CN106220042A - A kind of BDAPP type granolith sheet material and preparation method thereof - Google Patents

A kind of BDAPP type granolith sheet material and preparation method thereof Download PDF

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Publication number
CN106220042A
CN106220042A CN201610578960.5A CN201610578960A CN106220042A CN 106220042 A CN106220042 A CN 106220042A CN 201610578960 A CN201610578960 A CN 201610578960A CN 106220042 A CN106220042 A CN 106220042A
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epoxy resin
type
bdapp
glycidyl group
resin
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虞鑫海
周志伟
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Donghua University
Shanghai Ruitu Electronic Material Co Ltd
National Dong Hwa University
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Donghua University
Shanghai Ruitu Electronic Material Co Ltd
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Priority to CN201610578960.5A priority Critical patent/CN106220042A/en
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/14—Polyepoxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/54—Substitutes for natural stone, artistic materials or the like
    • C04B2111/542—Artificial natural stone
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention relates to a kind of BDAPP type granolith sheet material and preparation method thereof, described granite plates is made up of the granite powder that mass ratio is 100:5 10 and BDAPP type resin.Preparation method includes: mixed with BDAPP stirring by epoxy resin, and 115 DEG C 125 DEG C are reacted 0.5 1 hours, are cooled to less than 60 DEG C, adds latent curing agent LRC30 and liquid anhydride, stirring, obtains BDAPP type resin；BDAPP type resin is mixed homogeneously with granite powder, pressing preforming, heat-pressure curing molding, to obtain final product.Raw material sources of the present invention are convenient, production technology is simple, solvent-free, environmental friendliness, product combination property is superior, can be widely applied to building materials field, wait building and platform, family kitchen guarding, office business building etc. including high-grade hotel, airport lounge, high ferro, there is good market application foreground.

Description

A kind of BDAPP type granolith sheet material and preparation method thereof
Technical field
The invention belongs to organic/inorganic composite material and preparation field thereof, particularly to a kind of BDAPP type granolith Sheet material and preparation method thereof.
Background technology
Granite plates is the construction material of a kind of high-quality, is largely used to high-grade luxurious hotel, airport lounge, high ferro Wait building and platform, family kitchen guarding, office business building etc..Along with the raising of people's living standard, to granite plates Demand grows with each passing day, thus promotes the exploitation in granite mine, processing further, and scale amounts is more and more huger.And open at it Adopt, the course of processing necessarily leads to substantial amounts of stone slurry, granite powder scrap etc., causes serious ring to river, mountains and rivers, stockyard etc. Environment pollution, the secondary disaster such as simultaneously the most easily cave in, causes bigger potential threat to the people's lives and property.
To this end, people start actively to study the waste residue in granite stone pit carry out again with technology.Chinese invention is special Profit CN1037042A discloses a kind of inorganic artificial granite production technology, is primarily characterized in that: first with alumina cement, stone Sand, inorganic pigment powder, glycerol and water mixing furnishing thin pulp shape mill base, pour in shaping frame, after initial set, with high silicon water Mud, quartz sand, quartz, inorganic pigment powder, glycerol and water, mix furnishing thin pulp shape coat of colo(u)r, brokenly on color paste layer Portion, then add water after stirring with alumina cement, river sand, rubble, it is cast in shaping frame, as reinforcing after machinery shakes Layer, is finally putting into pond and soaks maintenance molding in 72 hours, then through ageing-resistant pickling processes, oil and can become product.
Chinese invention patent CN1035812A disclose a kind of high intensity, indeformable, do not chap, best bright finish, performance steady Fixed, the manufacture method of high-quality full-inorganic artificial marble, is primarily characterized in that: with water mud as a raw material, adds the most inorganic Auxiliary agent composition body, colored to vibrate in the ready made one-tenth flower agent addition body having special component, in water, maintenance crystallizes into Goods.
Chinese invention patent CN1088146A discloses a kind of high alumina cement artificial granite, marble and production work thereof Skill, is primarily characterized in that: use diffusant, Burnt ammonium alum, concentrated sulphuric acid, magnesium sulfate, Colophonium, ferrous sulfate, oxalic acid, boric acid and Triethanolamine and water, be 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 Become surface layer and bottom, spread out and put on surface layer top after having one to stir with cement, silica flour and fabric water between surface layer and bottom Basic unit, its maintenance uses wet saw end to carry out.
It is known that epoxy resin has many excellent performances: the adhesive property that (1) is good: adhesive strength is high, bonding Wide, it and many metals (such as ferrum, steel, copper, aluminum, metal alloy etc.) or nonmetallic materials are (such as glass, pottery, timber, plastics Deng) adhesive strength the highest, have even more than by the intensity of viscous material itself, therefore can be used for many stress members In, it is one of the main component of structural adhesive；(2) good processing characteristics: the motility of Formulaion of epoxy resin, processing work The multiformity of skill and product properties is the most prominent in macromolecular material；(3) good stability: the solidification of epoxy resin Mainly relying on the ring opening polyaddition of epoxy radicals, therefore do not produce low-molecular material in solidification process, its cure shrinkage is heat One of kind minimum in thermosetting resin, generally 1%-2%, if selecting suitable filler that shrinkage factor can be made to be down to 0.2% Left and right；Epoxy main chains after solidification is ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore has the resistance to acids and bases of excellence.
Therefore, epoxy resin is widely used in the every field of national economy: either high-technology field is still Field of general technology, either all 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 is open a kind of high temperature resistant without molten The preparation method of agent epoxy adhesive, is primarily characterized in that: TGBDAPP epoxy resin, toughener, hydrogenated bisphenol A, solidification Agent, accelerator mix homogeneously, prepared heat-resistant solvent-free epoxy adhesive.But its resistance to elevated temperatures still has bigger limitation Property, fail to meet the actual application under many hot environments.
Chinese patent CN101397486A discloses the preparation method of a kind 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 Carboxy terminated nitrile rubber；B component is double (2,4-diamino phenoxy) the benzene aromatic polyvalent amine hardener 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- 15-20% (the quality that addition is novolac epoxy resin of double (2,4-diamino phenoxy) benzene aromatic polyvalent amine hardener Percent), gained adhesive system good manufacturability.But its heat resistance is the most preferable.
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: use Isosorbide-5-Nitrae-bis-(2,4-dimaleimide phenoxyl) benzene Four maleimide resins and polyfunctional epoxy resin, nbr carboxyl terminal CTBN react the novel fire resistant obtaining high tenacity Resin, adds organic solvent, and stirring and dissolving is uniform, obtains the viscous liquid of homogeneous phase transparent, i.e. component A；Firming agent is with organic Solvent mixes, and stirring and dissolving is uniform, obtains B component；A, B component are mixed, stirs, obtain used for advanced composite material Heat resist modification multi-functional epoxy's substrate resin solution.
Yu Xinhai et al. [development [J] of high-temperature resistant single-component epoxy adhesive. bonding, 2008,29 (12): 16-19] public Open the preparation method of a kind of high-temperature resistant single-component epoxy adhesive, be primarily characterized in that: with maleic anhydride (MA) for end-blocking Agent, with 2, double (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) of 2-, 2, double [4-(4-amino-benzene oxygen) phenyl] third of 2- Double [4-(3,4-di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA) of alkane (BAPOPP), 2,2-is that main material synthesis obtains Phenolic hydroxy group polyetherimide resin (HPEI)；It it is resistant, toughened dose with the synthesized HPEI obtained, with N, N, N', N'-tetra- Glycidyl-4,4'-MDA (TGBDAPP), 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.
Summary of the invention
The technical problem to be solved is to provide a kind of BDAPP type granolith sheet material and preparation method thereof, In the method, sheet material raw material sources are convenient, and production technology is simple, and solvent-free, environmental friendliness, product combination property is superior, Ke Yiguang General it is applied to building materials field, waits building and platform, family kitchen guarding, office including high-grade hotel, airport lounge, high ferro Business buildings etc., have good market application foreground.Additionally, granite powder derives from the garbage in granite stone pit, Can be turned waste into wealth by the technology of the present invention, comprehensive environmental improvement etc. is respectively provided with very important realistic meaning.
A kind of BDAPP type granolith sheet material of the present invention, described granite plates is 100:5-10's by mass ratio Granite powder and BDAPP type resin composition；Wherein, BDAPP type resin is the ring of 100:2-4:10-20:10-30 by mass ratio Double [4-(2,4-diamino phenoxy) phenyl] propane BDAPP, the latent curing agent LRC30 of epoxy resins, 2,2-and liquid anhydride Composition.
Described epoxy resin be E-51 epoxy resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 epoxy resin, CE793 epoxy resin, glycidyl amine type epoxy resin, diglycidyl ether type epoxy resin, alicyclic type epoxy resin, phenol aldehyde type At least one in epoxy resin, glycidyl ester type epoxy resin.
Described glycidyl amine type epoxy resin is N, N, N ', N '-four glycidyl group-4,4 '-MDA Epoxy resin, N, N, N ', N '-four glycidyl group-3,3 '-dimethyl-4,4 '-MDA epoxy resin, N, N, N ', N '-four glycidyl group-3,3 '-diethyl-4,4 '-MDA epoxy resin, N, N, N ', N '-four shrinks sweet Oil base-3,3 '-two chloro-4,4 '-MDA epoxy resin, N, N, N ', N '-four glycidyl group-4,4 ' and-diaminourea Diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-DADPS epoxy resin, N, N, N ', N '-four Glycidyl-3,4 '-diaminodiphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-3,3 '-DADPS Epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-benzidine epoxy resin, N, N, N ', N '-four (+)-2,3-Epoxy-1-propanol Base p-phenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group m-diaminobenzene. epoxy resin, N, N, N ', N '-four shrinks sweet Oil base-1,4-double (4-amino-benzene oxygen) phenyl ring epoxy resins, N, N, N ', double (the 3-aminobenzene oxygen of N '-four glycidyl group-1,4- Base) phenyl ring epoxy resins, N, N, N ', N '-four glycidyl group-1,3-double (4-amino-benzene oxygen) phenyl ring epoxy resins, N, N, N ', N '-four glycidyl group-1,3-double (3-amino-benzene oxygen) phenyl ring epoxy resins, N, N, N ', N '-four glycidyl group-1,4-is double (2-trifluoromethyl-4-aminophenoxyl) phenyl ring epoxy resins, N, N, N ', N '-four glycidyl group-1,3-pair (2-trifluoromethyl- 4-amino-benzene oxygen) phenyl ring epoxy resins, N, N, N ', N ', O-five glycidyl-4,4 '-diaminourea-4 "-hydroxyl tritan. Epoxy resin, N, N, N ', N '-four glycidyl group-2,2-double [4-(4-amino-benzene oxygen) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group-2,2-double [4-(4-amino-benzene oxygen) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four Glycidyl-2,2-double [4-(3-amino-benzene oxygen) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group-2, 2-double [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group-2,2- Double [4-(3-amino-benzene oxygen) phenyl] HFC-236fa epoxy resin, N, N, N ', the double [4-(2-of N '-four glycidyl group-2,2- Trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4- Amino-benzene oxygen) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(2-trifluoromethyl-4-aminobenzenes Epoxide) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulphone (DPS) asphalt mixtures modified by epoxy resin Fat, N, N, N ', N '-four glycidyl group-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfide epoxy resin, N, N, N ', N '-four (+)-2,3-Epoxy-1-propanol Base-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group-4,4 ' and-bis-(2-fluoroforms Base-4-amino-benzene oxygen) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4-amino-benzene oxygens) Benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4,4 ' and-bis-(2-trifluoromethyl-4-aminophenoxyl) hexichol Ketone epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4-amino-benzene oxygen) biphenyl epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl epoxy resin, N, N, N ', N ', O, O '- Six glycidyl-2,2-double (3-amino-4-hydroxylphenyl) HFC-236fa epoxy resin, N, N, O triglycidyl group is to ammonia Base phenol epoxy resin, N, at least one in N, O triglycidyl meta-aminophenol epoxy resin.
Described diglycidyl ether type epoxy resin is 1,3-diglycidyl resorcinol, 1,4-diglycidyl pair Double (4-glycidyl phenyl) HFC-236fa of Benzodiazepines, 4,4 '-diglycidyl bisphenol S, 2,2-, 2,2-are double, and (4-shrinks Glyceryl cyclohexyl) propane, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, At least one in fatty alcohol polyglycidyl ether.
Described alicyclic type epoxy resin is 3,4-epoxycyclohexyethylSiOi acid-3 ', 4 '-epoxycyclohexyethylSiOi methyl ester, 3,4-epoxy radicals- 6-methyl cyclohexane acid-3 ', 4 '-epoxy radicals-6 '-methyl cyclohexane methyl ester, 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl At least one in ester, Dipentenedioxide.
Described phenol aldehyde type epoxy resin is P-F phenolic resin type epoxy resin, o-cresol-formaldehyde phenolic resin Type epoxy resin, resorcinol-formaldehyde phenolic resin type epoxy resin, m-cresol-formaldehyde phenolic resin type epoxy resin, neighbour Benzodiazepines-formaldehyde phenolic resin type epoxy resin, bisphenol A-formaldehyde phenolic resin type epoxy resin, bisphenol S-formaldehyde phenolic resin Type epoxy resin, bisphenol AF-formaldehyde phenolic resin type epoxy resin, '-biphenyl diphenol-formaldehyde phenolic resin type epoxy resin, adjacent benzene At least one in base P-F phenolic resin type epoxy resin, naphthols-formaldehyde phenolic resin type epoxy resin.
Described glycidyl ester type epoxy resin is terephthalic acid diglycidyl ester epoxy resin, M-phthalic acid two Ethylene oxidic ester epoxy resin, o-phthalic acid diglycidyl ester epoxy resin, interior methine tetrahydrophthalic acid two contract Water glyceride epoxy resin, 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl ester epoxy resin, adjacent benzene two octanoic acid bicyclo- At least one in oxygen propyl ester epoxy resin.
Described liquid anhydride is THPA, methyl tetrahydro phthalic anhydride, HHPA, dodecyl succinic anhydride, eleostearic acid Acid anhydride, with Oleum Terebinthinae and at least one in the liquid anhydride of maleic acid anhydride reactant.
Described granite powder is the garbage in granite stone pit, after removing mud, processing except ferrum, silane coupler surface The dried powder obtained.
A kind of BDAPP type granolith preparation of plates method of the present invention, including:
(1) by epoxy resin and 2, double [4-(2,4-diamino phenoxy) phenyl] the propane BDAPP of 2-puts in reactor, Stirring mixing, in 115 DEG C-125 DEG C reaction 0.5-1 hour after, be cooled to less than 60 DEG C, add latent curing agent LRC30 and Liquid anhydride, is uniformly mixed, and obtains BDAPP type resin；Wherein, epoxy resin, 2, double [4-(2, the 4-diaminobenzene oxygen of 2- Base) phenyl] mass ratio of propane BDAPP, latent curing agent LRC30 and liquid anhydride is 100:2-4:10-20:10-30；
(2), after BDAPP type resin being mixed homogeneously with granite powder, put in stainless steel flat plate frame, pressing preforming, Heat-pressure curing molding；Wherein, the temperature range of heating is that room temperature is to 180 DEG C；Pressurization pressure limit be 0.5MPa extremely 5MPa；Hardening time is 2-5 hour；The mass ratio of granite powder and BDAPP type resin is 100:5-10.
Beneficial effect
(1) preparation technology of the present invention is simple, low cost, easy to operate, raw material sources are convenient, can be in common apparatus Complete preparation process, be advantageously implemented industrialized production；
(2) the BDAPP type resin of the present invention has good combination property；
(3) present invention is solvent-free, environmental friendliness, and product combination property is superior, can be widely applied to building materials field, including High-grade hotel, airport lounge, high ferro are waited building and platform, family kitchen guarding, office business building etc., have good Market application foreground；Additionally, the granite powder of the present invention derives from the garbage in granite stone pit, pass through the technology of the present invention Can turn waste into wealth, comprehensive environmental improvement etc. is respectively provided with very important realistic meaning.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited Scope.
Embodiment 1
By 100 grams of hydrogenated bisphenol A diglycidyl ethers, 280 grams of N, N, N ', N '-four glycidyl group-4,4 '-diaminourea Diphenyl ether epoxy resin, 180 grams of E-44 epoxy resin, 230 grams of 1,3-diglycidyl resorcinol type epoxy, 210 grams N, N, O triglycidyl group para-aminophenol epoxy resin adds in reactor, after being uniformly mixed, adds 20 gram 2,2- Double [4-(2,4-diamino phenoxy) phenyl] propane (BDAPP), stirring mixing, after 115 DEG C of reactions 1 hour, it is cooled to 60 Below DEG C, add 150 grams of latent curing agent LRC30, add 100 grams of dodecyl succinic anhydrides and 100 grams of tung oil acid anhydrides Liquid anhydride, be uniformly mixed, obtain the BDAPP type resin of 1370 grams, be denoted as BDAPP-1.
Embodiment 2
By 120 grams of hydrogenated bisphenol A diglycidyl ethers, 100 grams of N, N, N ', N '-four glycidyl group-4,4 '-diaminourea Diphenyl ether epoxy resin, 280 grams of CE793 epoxy resin, 320 grams of N, N, N ', N '-four glycidyl group-4,4 ' and-diaminourea hexichol Methane type epoxy resins, 180 grams of o-phthalic acid diglycidyl ester epoxy resin add in reactor, after being uniformly mixed, Add 30 gram 2, double [4-(2, the 4-diamino phenoxy) phenyl] propane (BDAPP) of 2-, stirring mixing, react 1 hour in 120 DEG C After, it is cooled to less than 60 DEG C, adds 100 grams of latent curing agent LRC30, add the liquid anhydride of 300 grams of HHPAs, stir Mix mix homogeneously, obtain the BDAPP type resin of 1430 grams, be denoted as BDAPP-2.
Embodiment 3
By 200 grams of hydrogenated bisphenol A diglycidyl ethers, 300 grams of N, N, N ', N '-four glycidyl group-4,4 '-diaminourea Diphenyl ether epoxy resin, 50 grams of 1,3-diglycidyl resorcinol type epoxy, 300 grams of o-cresol-formaldehyde novolac trees Epoxy-type epoxy resin, 150 gram 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl ester adds in reactor, stirring mixing After Jun Yun, add 40 gram 2, double [4-(2, the 4-diamino phenoxy) phenyl] propane (BDAPP) of 2-, stirring mixing, anti-in 125 DEG C After answering 0.5 hour, be cooled to less than 60 DEG C, add 200 grams of latent curing agent LRC30, add 40 grams of methyl tetrahydro phthalic anhydrides, 20 grams of tung oil acid anhydrides and 40 grams of dodecyl succinic anhydrides, be uniformly mixed, and obtains the BDAPP type resin of 1340 grams, is denoted as BDAPP-3。
Embodiment 4
Take BDAPP-1～the BDAPP-3 resin of appropriate above-described embodiment 1～embodiment 3, and difference even application is in standard In rustless steel test piece and glass pieces of cloth, after hanging under room temperature 1 hour overlap, clamping (glass pieces of cloth 2 standard stainless steel substrates it Between, only lap-joint is resinous), put in convection oven and solidify: be heated to 110 DEG C from room temperature, be incubated 1 hour, continue It is warming up to 150 DEG C, is incubated 1 hour, is continuously heating to 180 DEG C, be incubated 2 hours, naturally cool to room temperature.Record tensile shear strong Degree is as shown in table 1.
Take BDAPP-1～the BDAPP-3 resin of appropriate above-described embodiment 1～embodiment 3, pour the stainless of a diameter of 10cm into In steel disk (disk coats releasing agent in advance), heat cure: be heated to 110 DEG C from room temperature, it is incubated 1 hour, is continuously heating to 150 DEG C, it is incubated 1 hour, is continuously heating to 180 DEG C, be incubated 2 hours, naturally cool to room temperature.Obtain thickness about 1mm, diameter 10cm Circular specimen, after distilled water immersion 72 hours, survey its water absorption rate, result is as shown in table 1.
Take BDAPP-1～the BDAPP-3 resin of appropriate above-described embodiment 1～embodiment 3, and difference even application is in standard On flat glass film, overlap after hanging under room temperature 1 hour, clamping, put in convection oven and solidify: be heated to from room temperature 110 DEG C, it is incubated 1 hour, is continuously heating to 150 DEG C, be incubated 1 hour, be continuously heating to 180 DEG C, be incubated 2 hours, natural cooling To room temperature.Record tensile shear strength as shown in table 1.
The tensile shear strength of table 1 BDAPP type resin and water absorption rate
Embodiment 5
After 10 grams of BDAPP-1 resins and 200 grams of granite powder mix homogeneously, put in stainless steel flat plate frame, pressing Preforming, in tabular, heat-pressure curing molding；Wherein, the temperature range of heating is that room temperature is to 180 DEG C；The pressure of pressurization Scope is 0.5MPa to 5MPa；Hardening time is 2-5 hour, and the sheet material obtained is denoted as BC-1, surveys its performance, as shown in table 2.
After 17 grams of BDAPP-2 resins and 200 grams of granite powder mix homogeneously, put in stainless steel flat plate frame, pressing Preforming, in tabular, heat-pressure curing molding；Wherein, the temperature range of heating is that room temperature is to 180 DEG C；The pressure of pressurization Scope is 0.5MPa to 5MPa；Hardening time is 2-5 hour, and the sheet material obtained is denoted as BC-2, surveys its performance, as shown in table 2.
After 6 grams of BDAPP-1 resins, 9 grams of BDAPP-3 resins and 200 grams of granite powder mix homogeneously, put into rustless steel In flat board frame, pressing preforming, in tabular, heat-pressure curing molding；Wherein, the temperature range of heating is that room temperature is to 180 ℃；The pressure limit of pressurization is 0.5MPa to 5MPa；Hardening time is 2-5 hour, and the sheet material obtained is denoted as BC-3, surveys its property Can, as shown in table 2.
By 5 grams of BDAPP-3 resins, 10 grams of BDAPP-1 resins, 5 grams of BDAPP-2 resins and 200 grams of granite powder mixing After Jun Yun, put in stainless steel flat plate frame, pressing preforming, in tabular, heat-pressure curing molding；Wherein, the temperature of heating Degree scope is that room temperature is to 180 DEG C；The pressure limit of pressurization is 0.5MPa to 5MPa；Hardening time is 2-5 hour, the sheet material obtained It is denoted as BC-4, surveys its performance, as shown in table 2.
The source of above-mentioned granite powder: the garbage in granite stone pit, through removing mud, except ferrum, silane coupler surface The dried powder obtained after process.
The performance of table 2 granolith plate
Sample BC-1 BC-2 BC-3 BC-4
Compressive strength, MPa/25 DEG C) 278 279 271 275
Water absorption rate, MPa/25 DEG C) 0.16 0.15 0.13 0.17
Bending strength, MPa (/ 25 DEG C) 21.4 21.5 22.2 21.7
Bending strength, MPa (/ 170 DEG C) 19.2 18.7 19.7 20.1
Bulk density, g/cm3(/25℃) 2.77 2.70 2.71 2.73

Claims (10)

1. a BDAPP type granolith sheet material, it is characterised in that described granite plates is 100:5-10's by mass ratio Granite powder and BDAPP type resin composition；Wherein, BDAPP type resin is the ring of 100:2-4:10-20:10-30 by mass ratio Double [4-(2,4-diamino phenoxy) phenyl] propane BDAPP, the latent curing agent LRC30 of epoxy resins, 2,2-and liquid anhydride Composition.
A kind of BDAPP type granolith sheet material the most according to claim 1, it is characterised in that described epoxy resin is E-51 epoxy resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 epoxy resin, CE793 epoxy resin, (+)-2,3-Epoxy-1-propanol Amine type epoxy resin, diglycidyl ether type epoxy resin, alicyclic type epoxy resin, phenol aldehyde type epoxy resin, glycidyl ester type At least one in epoxy resin.
A kind of BDAPP type granolith sheet material the most according to claim 2, it is characterised in that described glycidyl amine Type epoxy resin is N, N, N ', N '-four glycidyl group-4,4 '-MDA epoxy resin, N, N, N ', N '-four contracts Water glyceryl-3,3 '-dimethyl-4,4 '-MDA epoxy resin, N, N, N ', N '-four glycidyl group-3,3 '- Diethyl-4,4 '-MDA epoxy resin, N, N, N ', N '-chloro-4,4 '-diamino of four glycidyl group-3,3 '-two Base diphenyl-methane 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-diaminobenzene. epoxy resin, N, N, N ', double (the 4-aminobenzene oxygen of N '-four glycidyl group-1,4- Base) phenyl ring epoxy resins, N, N, N ', N '-four glycidyl group-1,4-double (3-amino-benzene oxygen) phenyl ring epoxy resins, N, N, N ', N '-four glycidyl group-1,3-double (4-amino-benzene oxygen) phenyl ring epoxy resins, N, N, N ', N '-four glycidyl group-1,3-is double (3-amino-benzene oxygen) phenyl ring epoxy resins, N, N, N ', the double (2-trifluoromethyl-4-aminobenzene oxygen of N '-four glycidyl group-1,4- Base) phenyl ring epoxy resins, N, N, N ', double (2-trifluoromethyl-4-aminophenoxyl) the phenyl ring oxygen tree of N '-four glycidyl group-1,3- Fat, N, N, N ', N ', O-five glycidyl-4,4 '-diaminourea-4 "-hydroxyl tritan. epoxy resin, N, N, N ', N '-four Glycidyl-2,2-double [4-(4-amino-benzene oxygen) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group-2, 2-double [4-(4-amino-benzene oxygen) phenyl] HFC-236fa epoxy resin, N, N, N ', the double [4-of N '-four glycidyl group-2,2- (3-amino-benzene oxygen) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group-2,2-double [4-(2-trifluoromethyl- 4-amino-benzene oxygen) phenyl] propane epoxy resin, N, N, N ', the double [4-(3-amino-benzene oxygen) of N '-four glycidyl group-2,2- Phenyl] HFC-236fa epoxy resin, N, N, N ', the double [4-(2-trifluoromethyl-4-aminobenzene oxygen of N '-four glycidyl group-2,2- Base) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4-amino-benzene oxygen) hexichol ether ring Epoxy resins, N, N, N ', N '-four glycidyl group-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four shrinks sweet Oil base-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4,4 ' and-bis-(2-fluoroforms Base-4-amino-benzene oxygen) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4-amino-benzene oxygens) Diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group-4,4 ' and-bis-(2-trifluoromethyl-4-aminophenoxyl) hexichol Methane type epoxy resins, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4-amino-benzene oxygen) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4-amino-benzene oxygen) biphenyl epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl epoxy resin, N, N, N ', N ', O, O '-six glycidyl-2,2-is double (3-amino-4-hydroxylphenyl) HFC-236fa epoxy resin, N, N, O triglycidyl group para-aminophenol epoxy resin, N, N, At least one in O triglycidyl meta-aminophenol epoxy resin.
A kind of BDAPP type granolith sheet material the most according to claim 2, it is characterised in that described glycidyl ether Type epoxy resin is 1,3-diglycidyl resorcinol, 1,4-diglycidyl hydroquinone, 4,4 '-2-glycidyl Double (4-glycidyl phenyl) HFC-236fa of base bisphenol S, 2,2-, 2,2-double (4-glycidyl cyclohexyl) propane, Bisphenol F In diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, fatty alcohol polyglycidyl ether extremely Few one.
A kind of BDAPP type granolith sheet material the most according to claim 2, it is characterised in that described alicyclic ring type epoxy Resin is 3,4-epoxycyclohexyethylSiOi acid-3 ', 4 '-epoxycyclohexyethylSiOi methyl ester, 3,4-epoxy radicals-6-methyl cyclohexane acid-3 ', 4 '-ring Epoxide-6 '-methyl cyclohexane methyl ester, 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl ester, in Dipentenedioxide extremely Few one.
A kind of BDAPP type granolith sheet material the most according to claim 2, it is characterised in that described phenolic epoxy Resin is P-F phenolic resin type epoxy resin, o-cresol-formaldehyde phenolic resin type epoxy resin, resorcinol-first Aldehyde 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 phenolic resin type epoxy resin, bisphenol AF-first Aldehyde phenolic resin type epoxy resin, '-biphenyl diphenol-formaldehyde phenolic resin type epoxy resin, o-phenyl phenol-formaldehyde phenolic resin At least one in type epoxy resin, naphthols-formaldehyde phenolic resin type epoxy resin.
A kind of BDAPP type granolith sheet material the most according to claim 2, it is characterised in that described ethylene oxidic ester Type epoxy resin is terephthalic acid diglycidyl ester epoxy resin, Diglycidyl M-phthalate epoxy resin, neighbour Phthalic acid 2-glycidyl ester epoxy resin, interior methine tetrahydrophthalic acid 2-glycidyl ester epoxy resin, 4,5- In 7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl ester epoxy resin, adjacent benzene two octanoic acid diglycidyl ether epoxy resin extremely Few one.
A kind of BDAPP type granolith sheet material the most according to claim 1, it is characterised in that described liquid anhydride is THPA, methyl tetrahydro phthalic anhydride, HHPA, dodecyl succinic anhydride, tung oil acid anhydride, with Oleum Terebinthinae and maleic acid At least one in the liquid anhydride of anhydride reactant.
A kind of BDAPP type granolith sheet material the most according to claim 1, it is characterised in that described granite powder For the garbage in granite stone pit, the dried powder obtained after removing mud, processing except ferrum, silane coupler surface.
10. a BDAPP type granolith preparation of plates method, including:
(1) by epoxy resin and 2, double [4-(2,4-diamino phenoxy) phenyl] the propane BDAPP of 2-stirs mixing, 115 DEG C- 125 DEG C are reacted 0.5-1 hour, are cooled to less than 60 DEG C, add latent curing agent LRC30 and liquid anhydride, stirring, obtain BDAPP type resin；Wherein, epoxy resin, 2, double [4-(2,4-diamino phenoxy) phenyl] the propane BDAPP of 2-, latency are solid The mass ratio of agent LRC30 and liquid anhydride is 100:2-4:10-20:10-30；
(2) being mixed homogeneously with granite powder by the BDAPP type resin in step (1), pressing preforming, heat-pressure curing becomes Type；Wherein, the temperature of heating is that room temperature is to 180 DEG C；The pressure of pressurization is 0.5MPa to 5MPa；Hardening time is 2-5 hour；Flower The mass ratio of rock dust end, hilllock and BDAPP type resin is 100:5-10.
CN201610578960.5A 2016-07-21 2016-07-21 A kind of BDAPP type granolith sheet material and preparation method thereof Pending CN106220042A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0368661A (en) * 1989-08-09 1991-03-25 Kuraray Co Ltd Marbled plastic molding having mottled pattern and production thereof
CN104446138A (en) * 2014-11-11 2015-03-25 济南大学 Method for preparing epoxy resin based artificial granite from GFRP waste
CN104559059A (en) * 2014-12-26 2015-04-29 东华大学 High-temperature-resistant matrix resin for high-Tg copper-clad plate and preparation method of high-temperature-resistant matrix resin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0368661A (en) * 1989-08-09 1991-03-25 Kuraray Co Ltd Marbled plastic molding having mottled pattern and production thereof
CN104446138A (en) * 2014-11-11 2015-03-25 济南大学 Method for preparing epoxy resin based artificial granite from GFRP waste
CN104559059A (en) * 2014-12-26 2015-04-29 东华大学 High-temperature-resistant matrix resin for high-Tg copper-clad plate and preparation method of high-temperature-resistant matrix resin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王孟钟: "《胶粘剂应用手册》", 30 November 1987, 化学工业出版社 *

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Application publication date: 20161214