CN106751494B - A kind of preparation method of crystal waste slag/BAHPP type epoxy matrix resin composite materials - Google Patents

Abstract

The present invention relates to a kind of preparation methods of crystal waste slag/BAHPP type epoxy matrix resin composite materials, including：By crystal waste slag drying, powdered, coupling agent surface treatment is carried out；Then crystal waste slag powder is uniformly mixed with BAHPP types epoxy matrix resin, staple fiber, obtains BAHPP type ring epoxy resin-based composite systems, be packed into mold, heat-pressure curing molding to get.The composite material 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, realizes recycling, very important realistic meaning is all had to comprehensive environmental improvement etc., can get good Social benefit and economic benefit.

Description

A kind of preparation method of crystal waste slag/BAHPP type epoxy matrix resin composite materials

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 BAHPP type epoxy matrix resin composite materials.

Background technology

China is earliest one of the country for grasping glass manufacturing techniques, 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 when the Tang and Song Dynasty.Largely 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, And the mineral crystal of water white transparency and diamond are rare in the world, it is expensive, so several crystal glass to look 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 start to walk before 20 years by this beading, arrives 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 craftwork and enjoy a widespread reputation, crystal glass cuts a conspicuous figure because the consummate craftsmanship of Pujiang people is obtained.In 1993, Seiko It is selected in Pujiang crystal glass lamp decoration decorative hanging piece one action of fine grinding, the Great Hall of the People is decorateeed more glorious and magnificent, Pujiang people is deep 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 with its sage Moral character, the skill of superb craftsmanship of clean elegance, be chosen as Hong Kong, Macao's return to the motherland and China Millennium Altar completion grand ceremony gift.

By 2011, the crystal of Pujiang production accounted for the 80% of national total amount, more than 22000 Duo Jia crystals factories and workshop It takes 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 creating the wealth to Pujiang The heavy environmental pressure of a small county town back.In extensive crystal process, the waste water quilt containing a large amount of glass powders Be discharged into river, in addition solid waste rubbish, house refuse are poured into korneforos by locals's custom, " the milk river " of off-white color, rubbish river at The grey label of Pujiang.It 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 worst one of the river of Zhejiang Province's river water quality.2011, become Zhejiang only one here The county of " twice in succession region limit batch ", it is last that the environmental sanitation evaluation satisfaction of Pujiang also ranks the whole province for many years, is referred to as " the worst county of Zhejiang hygienic conditions ".How to be depressurized to ecological environment2006,2011, Pujiang county government all once put into effect policy, Plan is managed and limits to the discharge of crystal industry, but all stagnates because of various reasons.

It is reported that since 2015, Pujiang County organizes strike environmental illegality behavior and jointly acts more than 1000 times, bans Crystal processes 18450, family, and 726 crystal self-employed workers realize " a turn of enterprise ".Fall sharply from original family more than 22000 to more than 3000 Family, this " crystal all " in the past, just forces industrial transformation to upgrade by the chance of " five water are controlled altogether ".However, crystal waste slag Problem not yet solves so far, and the 4 of Pujiang crystal Industrial Zones generate 300 tons of -500 tons of crystal waste slags, number daily at present It measures huge, causes huge pressure to environment, while also seriously constraining the fast development of crystal industry, to crystal industry Sustainable development is provided with great obstacle.

Currently, to the processing of crystal waste slag mainly by following methods：

Cement additive：In cement manufacture production, a small amount of crystal waste slag is added, high-temperature fusion calcining crushes, packaging, Manufacture, obtains cement.

There are obvious shortcomings for this method, are mainly manifested in：Additive amount is very little, it is difficult to be effectively treated daily 300 tons -500 tons Crystal waste slag amount；Cement quality is caused to decline significantly after being added to a small amount of crystal waste slag, there is the serious of cement applications Security risk can not be promoted and applied actually on a large scale.

Glass block additive：Glass block made from the crystal waste slag of≤25% weight, Bu Neng is added in brick making It is applied in building field, especially load bearing construction, can be only applied to enclosure wall.But in the natural environment, expose to the weather and drench with rain, The glass block is easy to weathering and falls off, and intensity drastically declines, it is difficult to and it is practical to promote and apply, crystal waste slag is greatly limited in brickmaking The application in field.The defects of in addition, that there is also energy consumptions is big, additive amount is few, surface is too smooth and not applying lime etc..

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

For this purpose, crystal waste slag additive amount is big, low energy consumption, does not generate secondary pollution, and the height needed for society, market can be made Cost performance material or new product are the development trends of crystal waste slag treatment technology from now on.Crystal waste slag may be used and organic tree Fat, including epoxy resin, unsaturated-resin, polyurethane resin, phenolic resin, vinylite etc. are compound, prepare composite material, It can be applied to the fields such as building, traffic, gardening.Currently, 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 good construction materials, are largely used to high-grade luxurious hotel, airport lounge, high ferro It waits building and platform, family kitchen and bath, office business building etc..As the improvement of people's living standards, to granite plates Demand is growing day by day, to further promote exploitation, the processing in granite mine, scale amounts more and more huger.And it opens at it Adopt, process necessarily leads to a large amount of stone slurry, granite powder scrap etc., cause serious ring to river, mountains and rivers, stockyard etc. Border is polluted, while the secondary disasters such as also easily cave in, and larger potential threat is caused to the people's lives and property.

For this purpose, people start actively to study the technology that the waste residue in granite stone pit is utilized again.Chinese invention is special Sharp CN1037042A discloses a kind of inorganic artificial granite production technology, is primarily characterized in that：High alumina cement, stone are used first Sand, inorganic pigment powder, glycerine and water mixing are tuned into thin pulp shape mill base, pour into shaping frame, after initial set, use high silicon water Mud, quartz sand, quartz, inorganic pigment powder, glycerine and water, mixing is tuned into thin pulp shape coat of colo(u)r, irregularly on color paste layer Portion, then after adding water to stir evenly with high alumina cement, river sand, rubble, be cast in shaping frame, as reinforcing after machinery shakes Layer is finally putting into pond and impregnates maintenance molding in 72 hours, and using ageing-resistant pickling processes, product can be become 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 manufacturing method of fixed, high quality full-inorganic artificial marble, is primarily characterized in that：Using cement as raw material, it is added a small amount of inorganic Auxiliary agent forms ontology, with it is pre-fabricated have a special component vibration is added in ontology into flower at flower agent, conserve and crystallize 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 bottom material water, then go to mix cement and silica flour with fabric water and bottom material water, make respectively At face layer and bottom, have between face layer and bottom one stirred with cement, silica flour and fabric water after spread out and put on face layer top Base, 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, some, which is even more than, is glued the intensity of material itself, therefore can be used for many stress members In, it is one of main component of structural adhesive；(2) good processing performance：The flexibility of Formulaion of epoxy resin, processing work The diversity of skill and product properties is the most outstanding in high molecular material；(3) good stability：The solidification of epoxy resin The ring opening polyaddition of epoxy group is mainly relied on, therefore does not generate low-molecular material in solidification process, cure shrinkage is heat Minimum one of kind, generally 1%-2% in thermosetting resin, if filler appropriate is selected shrinking percentage can be made to be down to 0.2% Left and right；Epoxy main chains after solidification are ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore have excellent resistance to acid and alkali.

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

Related high-temperature resistant epoxy oxygen system is 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, Accelerating agent is uniformly mixed, and heat-resistant solvent-free epoxy adhesive has been made.But its high temperature resistance 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, 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 Carboxy nitrile rubber；B component is bis- (2,4- diamino phenoxies) the benzene aromatic polyvalent amine hardeners of 1,4-.Alicyclic ring type asphalt mixtures modified by epoxy resin The additive amount of fat and nbr carboxyl terminal is respectively the 20-35% and 12% (mass percent) of novolac epoxy resin.1,4- The additive amount of bis- (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 ideal 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 bis- (the 2,4- dimaleimides phenoxyl) benzene of 1,4- The novel fire resistant of high tenacity is obtained by the reaction with polyfunctional epoxy resin, nbr carboxyl terminal CTBN for four maleimide resins Organic solvent is added in resin, 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 uniformly to get B component；A, B component are mixed, stirred evenly to get used for advanced composite material Heat resist modification multi-functional epoxy's substrate resin solution.

Seas Yu Xin et al.【The &#91 of high-temperature resistant single-component epoxy adhesive;J]It is bonded, 2008,29 (12)：16-19】It is public A kind of preparation method of high-temperature resistant single-component epoxy adhesive has been opened, has been primarily characterized in that：It is sealing end with maleic anhydride (MA) Agent, with bis- (3- amino-4-hydroxylphenyls) hexafluoropropane (BAHPFP) of 2,2-, the bis- &#91 of 2,2-;4- (4- amino-benzene oxygens) Ben Ji ]Third Alkane (BAPOPP), the bis- &#91 of 2,2-;4- (3,4- di carboxyl phenyloxies) Ben Ji ]Propane dianhydride (BPADA) is that main Material synthesis obtains Phenolic hydroxy group polyetherimide resin (HPEI)；With synthesized obtained HPEI for resistant, toughened dose, with N, N, N',N'- four Glycidyl -4,4'Diaminodiphenylmethane (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent Deng, preparation obtained the high-temperature resistant single-component epoxy adhesive of excellent combination property.

Invention content

Technical problem to be solved by the invention is to provide a kind of crystal waste slag/BAHPFP type epoxy matrix resin compounded materials The preparation method of material, the composite material that this method is prepared not only can efficient process crystal waste slag, eliminate environmental pollution, and It can turn waste into wealth, realize recycling, very important realistic meaning is all had to comprehensive environmental improvement etc., can get good Social benefit and economic benefit.

A kind of preparation method of crystal waste slag/BAHPP type epoxy matrix resin composite materials of the present invention, including：

By crystal waste slag drying, powdered, coupling agent surface treatment is carried out；Then by crystal waste slag powder and BAHPP types Epoxy matrix resin, staple fiber are uniformly mixed, and are obtained BAHPP type ring epoxy resin-based composite systems, are packed into mold, are heated Cure under pressure is molded to get crystal waste slag/BAHPP type epoxy matrix resin composite materials；Wherein, crystal waste slag powder, BAHPP Type epoxy matrix resin and the mass ratio of staple fiber are 30-60:32-45:5-25.

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

The coupling agent surface treatment technique is：It is 1 by mass ratio:After the coupling agent and water of 32-99 is uniformly mixed, The crystal waste slag powder of drying is added, stirs -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 the crystal waste slag powder by coupling agent surface treatment；Wherein, crystal waste slag powder and coupling agent The mass ratio of 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-aminopropyltriethoxies two Methoxy silane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-methacryloxypropyl Triethoxysilane, γ-methacryloxypropylmethyl dimethoxysilane, γ-methacryloxypropyl front three One or more of oxysilane.

It is 100 that the BAHPP types epoxy matrix resin, which is by mass ratio,:1-5:20-200:5-10:1-5:The ring of 50-200 Oxygen resin, mass ratio 1:5 bis- (3- amino-4-hydroxylphenyls) propane of 2,2- and the copolymer of ES216 epoxy resin, activity Diluent, endurable active toughener, alpha-cyano-β-ethoxy ethyl acrylate and curing agent composition.

The copolymer of 2,2- bis- (3- amino-4-hydroxylphenyls) propane and ES216 epoxy resin, is to be by mass ratio 1:5 bis- (3- amino-4-hydroxylphenyls) propane of 2,2- and ES216 epoxy resin, obtain after being reacted 0.5 hour at 100 DEG C Homogeneous copolymers.

The preparation method of the BAHPP types epoxy matrix resin includes the following steps：By epoxy resin, mass ratio 1:5 Copolymer, the endurable active toughener of bis- (3- amino-4-hydroxylphenyls) propane of 2,2- and ES216 epoxy resin be put into reaction kettle In, after 80 DEG C -100 DEG C are stirred to react -1 hour 0.5 hour, reactive diluent, alpha-cyano-β-ethoxy-c olefin(e) acid second is added Ester is cooled to room temperature after 50 DEG C -70 DEG C are uniformly mixed, and curing agent is added, is 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 groups -4,4 '-diamino hexichol first Alkane epoxy resin, N, N, N ', N '-four glycidyl groups -3,3 '-dimethyl -4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N ', O- five glycidyls -4,4 '-diamino -4 "-hydroxyl triphenylmenthane, N, N, N ', N '-four glycidyl groups 3, 3 '-diethyl -4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl groups 3,3 '-two chloro- 4,4 '-two Diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-diaminodiphenyl ether epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-diaminodiphenylsulfone epoxy resin, N, N, N ', N '-four glycidyl groups -3,4 '-diamino Diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl groups -3,3 '-diaminodiphenylsulfone 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)s epoxy resin, N, N, N ', bis- (the 4- aminobenzene oxygen of N '-four glycidyl groups -1,4- Base) benzene epoxy resin, N, N, N ', bis- (3- amino-benzene oxygens) the benzene epoxy resin of N '-four glycidyl groups -1,4-, N, N, N ', Bis- (4- amino-benzene oxygens) the benzene epoxy resin of N '-four glycidyl groups -1,3-, N, N, N ', N '-four glycidyl groups -1,3- is double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N ', the bis- (2- trifluoromethyl -4- aminobenzene oxygen of N '-four glycidyl groups -1,4- Base) benzene epoxy resin, N, N, N ', bis- (2- trifluoromethyl-4-aminophenoxyls) the benzene asphalt mixtures modified by epoxy resin of N '-four glycidyl groups -1,3- Fat, N, N, N ', the double &#91 of N '-four glycidyl groups -2,2-;4- (4- amino-benzene oxygens) Ben Ji ]Propane epoxy resin, N, N, N ', N '- The double &#91 of four glycidyl group -2,2-;4- (4- amino-benzene oxygens) Ben Ji ]Hexafluoropropane epoxy resin, N, N, N ', N '-four shrinks sweet The double &#91 of oil base -2,2-;4- (3- amino-benzene oxygens) Ben Ji ]Propane epoxy resin, N, N, N ', N '-four glycidyl groups -2,2- is double [4- (2- trifluoromethyl-4-aminophenoxyls) Ben Ji ]Propane epoxy resin, N, N, N ', N '-four glycidyl groups -2,2- is double [4- (3- amino-benzene oxygens) Ben Ji ]Hexafluoropropane epoxy resin, N, N, N ', the double &#91 of N '-four glycidyl groups -2,2-;4- (2- tri- Methyl fluoride -4- amino-benzene oxygens) Ben Ji ]Hexafluoropropane epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- ammonia Phenoxyl) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyl -4- aminobenzene oxygen Base) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl groups - 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 ' - Bis- (4- amino-benzene oxygens) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyls -4- Amino-benzene oxygen) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino-benzene oxygens) hexichol Ketone epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone Epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino-benzene oxygens) biphenyl epoxy resin, N, N, N ', N ' - Bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl epoxy resins of four glycidyl group -4,4 ' -, N, N, N ', N ', O, O '-six contracting Bis- (3- amino-4-hydroxylphenyls) the hexafluoropropane epoxy resin of water glyceryl -2,2-, N, N, O-triglycidyl group p-aminophenyl Phenol epoxy resin, N, one or more of N, O-triglycidyl meta-aminophenol epoxy resin.

The diglycidyl ether type epoxy resin is selected from 1,3- diglycidyls resorcinol, 1,4- diglycidyls Bis- (4- glycidyl phenyls) hexafluoropropane of hydroquinone, 4,4 '-diglycidyl bisphenol Ss, 2,2-, 2,2- are bis-, and (4- contracts Water glycerine butylcyclohexyl) propane, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol-A 2-glycidyl One or more of ether, fatty alcohol polyglycidyl ether.

The phenol aldehyde type epoxy resin is selected from phenol-formaldehyde 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 of 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, two octanoic acid two of adjacent benzene One or more of polyglycidyl epoxy resin.

The reactive diluent is selected from sour -3 ', the 4 '-epoxycyclohexyethylSiOi methyl esters of 3,4- epoxycyclohexyethylSiOis, 3,4- epoxy groups -6- Methyl cyclohexane acid -3 ', 4 '-epoxy groups -6 '-methyl cyclohexane methyl esters, ethylene glycol diglycidylether, propylene glycol 2-glycidyl Ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, hexylene glycol two shrink One or more of 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 of 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 methanes, 3,3 '-dimethyl -4,4 '-two Amino bicyclic hexyl methane, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride, tung oil acid anhydride, with One or more of turpentine oil and liquid acid anhydrides made of maleic acid anhydride reactant.

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

The staple fiber being surface-treated by silane coupling agent that the staple fiber is length 1mm-13mm.

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

The composite material is for tablet, flowerpot, cable bearer, sink, guardrail, ammeter tank shell, dustbin, mail box Body, billboard, motorway guide planks, inspection well cover, cable duct capping, flower bed fence or seat.

Advantageous effect

(1) present invention's is simple for process, at low cost, easy to operate, and raw material sources are convenient, can be completed in common apparatus Preparation process is advantageously implemented industrialized production；

(2) present invention is solvent-free, and environmental-friendly, equipment investment is few, and crystal waste slag loading is big, and low energy consumption, 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 all had to comprehensive environmental improvement etc., can get good social benefit and economy is imitated Benefit.

Specific implementation mode

Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.

Embodiment 1

It is 1 by 100 grams of E-51 epoxy resin, 1 gram mass ratio:5 bis- (3- amino-4-hydroxylphenyls) propane of 2,2- with The copolymer of ES216 epoxy resin and 5 grams of nbr carboxyl terminals are put into reaction kettle, after 80 DEG C are stirred to react 1 hour, are added Enter sour -3 ', the 4 '-epoxycyclohexyethylSiOi methyl esters of 20 grams of 3,4- epoxycyclohexyethylSiOis, 1 gram of alpha-cyano-β-ethoxy ethyl acrylate, in 70 It after DEG C being uniformly mixed, is cooled to room temperature, 48 grams of m-xylene diamines and 2 grams of 2-ethyl-4-methylimidazoles is added, are stirred Uniformly, 177 grams of BAHPP type epoxy matrix resins are obtained, BAHPP-1 is denoted as.Using it is rich strangle fly CAP2000+ viscosity measure its 50 DEG C viscosity be 1024mPa.s；The gel time that 120 DEG C are measured using GT-H gelation time testers is 997s.

Embodiment 2

By 60 grams of E-44 epoxy resin, 40 grams of N, N, N ', N '-four glycidyl groups -4,4 '-diaminodiphenylmethane epoxy Resin, 2 gram mass ratios are 1:The copolymer and 8 of 5 2,2- bis- (3- amino-4-hydroxylphenyls) propane and ES216 epoxy resin Gram amino terminated butadiene acrylonitrile rubber is put into reaction kettle, and after 90 DEG C are stirred to react 0.5 hour, 100 grams of 3,4- epoxycyclohexyethylSiOis are added Sour -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3 grams of alpha-cyano-β-ethoxy ethyl acrylates, it is cold after 60 DEG C are uniformly mixed But to room temperature, 100 grams of methyl tetrahydro phthalic anhydrides is added and 10 grams of DMP-30 are uniformly mixed, obtain 323 grams of BAHPP type ring oxygroups Body resin, is denoted as BAHPP-2.Fly CAP2000+ viscosity to measure its 50 DEG C viscosity to be 954mPa.s using rich strangle；Utilize GT-H The gel time that gelation time tester measures 120 DEG C is 910s.

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 gram mass ratios are 1:5 bis- (3- amino-4-hydroxylphenyls) propane of 2,2- and the copolymer of ES216 epoxy resin and 10 grams Nbr carboxyl terminal is put into reaction kettle, and after 100 DEG C are stirred to react 0.5 hour, 200 grams of 3,4- epoxycyclohexyethylSiOis are added Sour -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 5 grams of alpha-cyano-β-ethoxy ethyl acrylates, it is cold after 70 DEG C are uniformly mixed But to room temperature, 180 grams of methyl tetrahydro phthalic anhydrides, 10 grams of dodecyl succinic anhydrides and 10 grams of DBU is added, is uniformly mixed, obtains To 520 grams of BAHPP type epoxy matrix resins, it is denoted as BAHPP-3.Fly CAP2000+ viscosity using rich Le and measures its 50 DEG C of viscosity For 875mPa.s；The gel time that 120 DEG C are measured using GT-H gelation time testers is 764s.

Embodiment 4

By 1000 grams of drying powdereds, (crystal waste slag stoving process is：120 DEG C retain 10 hours) crystal waste slag (contain Water is 1 no more than 10 kilogram-mass ratios 0.1%) are added:In 32 3- aminopropyl trimethoxysilane aqueous solutions, stir at room temperature It mixes 0.5 hour, filters, take solids, it is 3 hours dry in 100 DEG C, obtain the crystal waste slag powder by 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 Water is 1 no more than 15 kilogram-mass ratios 0.1%) are added:In 60 3- aminopropyl triethoxysilane aqueous solutions, stir at room temperature It mixes 1 hour, filters, take solids, it is 2 hours dry in 110 DEG C, the crystal waste slag powder by coupling agent surface treatment is obtained, 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 Water is 1 no more than 20 kilogram-mass ratios 0.1%) are added:In 99 3- aminopropyl triethoxysilane aqueous solutions, stir at room temperature It mixes 0.5 hour, filters, take solids, it is 1 hour dry in 120 DEG C, obtain the crystal waste slag powder by coupling agent surface treatment End is denoted as C-3.

Embodiment 5

30 grams of C-1 crystal waste slags powder, 32 grams of BAHPP-1 epoxy matrix resins, 5 grams of Staple carbon fibers are mixed equal It is even, 67 grams of BAHPP type ring epoxy resin-based composite systems are obtained, flat plate mold is packed into, heating is pressurizeed, curing molding, Temperature range is room temperature to 180 DEG C；Pressure limit is 1MPa to 10MPa；Pressing time is -5 hours 0.5 hour, and tablet is made, 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 BAHPP-2 epoxy matrix resins, 5 grams of carbon fibers and 5 grams of glass fibres Staple fiber be uniformly mixed, obtain 85 grams of BAHPP type ring epoxy resin-based composite systems, be packed into flat plate mold, heating plus Pressure, curing molding, temperature range are room temperature to 180 DEG C；Pressure limit is 1MPa to 10MPa；Pressing time is 0.5 hour -5 Hour, tablet is made, 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 BAHPP-3 epoxy matrix resins, 15 grams of carbon fibers and 10 grams of glass fibers The staple fiber of dimension is uniformly mixed, and is obtained 100 grams of BAHPP type ring epoxy resin-based composite systems, is packed into flat plate mold, is heated Pressurization, curing molding, temperature range are room temperature to 180 DEG C；Pressure limit is 1MPa to 10MPa；Pressing time is 0.5 small When -5 hours, be made tablet, 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 BAHPP-3 epoxy matrix resins, 15 Gram Staple carbon fibers are uniformly mixed, and are obtained 120 grams of BAHPP type ring epoxy resin-based composite systems, are packed into flat plate mold, Heating pressurization, curing molding, temperature range are room temperature to 180 DEG C；Pressure limit is 1MPa to 10MPa；Pressing time is 0.5 - 5 hours hours were made tablet, and were 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 BAHPP-1 epoxy matrix resins, 15 Gram BAHPP-3 epoxy matrix resins, 20 grams of glass fibre staple fibers are uniformly mixed, and it is epoxy resin-based multiple to obtain 90 grams of BAHPP type rings Condensation material system is packed into flat plate mold, and heating pressurization, curing molding, temperature range is room temperature to 180 DEG C；Pressure limit For 1MPa to 10MPa；Pressing time is -5 hours 0.5 hour, and tablet is made, is denoted as F-5.Its performance data is as shown in table 1.

1 crystal waste slag of table/BAHPP type ring epoxy resin-based composite tablet performance datas

Claims (9)

1. a kind of preparation method of crystal waste slag/BAHPP type epoxy matrix resin composite materials, including：

By crystal waste slag drying, powdered, coupling agent surface treatment is carried out；Then by crystal waste slag powder and BAHPP type ring oxygen Matrix resin, staple fiber are uniformly mixed, and obtain BAHPP type ring epoxy resin-based composite systems, are packed into mold, heating pressurization Curing molding is to get crystal waste slag/BAHPP type epoxy matrix resin composite materials；Wherein, crystal waste slag powder, BAHPP type rings Oxygen matrix resin and the mass ratio of staple fiber are 30-60:32-45:5-25；The BAHPP types epoxy matrix resin is by quality Than being 100:1-5:20-200:5-10:1-5:Epoxy resin, the mass ratio 1 of 50-200:5 bis- (3- amino -4- the hydroxyls of 2,2- Base phenyl) propane and ES216 epoxy resin copolymer, reactive diluent, endurable active toughener, alpha-cyano-β-ethoxy propylene Acetoacetic ester and curing agent composition.

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

3. a kind of preparation method of crystal waste slag according to claim 1/BAHPP type epoxy matrix resin composite materials, 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 is uniformly mixed Afterwards, the crystal waste slag powder of drying is added, stirs -1 hour 0.5 hour at room temperature, filtering takes solids, in 100 DEG C -120 DEG C It is -3 hours 1 hour dry, obtain the crystal waste slag powder by coupling agent surface treatment；Wherein, crystal waste slag powder and coupling The mass ratio of agent aqueous solution is 1:10-20.

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

5. a kind of preparation method of crystal waste slag according to claim 1/BAHPP type epoxy matrix resin composite materials, It is characterized in that：The preparation method of the BAHPP types epoxy matrix resin includes the following steps：It is by epoxy resin, mass ratio 1:5 bis- (3- amino-4-hydroxylphenyls) propane of 2,2- are put into the copolymer of ES216 epoxy resin, endurable active toughener to react In kettle, after 80 DEG C -100 DEG C are stirred to react -1 hour 0.5 hour, reactive diluent, alpha-cyano-β-ethoxy-c olefin(e) acid is added Ethyl ester is cooled to room temperature after 50 DEG C -70 DEG C are uniformly mixed, and curing agent is added, is uniformly mixed.

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

7. a kind of preparation side of crystal waste slag according to claim 1 or 6/BAHPP type epoxy matrix resin composite materials Method, it is characterised in that：The staple fiber being surface-treated by silane coupling agent that the staple fiber is length 1mm-13mm.

8. a kind of preparation method of crystal waste slag according to claim 1/BAHPP type epoxy matrix resin composite materials, It is characterized in that：The molding technological parameter of heat-pressure curing is：Temperature is room temperature to 180 DEG C, pressure 1MPa- 10MPa, pressing time are -5 hours 0.5 hour.

9. a kind of preparation method of crystal waste slag according to claim 1/BAHPP type epoxy matrix resin composite materials, It is characterized in that：The composite material is for tablet, flowerpot, cable bearer, sink, guardrail, ammeter tank shell, dustbin, postal Political affairs babinet, billboard, motorway guide planks, inspection well cover, cable duct capping, flower bed fence or seat.