into wealth, realize recycling, very important realistic meaning is respectively provided with to comprehensive environmental improvement etc., good Social benefit and economic benefit can be obtained.

Description

A kind of preparation method of crystal waste slag/BAHPFP type epoxy matrix resin composites

Technical field

The invention belongs to inorganic wastes efficient process and its recycling field, more particularly to a kind of crystal waste slag/ The preparation method of BAHPFP type epoxy matrix resin composites.

Background technology

China is to grasp one of country of glass manufacturing techniques earliest, to the stained glass system manufactured by period in Spring and Autumn and Warring States's epoch Product start for decorating.Transparent vial, cup are made to very exquisite during the Tang and Song Dynasty.Substantial amounts of imitative cameo glass to the Ming Dynasty just It is sold abroad.End of the Ming Dynasty poet Wu Mei, village had poem to praise cloud：" imperial flower peace phoenix kiss is inserted partially, it is deep red to help wide cold ladder by force." illustrate glass Product be produced on the Ming Dynasty it is high over one's competence and superb technique.But the glassware of first, bright, clear three generations aims at imperial palace and is exclusively enjoyed, Common people disable without exception.With the raising of modern life level, people need pure and fresh transparent, bedecked with jewels lucky ornaments, It is expensive and the mineral crystal of water white transparency is rare in the world with diamond, so several crystal glass for looking genuine just substitutings, Enter the family of thousands upon thousands common peoples.Single-eyed Pujiang people exactly utilizes this advantage, captures this opportunity to develop, Crystal glass industry is run business big and strong.

Pujiang crystal glass industry just this beading starting from before 20 years, to Quartz lamp decoration, developing deeply to crystal glass work Skill product.Pujiang is referred to as " township of Chinese art ", and art creates Pujiang, and Pujiang advances art.Pujiang is because there is crystal glass Glass handicraft and enjoy a widespread reputation, crystal glass cuts a conspicuous figure because the consummate craftsmanship of Pujiang people is obtained.In 1993, Seiko The Pujiang crystal glass lamp decoration decorative hanging piece of fine grinding is selected at one stroke, the Great Hall of the People is decorateeed more glorious and magnificent, Pujiang people's depth Sense pride.Hong Kong, Macao's return to the motherland are Hundred Years of China major issues, and the world attractes attention for it.Pujiang crystal glass handicraft is holy with it Clean graceful moral character, the skill of superb craftsmanship, are chosen as the gift of Hong Kong, Macao's return to the motherland and China Millennium Altar completion grand ceremony.

By 2011, the crystal of Pujiang production accounted for the 80% of national total amount, more than 22000 Duo Jia crystals factories and workshop Take root herein, practitioner surpasses 20,000,000,000 yuan up to more than 20 ten thousand people, the output value.Crystal also allows this while being created the wealth to Pujiang The heavy environmental pressure of individual small county town back.In extensive crystal process, the waste water quilt containing a large amount of glass powders Enter in river, add locals's custom and solid waste rubbish, house refuse are poured into korneforos, " the milk river " of off-white color, rubbish river into The grey label of Pujiang.Be can see from the examination of water quality of river section, departure of the Pu Yangjiang in Pujiang County from 2006 Section water quality is bad five class, is one of worst river of Zhejiang Province's river water quality.2011, here as Zhejiang only one The county of " double region limit batch ", the environmental sanitation of Pujiang evaluates satisfaction, and also to rank the whole province for many years last, is referred to as " the worst county of Zhejiang hygienic conditions ".How ecological environment decompression is given2006,2011, Pujiang county government all once put into effect policy, Intend to be managed the discharge of crystal industry with limitation, but all stagnate because of various reasons.

It is reported that, since 2015, Pujiang County is organized the behavior of strike environmental illegality and is jointly acted more than 1000 times, is banned Crystal processes 18450, family, and 726 crystal self-employed workers realize " individual turn of enterprise ".Fall sharply to more than 3000 from original family more than 22000 Family, this " crystal all " in the past just falls to force industrial transformation to upgrade by the chance of " five water are controlled altogether ".However, crystal waste slag Problem is not yet solved so far, and 4 crystal Industrial Zones of current Pujiang produce 300 tons of -500 tons of crystal waste slags, number daily Amount is huge, and huge pressure is caused to environment, while the fast development of crystal industry is also seriously constrained, to crystal industry Sustainable development is provided with great obstacle.

At present, the treatment to crystal waste slag is main by following several ways：

Cement additire：In cement manufacture production, a small amount of crystal waste slag is added, high-temperature fusion calcining is crushed, packaging, Dispatch from the factory, obtain cement.

Be present open defect in the method, be mainly manifested in：Addition is very little, it is difficult to effectively process daily 300 tons -500 tons Crystal waste slag amount；Cause cement quality to decline significantly after with the addition of a small amount of crystal waste slag, there is the serious of cement applications Potential safety hazard, it is impossible to actual large-scale popularization and application.

Glass block additive：Glass block obtained in the crystal waste slag of≤25% weight is added in fragment of brick making, it is impossible to Applied in building field, particularly load bearing construction, can be only applied to enclosure wall.But, in natural environment, expose to the weather and drench with rain, The glass block is easy to weathering and comes off, and intensity drastically declines, it is difficult to actual popularization and application, greatly limit crystal waste slag in brickmaking The application in field.Additionally, there is also, energy consumption is big, addition is few, surface is too smooth and does not apply lime etc. defect.

Other：Such as glass microballoon, foaming building thermal insulation material, but have that energy consumption is big, be also easy to produce secondary pollution, produce Product added value is low and is difficult to cost equivalent risk of recouping capital outlay.

Therefore, crystal waste slag addition is big, energy consumption is low, do not produce secondary pollution, and the height needed for society, market can be obtained Cost performance material or new product, are the development trends of crystal waste slag treatment technology from now on.Crystal waste slag can be used and organic tree Fat, is combined including epoxy resin, unsaturated-resin, polyurethane resin, phenolic resin, vinylite etc., prepares composite, Can apply to the fields such as building, traffic, gardening.At present, the application technology as the second resource turned waste into wealth also has patent or document report Road, such as granolith plate material.

Granite plates are a kind of construction materials of high-quality, are largely used to high-grade luxurious hotel, airport lounge, high ferro Wait building and platform, family kitchen and bath, office business building etc..With the improvement of people ' s living standards, to granite plates Demand is growing day by day, so as to further promote the exploitation in granite mine, processing, scale amounts are more and more huger.And opened at it Adopt, process necessarily leads to substantial amounts of stone slurry, granite powder scrap etc., and serious ring is caused to river, mountains and rivers, stockyard etc. Border is polluted, while the secondary disaster such as also easily cave in, larger potential threat is caused to the people's lives and property.

Therefore, people start actively to study the technology that the waste residue in granite stone pit is reused.Chinese invention is special Sharp CN1037042A discloses a kind of inorganic artificial granite production technology, is primarily characterized in that：Alumina cement, stone are used first The mixing of sand, inorganic pigment powder, glycerine and water is tuned into thin pulp shape mill base, pours into shaping frame, after after initial set, uses high silicon water Mud, quartz sand, quartz, inorganic pigment powder, glycerine and water, mixing are tuned into thin pulp shape coat of colo(u)r, brokenly on color paste layer Portion, then after being added water with alumina cement, river sand, rubble and stirring, be cast in shaping frame, as reinforcing after machinery shaking Layer, is finally putting into pond immersion maintenance and is molded for 72 hours, then by ageing-resistant pickling processes, product is turned into by oiling.

Chinese invention patent CN1035812A disclose a kind of high intensity, it is indeformable, be not cracked, best bright finish, performance it is steady The fixed, manufacture method of high-quality full-inorganic artificial marble, is primarily characterized in that：With cement as raw material, add a small amount of inorganic Auxiliary agent constitutes body, with it is pre-fabricated have special component add body into flower agent in vibrate into flower, maintenance is crystallized into water Product.

Chinese invention patent CN1088146A discloses a kind of high alumina cement artificial granite, marble and its production work Skill, is primarily characterized in that：Using diffusant, alum, the concentrated sulfuric acid, magnesium sulfate, rosin, ferrous sulfate, oxalic acid, boric acid and Triethanolamine and water, are configured to fabric water and bed material water, then go to mix cement and silica flour with fabric water and bed material water, make respectively Into surface layer and bottom, spread out and put on surface layer top after thering is one to be stirred with cement, silica flour and fabric water between surface layer and bottom Basic unit, its maintenance is carried out using wet saw end.

It is well known that epoxy resin has many excellent performances：(1) good adhesive property：Adhesive strength is high, bonding Wide, it is with many metals (such as iron, steel, copper, aluminium, metal alloy) or nonmetallic materials (such as glass, ceramics, timber, plastics Deng) adhesive strength it is very high, the even more than intensity by viscous material in itself having, therefore can be used for many stress members In, it is one of main component of structural adhesive；(2) good processing characteristics：The flexibility of Formulaion of epoxy resin, processing work The diversity of skill and product properties is the most prominent in macromolecular material；(3) good stability：The solidification of epoxy resin Mainly by the ring opening polyaddition of epoxy radicals, therefore low-molecular material is not produced in solidification process, its cure shrinkage is heat One of minimum kind, generally 1%-2% in thermosetting resin, if the appropriate filler of selection can make shrinkage factor be down to 0.2% Left and right；Epoxy main chains after solidification are ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore with excellent resistance to acids and bases.

Therefore, epoxy resin is widely used in the every field of national economy：Either high-technology field is still Field of general technology, either can see its trace in defence and military or civilian industry, or even daily life.

Relevant high-temperature resistant epoxy oxygen system has been reported：Chinese patent CN101148656A discloses a kind of high temperature resistant without molten The preparation method of agent epoxy adhesive, is primarily characterized in that：TGDDM epoxy resin, toughener, hydrogenated bisphenol A, curing agent, Accelerator is well mixed, and heat-resistant solvent-free epoxy adhesive has been obtained.But its resistance to elevated temperatures still has larger limitation, Fail to meet the practical application under many hot environments.

Chinese patent CN101397486A discloses a kind of preparation method of bi-component solvent-free epoxy resin adhesive, its It is characterized mainly in that：It includes component A and B component, and wherein component A contains novolac epoxy resin, alicyclic type epoxy resin and end XNBR；B component is double (2,4- diamino phenoxies) the benzene aromatic polyvalent amine hardeners of 1,4-.Alicyclic ring type asphalt mixtures modified by epoxy resin The addition of fat and nbr carboxyl terminal is respectively the 20-35% and 12% (mass percent) of novolac epoxy resin.1,4- The addition of double (2,4- diamino phenoxies) benzene aromatic polyvalent amine hardeners is the 15-20% (quality of novolac epoxy resin Percentage), gained adhesive system good manufacturability.But its heat resistance is preferable not enough.

Chinese invention patent CN101962436A discloses a kind of heat resist modification multi-functional epoxy used for advanced composite material Matrix resin and preparation method thereof, is primarily characterized in that：Using double (the 2,4- dimaleimides phenoxyl) benzene of 1,4- Four maleimide resins obtain the novel fire resistant of high tenacity with polyfunctional epoxy resin, nbr carboxyl terminal CTBN reactions Resin, adds organic solvent, and stirring and dissolving is uniform, obtains the viscous liquid of homogeneous phase transparent, i.e. component A；Curing agent with it is organic Solvent mixes, and stirring and dissolving is uniform, obtains final product B component；A, B component are mixed, is stirred, obtained final product used for advanced composite material Heat resist modification multi-functional epoxy's substrate resin solution.

Yu Xin seas et al.【Development [J] bondings of high-temperature resistant single-component epoxy adhesive, 2008,29 (12)：16-19】It is public A kind of preparation method of high-temperature resistant single-component epoxy adhesive is opened, has been primarily characterized in that：It is end-blocking with maleic anhydride (MA) Agent, with double (3- amino-4-hydroxylphenyls) HFC-236fas (BAHPFP) of 2,2-, double [4- (4- amino-benzene oxygens) phenyl] third of 2,2- Double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides (BPADA) of alkane (BAPOPP), 2,2- are obtained for main Material synthesis Phenolic hydroxy group polyetherimide resin (HPEI)；It it is resistant, toughened dose with the synthesized HPEI for obtaining, with N, N, N', N'- tetra- Glycidyl -4,4'- MDAs (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent Deng preparation has obtained the high-temperature resistant single-component epoxy adhesive of excellent combination property.

The content of the invention

The technical problems to be solved by the invention are to provide a kind of crystal waste slag/BAHPFP type epoxy matrix resin composite woods The preparation method of material, the composite that the method is prepared not only can efficient process crystal waste slag, eliminate environmental pollution, and Can turn waste into wealth, realize recycling, very important realistic meaning is respectively provided with to comprehensive environmental improvement etc., can obtain good Social benefit and economic benefit.

A kind of preparation method of crystal waste slag of the invention/BAHPFP type epoxy matrix resin composites, including：

By crystal waste slag drying, powdered, coupling agent surface treatment is carried out；Then by crystal waste slag powder and BAHPFP types Epoxy matrix resin, chopped fiber are well mixed, and obtain BAHPFP type epoxy resin-base composite material systems, are packed into mould, plus Hot cure under pressure shaping, obtains final product crystal waste slag/BAHPFP type epoxy matrix resin composites；Wherein, crystal waste slag powder, BAHPFP types epoxy matrix resin is 30-60 with the mass ratio of chopped fiber:32-45:5-25.

The crystal waste slag stoving process is：120 DEG C retain -12 hours 10 hours, are not more than crystal waste slag water content 0.1%.

The coupling agent surface treatment technique is：It is 1 by mass ratio:After the coupling agent and water of 32-99 are uniformly mixed, The crystal waste slag powder of drying is added, is stirred -1 hour 0.5 hour at room temperature, filtering takes solids, dry in 100 DEG C -120 DEG C Dry -3 hours 1 hour, obtain by the crystal waste slag powder of coupling agent surface treatment；Wherein, crystal waste slag powder and coupling agent The mass ratio of the aqueous solution is 1:10-20.

The coupling agent is selected from 3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes, γ-(2,3- epoxies Third oxygen) propyl trimethoxy silicane, γ-aminopropyltriethoxy diethoxy silane, N- (β-aminoethyl)-γ-aminopropyltriethoxy two Methoxy silane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-methacryloxypropyl Triethoxysilane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl front three One or more in TMOS.

The BAHPFP types epoxy matrix resin be by mass ratio be 100:1-5:20-200:5-10:1-5:50-200's Epoxy resin, N, N, N ', double (3- amino-4-hydroxylphenyls) HFC-236fas of the glycidyl -2,2- of N ', O, O- six, activity are dilute Release agent, endurable active toughener, alpha-cyano-β-ethoxy ethyl acrylate and curing agent composition.

The preparation method of the BAHPFP types epoxy matrix resin comprises the following steps：By epoxy resin, N, N, N ', N ', Glycidyl -2 of O, O- six, double (3- amino-4-hydroxylphenyls) HFC-236fas of 2-, endurable active toughener are put into reactor, in 80 DEG C of -100 DEG C of stirring reactions add reactive diluent, alpha-cyano-β-ethoxy ethyl acrylate after -1 hour 0.5 hour, in After 50 DEG C -70 DEG C are uniformly mixed, room temperature is cooled to, adds curing agent, be uniformly mixed.

The epoxy resin is selected from E-51 epoxy resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 asphalt mixtures modified by epoxy resin Fat, CE793 epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, Dipentenedioxide, glycidol One kind in amine type epoxy resin, diglycidyl ether type epoxy resin, phenol aldehyde type epoxy resin, glycidyl ester type epoxy resin Or it is several.

The glycidyl amine type epoxy resin is selected from N, N, N ', N '-four glycidyl group -4,4 '-diaminourea hexichol first Alkane epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-dimethyl -4,4 '-MDA epoxy resin, N, N, N ', the glycidyl -4,4 of N ', O- five '-diaminourea -4 "-hydroxyl triphenylmenthane, N, N, N ', N '-four glycidyl group 3, 3 '-diethyl -4,4 '-MDA epoxy resin, N, N, N ', N '-four glycidyl group 3,3 '-two chloro- 4,4 '-two Diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-DADPS epoxy resin, N, N, N ', N '-four glycidyl group -3,4 '-diaminourea Diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-DADPS epoxy resin, N, N, N ', N '-four Glycidyl -4,4 '-benzidine epoxy resin, N, N, N ', N '-four glycidyl group p-phenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group m-phenylene diamine (MPD) epoxy resin, N, N, N ', double (the 4- aminobenzene oxygen of N '-four glycidyl group -1,4- Base) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,4- double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,3- double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,3- is double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N ', the double (2- trifluoromethyl -4- aminobenzene oxygen of N '-four glycidyl group -1,4- Base) benzene epoxy resin, N, N, N ', double (2- trifluoromethyl-4-aminophenoxyls) the phenyl ring oxygen trees of N '-four glycidyl group -1,3- Fat, N, N, N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', N ' - Four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four shrinks sweet Oil base -2,2- double [4- (3- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- is double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- is double [4- (3- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N ', the double [4- (2- tri- of N '-four glycidyl group -2,2- Methyl fluoride -4- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- ammonia Phenoxyl) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl -4- aminobenzene oxygen Base) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group - 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 ' - Double (4- amino-benzene oxygens) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyls -4- Amino-benzene oxygen) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) hexichol Ketone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone Epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) biphenyl epoxy resin, N, N, N ', N ' - Four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl epoxy resins, N, N, N ', N ', O, O '-six contracting Water glyceryl -2,2- double (3- amino-4-hydroxylphenyls) HFC-236fa epoxy resin, N, N, O-triglycidyl group p-aminophenyl Phenol epoxy resin, N, one or more in N, O-triglycidyl meta-aminophenol epoxy resin.

The diglycidyl ether type epoxy resin is selected from 1,3- diglycidyls resorcinol, 1,4- diglycidyls Double (4- glycidyl phenyls) HFC-236fas of hydroquinones, 4,4 '-diglycidyl bisphenol S, 2,2-, 2,2- are double, and (4- contracts Water glycerine butylcyclohexyl) propane, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol-A 2-glycidyl One or more in ether, fatty alcohol polyglycidyl ether.

The phenol aldehyde type epoxy resin is selected from P-F phenolic resin type epoxy resin, o-cresol-formaldehyde novolac tree Epoxy-type epoxy resin, resorcinol-formaldehyde phenolic resin type epoxy resin, m-cresol-formaldehyde phenolic resin type epoxy resin, Catechol-formaldehyde phenolic resin type epoxy resin, bisphenol A-formaldehyde phenolic resin type epoxy resin, bisphenol S-formaldehyde novolac tree Epoxy-type epoxy resin, bisphenol AF-formaldehyde phenolic resin type epoxy resin, '-biphenyl diphenol-formaldehyde phenolic resin type epoxy resin, neighbour One or more in phenylphenol-formaldehyde phenolic resin type epoxy resin, naphthols-formaldehyde phenolic resin type epoxy resin.

The glycidyl ester type epoxy resin is selected from terephthalic acid diglycidyl ester epoxy resin, M-phthalic acid 2-glycidyl ester epoxy resin, o-phthalic acid diglycidyl ester epoxy resin, interior methine tetrahydrophthalic acid two Ethylene oxidic ester epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters epoxy resin, the adjacent octanoic acid two of benzene two One or more in polyglycidyl epoxy resin.

The reactive diluent is selected from 3,4- epoxycyclohexyethylSiOis acid -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3,4- epoxy radicals -6- Methyl cyclohexane acid -3 ', 4 '-epoxy radicals -6 '-methyl cyclohexane methyl esters, ethylene glycol diglycidylether, propane diols 2-glycidyl Ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, hexylene glycol two shrink One or more in glycerin ether.

The endurable active toughener is selected from nbr carboxyl terminal, amino terminated butadiene acrylonitrile rubber, hydroxy'terminated butadiene nitrile rubber, end ring oxygen One or more in base nitrile rubber, end-vinyl nitrile rubber, liquid polysulfide rubber, sulfydryl polysulfide rubber.

The curing agent be selected from m-xylene diamine, 2-ethyl-4-methylimidazole, imidazoles, methylimidazole, DMP-30, DBU, Adjacent hydrogenated methyl m-phenylene diamine (MPD), 1,4- cyclohexyl diamines, 4,4 '-diamino-dicyclohexyl methane, '-two of 3,3 '-dimethyl -4,4 Amino bicyclic hexyl methane, THPA, methyl tetrahydro phthalic anhydride, HHPA, dodecyl succinic anhydride, tung oil acid anhydride, with One or more in the liquid acid anhydrides of turpentine oil and maleic acid anhydride reactant.

It is sub- that the chopped fiber is selected from staple glass fibre, Staple carbon fibers, short basalt fiber, aramid fiber short fibre, polyamides Amine chopped fiber, polyester staple fiber, polyamide staple fibre, acrylic staple fibre, short fiber of cellulose, polyformaldehyde chopped fiber, cotton fiber, sheep One or more in wool fibre, rabbit fur fibre, polyvinyl chloride fibre chopped fiber, polyvinyl alcohol chopped fiber.

The chopped fiber is the chopped fiber being surface-treated by silane coupler of length 1mm-13mm.

The technological parameter of heat-pressure curing shaping is：Temperature be room temperature to 180 DEG C, pressure is 1MPa-10MPa, Press time is -5 hours 0.5 hour.

The composite is used for flat board, flowerpot, cable bearer, tank, guardrail, ammeter tank shell, dustbin, mail box Body, billboard, motorway guide planks, inspection well cover, cable duct groove lid, flower bed fence or seat.

Beneficial effect

(1) process is simple of the invention, low cost, easy to operate, raw material sources convenience, can complete in common apparatus Preparation process, is advantageously implemented industrialized production；

(2) present invention is solvent-free, and environment-friendly, equipment investment is few, and crystal waste slag loading is big, and energy consumption is low, its composite wood The excellent combination property of material products, it is widely used；

(3) present invention not only can efficient process crystal waste slag, eliminate environmental pollution, and can turn waste into wealth, realize resource Change and utilize, very important realistic meaning is respectively provided with to comprehensive environmental improvement etc., good social benefit and economic effect can be obtained Benefit.

Specific embodiment

With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.

Embodiment 1

By 100 grams of E-51 epoxy resin, 1 gram of N, N, N ', the double (3- amino -4- hydroxyls of N ', O, the O glycidyl of '-six -2,2- Base phenyl) HFC-236fa and 5 grams of nbr carboxyl terminals are put into reactor, in after 80 DEG C of stirring reactions 1 hour, add 20 grams 3,4- epoxycyclohexyethylSiOis acid -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 1 gram of alpha-cyano-β-ethoxy ethyl acrylate, in 70 DEG C of stirrings After well mixed, room temperature is cooled to, adds 48 grams of m-xylene diamines and 2 grams of 2-ethyl-4-methylimidazoles, be uniformly mixed, 177 grams of BAHPFP type epoxy matrix resins are obtained, BAHPFP-1 is denoted as.Fly CAP2000+ viscosity and measure its 50 DEG C using rich Le Viscosity is 944mPa.s；The gel time for measuring 120 DEG C using GT-H gelation time testers is 952s.

Embodiment 2

By 60 grams of E-44 epoxy resin, 40 grams of N, N, N ', N '-four glycidyl group -4,4 '-MDA epoxy Resin, 2 grams of N, N, N ', double (3- amino-4-hydroxylphenyls) HFC-236fas of N ', O, the O glycidyl of '-six -2,2- and 8 grams of ends Aminobutyronitrile rubber is put into reactor, in after 90 DEG C of stirring reactions 0.5 hour, add 100 grams of 3,4- epoxycyclohexyethylSiOis acid- 3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3 grams of alpha-cyano-β-ethoxy ethyl acrylates, after being uniformly mixed in 60 DEG C, are cooled to Room temperature, adds 100 grams of methyl tetrahydro phthalic anhydrides and 10 grams of DMP-30 to be uniformly mixed, and obtains 323 grams of BAHPFP type epoxy matrixes Resin, is denoted as BAHPFP-2.Fly CAP2000+ viscosity using rich Le and measure its 50 DEG C viscosity for 738mPa.s；It is solidifying using GT-H The gel time that gel time tester measures 120 DEG C is 856s.

Embodiment 3

By 50 grams of Diglycidyl M-phthalate epoxy resin, 50 grams of hydrogenated bisphenol A diglycidyl ether asphalt mixtures modified by epoxy resin Fat, 5 grams of N, N, N ', double (3- amino-4-hydroxylphenyls) HFC-236fas of N ', O, the O glycidyl of '-six -2,2- and 10 grams of end carboxylics Base nitrile rubber is put into reactor, in after 100 DEG C of stirring reactions 0.5 hour, adding 200 grams of 3,4- epoxycyclohexyethylSiOis acid -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 5 grams of alpha-cyano-β-ethoxy ethyl acrylates, after being uniformly mixed in 70 DEG C, are cooled to room Temperature, adds 180 grams of methyl tetrahydro phthalic anhydrides, 10 grams of dodecyl succinic anhydrides and 10 grams of DBU, is uniformly mixed, and obtains 520 grams BAHPFP type epoxy matrix resins, are denoted as BAHPFP-3.Measuring its 50 DEG C viscosity using the winged CAP2000+ viscosity of rich Le is 549mPa.s；The gel time for measuring 120 DEG C using GT-H gelation time testers is 995s.

Embodiment 4

By 1000 grams of drying powdereds, (crystal waste slag stoving process is：120 DEG C retain 10 hours) crystal waste slag (contain It is 1 that water is not more than and 0.1%) add 10 kilogram-mass ratios:In the 32 3- aminopropyl trimethoxysilane aqueous solution, stir at room temperature Mix 0.5 hour, filter, take solids, in 100 DEG C of dryings 3 hours, obtain by the crystal waste slag powder of coupling agent surface treatment End, is denoted as C-1.

By 1000 grams of drying powdereds, (crystal waste slag stoving process is：120 DEG C retain 11 hours) crystal waste slag (contain It is 1 that water is not more than and 0.1%) add 15 kilogram-mass ratios:In the 60 3- aminopropyl triethoxysilane aqueous solution, stir at room temperature Mix 1 hour, filter, take solids, in 110 DEG C of dryings 2 hours, obtain by the crystal waste slag powder of coupling agent surface treatment, It is denoted as C-2.

By 1000 grams of drying powdereds, (crystal waste slag stoving process is：120 DEG C retain 12 hours) crystal waste slag (contain It is 1 that water is not more than and 0.1%) add 20 kilogram-mass ratios:In the 99 3- aminopropyl triethoxysilane aqueous solution, stir at room temperature Mix 0.5 hour, filter, take solids, in 120 DEG C of dryings 1 hour, obtain by the crystal waste slag powder of coupling agent surface treatment End, is denoted as C-3.

Embodiment 5

30 grams of C-1 crystal waste slags powder, 32 grams of BAHPFP-1 epoxy matrix resins, 5 grams of Staple carbon fibers are mixed equal It is even, 67 grams of BAHPFP type epoxy resin-base composite material systems are obtained, flat plate mold is packed into, heating is pressurizeed, curing molding, its Temperature range is room temperature to 180 DEG C；Pressure limit is 1MPa to 10MPa；Press time is -5 hours 0.5 hour, and flat board is obtained, It is denoted as F-1.Its performance data is as shown in table 1.

By 30 grams of C-2 crystal waste slags powder, 45 grams of BAHPFP-2 epoxy matrix resins, 5 grams of carbon fibers and 5 grams of glass fibres Chopped fiber be well mixed, obtain 85 grams of BAHPFP type epoxy resin-base composite material systems, be packed into flat plate mold, heating plus Pressure, curing molding, its temperature range is room temperature to 180 DEG C；Pressure limit is 1MPa to 10MPa；Press time is 0.5 hour -5 Hour, flat board is obtained, it is denoted as F-2.Its performance data is as shown in table 1.

By 30 grams of C-3 crystal waste slags powder, 45 grams of BAHPFP-3 epoxy matrix resins, 15 grams of carbon fibers and 10 grams of glass fibers The chopped fiber of dimension is well mixed, and obtains 100 grams of BAHPFP type epoxy resin-base composite material systems, is packed into flat plate mold, plus Heat pressurization, curing molding, its temperature range is room temperature to 180 DEG C；Pressure limit is 1MPa to 10MPa；Press time is 0.5 small When -5 hours, be obtained flat board, be denoted as F-3.Its performance data is as shown in table 1.

By 30 grams of C-1 crystal waste slags powder, 30 grams of C-3 crystal waste slags powder, 45 grams of BAHPFP-3 epoxy matrix resins, 15 Gram Staple carbon fibers are well mixed, and obtain 120 grams of BAHPFP type epoxy resin-base composite material systems, are packed into flat board mould Tool, heating pressurization, curing molding, its temperature range is room temperature to 180 DEG C；Pressure limit is 1MPa to 10MPa；Press time is - 5 hours 0.5 hour, flat board is obtained, is denoted as F-4.Its performance data is as shown in table 1.

By 30 grams of C-1 crystal waste slags powder, 10 grams of C-2 crystal waste slags powder, 15 grams of BAHPFP-1 epoxy matrix resins, 15 Gram BAHPFP-3 epoxy matrix resins, 20 grams of glass fibre chopped fibers are well mixed, and obtain 90 grams of BAHPFP type epoxy resin-matrixes Composite system, is packed into flat plate mold, and heating is pressurizeed, curing molding, and its temperature range is room temperature to 180 DEG C；Pressure model Enclose for 1MPa to 10MPa；Press time is -5 hours 0.5 hour, and flat board is obtained, and is denoted as F-5.Its performance data is as shown in table 1.

1 crystal waste slag of table/BAHPFP type epoxy resin-base composite material flat board performance datas

Claims

1. the preparation method of a kind of crystal waste slag/BAHPFP type epoxy matrix resin composites, including：

By crystal waste slag drying, powdered, coupling agent surface treatment is carried out；Then by crystal waste slag powder and BAHPFP type epoxies Matrix resin, chopped fiber are well mixed, and obtain BAHPFP type epoxy resin-base composite material systems, are packed into mould, and heating adds Cured shaping, obtains final product crystal waste slag/BAHPFP type epoxy matrix resin composites；Wherein, crystal waste slag powder, BAHPFP Type epoxy matrix resin is 30-60 with the mass ratio of chopped fiber:32-45:5-25.

2. the preparation method of a kind of crystal waste slag according to claim 1/BAHPFP type epoxy matrix resin composites, It is characterized in that：The crystal waste slag stoving process is：120 DEG C retain -12 hours 10 hours, make crystal waste slag water content little In 0.1%.

3. the preparation method of a kind of crystal waste slag according to claim 1/BAHPFP type epoxy matrix resin composites, It is characterized in that：The coupling agent surface treatment technique is：It is 1 by mass ratio:The coupling agent and water of 32-99 are uniformly mixed Afterwards, the crystal waste slag powder of drying is added, is stirred -1 hour 0.5 hour at room temperature, filtering takes solids, in 100 DEG C -120 DEG C Dry -3 hours 1 hour, obtain by the crystal waste slag powder of coupling agent surface treatment；Wherein, crystal waste slag powder and coupling The mass ratio of the agent aqueous solution is 1:10-20.

4. the preparation side of a kind of crystal waste slag according to claim 1 or 3/BAHPFP type epoxy matrix resin composites Method, it is characterised in that：The coupling agent be selected from 3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes, γ-(2, The oxygen of 3- epoxies third) propyl trimethoxy silicane, γ-aminopropyltriethoxy diethoxy silane, N- (β-aminoethyl)-γ-aminopropyl Methyl dimethoxysilane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-methacryloxypropyl Base propyl-triethoxysilicane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloxy third One or more in base trimethoxy silane.

5. the preparation method of a kind of crystal waste slag according to claim 1/BAHPFP type epoxy matrix resin composites, It is characterized in that：The BAHPFP types epoxy matrix resin be by mass ratio be 100:1-5:20-200:5-10:1-5:50-200 Epoxy resin, N, N, N ', the glycidyl -2,2- of N ', O, O- six double (3- amino-4-hydroxylphenyls) HFC-236fa, activity Diluent, endurable active toughener, alpha-cyano-β-ethoxy ethyl acrylate and curing agent composition.

6. the preparation side of a kind of crystal waste slag/BAHPFP type epoxy matrix resin composites according to claim 1 or 5 Method, it is characterised in that：The preparation method of the BAHPFP types epoxy matrix resin comprises the following steps：By epoxy resin, N, N, N ', N ', double (3- amino-4-hydroxylphenyls) HFC-236fas of the glycidyl -2,2- of O, O- six, endurable active toughener are put into reactor In, in after 80 DEG C of -100 DEG C of stirring reactions -1 hour 0.5 hour, add reactive diluent, alpha-cyano-β-ethoxy-c olefin(e) acid second Ester, after being uniformly mixed in 50 DEG C -70 DEG C, is cooled to room temperature, adds curing agent, is uniformly mixed.

7. the preparation method of a kind of crystal waste slag according to claim 1/BAHPFP type epoxy matrix resin composites, It is characterized in that：The chopped fiber is selected from staple glass fibre, Staple carbon fibers, short basalt fiber, aramid fiber short fibre, polyamides Imines chopped fiber, polyester staple fiber, polyamide staple fibre, acrylic staple fibre, short fiber of cellulose, polyformaldehyde chopped fiber, cotton fiber, One or more in wool fiber, rabbit fur fibre, polyvinyl chloride fibre chopped fiber, polyvinyl alcohol chopped fiber.

8. the preparation side of a kind of crystal waste slag according to claim 1 or 7/BAHPFP type epoxy matrix resin composites Method, it is characterised in that：The chopped fiber is the chopped fiber being surface-treated by silane coupler of length 1mm-13mm.

9. the preparation method of a kind of crystal waste slag according to claim 1/BAHPFP type epoxy matrix resin composites, It is characterized in that：The technological parameter of heat-pressure curing shaping is：Temperature be room temperature to 180 DEG C, pressure is 1MPa- 10MPa, the press time is -5 hours 0.5 hour.

10. the preparation side of a kind of crystal waste slag according to claim 1/BAHPFP type epoxy matrix resin composites Method, it is characterised in that：The composite be used for flat board, flowerpot, cable bearer, tank, guardrail, ammeter tank shell, dustbin, Postal casing, billboard, motorway guide planks, inspection well cover, cable duct groove lid, flower bed fence or seat.