CN106277931A - A kind of BAPP type granolith sheet material and preparation method thereof - Google Patents

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

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Publication number
CN106277931A
CN106277931A CN201610578936.1A CN201610578936A CN106277931A CN 106277931 A CN106277931 A CN 106277931A CN 201610578936 A CN201610578936 A CN 201610578936A CN 106277931 A CN106277931 A CN 106277931A
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epoxy resin
type
bapp
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 CN201610578936.1A priority Critical patent/CN106277931A/en
Publication of CN106277931A publication Critical patent/CN106277931A/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
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • 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)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention relates to a kind of BAPP 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 BAPP type resin.Preparation method includes: mixed with BAPP 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 BAPP type resin；BAPP 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 BAPP 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 BAPP type granolith plate 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: TGBAPP epoxy resin, toughener, hydrogenated bisphenol A, firming agent, Accelerator mix homogeneously, has prepared heat-resistant solvent-free epoxy adhesive.But its resistance to elevated temperatures still has bigger limitation, 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 (TGBAPP), 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 BAPP type granolith sheet material and preparation method thereof, should In method, sheet material raw material sources are convenient, and production technology is simple, and solvent-free, environmental friendliness, product combination property is superior, can be extensive It is applied to building materials field, waits building with platform, family kitchen guarding, handle official business business 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, logical Cross the technology of the present invention can turn waste into wealth, comprehensive environmental improvement etc. is respectively provided with very important realistic meaning.
A kind of BAPP type granolith sheet material of the present invention, described granite plates is the flower of 100:5-10 by mass ratio Rock dust end, hilllock and BAPP type resin form；Wherein, BAPP type resin is the asphalt mixtures modified by epoxy resin of 100:2-4:10-20:10-30 by mass ratio Double [4-(4-amino-benzene oxygen) phenyl] propane BAPP, the latent curing agent LRC30 of fat, 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 BAPP type granolith preparation of plates method of the present invention, including:
(1) by epoxy resin and 2, double [4-(4-amino-benzene oxygen) phenyl] the propane BAPP of 2-puts in reactor, stirring Mixing, after 115 DEG C-125 DEG C reactions 0.5-1 hour, is cooled to less than 60 DEG C, adds latent curing agent LRC30 and liquid Anhydride, is uniformly mixed, and obtains BAPP type resin；Wherein, epoxy resin, 2, double [4-(4-amino-benzene oxygen) phenyl] third of 2- The mass ratio of alkane BAPP, latent curing agent LRC30 and liquid anhydride is 100:2-4:10-20:10-30；
(2), after BAPP 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 BAPP 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 BAPP 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
', N '-four glycidyl group-4,4 '-diaminodiphenyl ether epoxy resin, 300 grams of E-44 epoxies by 200 grams of N, N, N Resin, 350 grams of 1,3-diglycidyl resorcinol type epoxy, 150 grams of N, N, O triglycidyl group para-aminophenol Epoxy resin adds in reactor, after being uniformly mixed, adds 20 gram 2, double [4-(4-amino-benzene oxygen) phenyl] propane of 2- (BAPP), stirring mixing, after 115 DEG C of reactions 1 hour, it is cooled to less than 60 DEG C, adds 150 grams of latent curing agent LRC30, Add the liquid anhydride of 100 grams of dodecyl succinic anhydrides and 100 grams of tung oil acid anhydrides, be uniformly mixed, obtain 1370 grams BAPP type resin, be denoted as BAPP-1.
Embodiment 2
', N '-four glycidyl group-4,4 '-diaminodiphenyl ether epoxy resin, 380 grams of CE793 rings by 120 grams of N, N, N Epoxy resins, 220 grams of N, N, N ', N '-four glycidyl group-4,4 '-MDA epoxy resin, 280 grams of O-phthalics Acid 2-glycidyl ester epoxy resin adds in reactor, after being uniformly mixed, adds 30 gram 2, double [4-(the 4-aminobenzene of 2- Epoxide) phenyl] propane (BAPP), stirring mixing, after 120 DEG C of reactions 1 hour, it is cooled to less than 60 DEG C, adds 100 grams and hide Property firming agent LRC30, adds the liquid anhydride of 300 grams of HHPAs, is uniformly mixed, obtain the BAPP type tree of 1430 grams Fat, is denoted as BAPP-2.
Embodiment 3
By 200 grams of N, N, N, ', N '-four glycidyl group-4,4 '-diaminodiphenyl ether epoxy resin, 150 grams of 1,3-bis-contract Water glyceryl resorcinol type epoxy, 150 grams of N, N, O triglycidyl meta-aminophenol epoxy resin, 300 grams of adjacent first P-F phenolic resin type epoxy resin, 200 grams of 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl esters add anti- Answering in still, after being uniformly mixed, add 40 gram 2, double [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-, stirring is mixed Close, after 125 DEG C of reactions 0.5 hour, be cooled to less than 60 DEG C, add 200 grams of latent curing agent LRC30, add 30 grams Methyl tetrahydro phthalic anhydride, 10 grams of tung oil acid anhydrides and 60 grams of dodecyl succinic anhydrides, be uniformly mixed, obtain the BAPP of 1340 grams Type resin, is denoted as BAPP-3.
Embodiment 4
Take BAPP-1～the BAPP-3 resin of appropriate above-described embodiment 1～embodiment 3, and difference even application is in standard not Rust steel test piece and glass pieces of cloth on, 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 BAPP-1～the BAPP-3 resin of appropriate above-described embodiment 1～embodiment 3, pour the rustless steel of a diameter of 10cm into In 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 BAPP-1～the BAPP-3 resin of appropriate above-described embodiment 1～embodiment 3, and even application is put down in standard respectively On glass sheet sheet, overlap after hanging under room temperature 1 hour, clamping, put in convection oven and solidify: be heated to 110 from room temperature 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, naturally cool to room Temperature.Record tensile shear strength as shown in table 1.
The tensile shear strength of table 1BAPP type resin and water absorption rate
Sample BAPP-1 BAPP-2 BAPP-3
Water absorption rate, % 0.31 0.30 0.27
Tensile shear strength (rustless steel test piece and glass pieces of cloth), MPa (/ 25 DEG C) 29.2 28.8 29.3
Hot strength (rustless steel test piece and glass pieces of cloth), MPa (/ 170 DEG C) 25.1 25.3 25.7
Tensile shear strength (flat glass film), MPa (/ 25 DEG C) 23.2 23.7 25.6
Hot strength (flat glass film), MPa (/ 170 DEG C) 20.1 21.2 21.7
Embodiment 5
After 10 grams of BAPP-1 resins and 200 grams of granite powder mix homogeneously, putting in stainless steel flat plate frame, pressing is pre- Molding, in tabular, heat-pressure curing molding；Wherein, the temperature range of heating is that room temperature is to 180 DEG C；The pressure model of pressurization Enclose for 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 BAPP-2 resins and 200 grams of granite powder mix homogeneously, putting in stainless steel flat plate frame, pressing is pre- Molding, in tabular, heat-pressure curing molding；Wherein, the temperature range of heating is that room temperature is to 180 DEG C；The pressure model of pressurization Enclose for 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 BAPP-1 resins, 9 grams of BAPP-3 resins and 200 grams of granite powder mix homogeneously, put into rustless steel and put down In sheet 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 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 performance, as Shown in table 2.
By 5 grams of BAPP-3 resins, 10 grams of BAPP-1 resins, 5 grams of BAPP-2 resins and 200 grams of granite powder mix homogeneously After, put in stainless steel flat plate frame, pressing preforming, in tabular, heat-pressure curing molding；Wherein, the temperature model of heating Enclose for room temperature to 180 DEG C；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-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) 317 311 309 314
Water absorption rate, MPa (/ 25 DEG C) 0.13 0.18 0.10 0.15
Bending strength, MPa (/ 25 DEG C) 29.2 29.7 29.5 28.6
Bending strength, MPa (/ 170 DEG C) 24.1 23.2 23.1 23.8
Bulk density, g/cm3(/25℃) 2.81 2.80 2.83 2.81

Claims (10)

1. a BAPP type granolith sheet material, it is characterised in that described granite plates is 100:5-10's by mass ratio Granite powder and BAPP type resin composition；Wherein, BAPP type resin is the epoxy of 100:2-4:10-20:10-30 by mass ratio Double [4-(4-amino-benzene oxygen) phenyl] propane BAPP, the latent curing agent LRC30 of resin, 2,2-and liquid anhydride composition.
A kind of BAPP 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, glycidyl amine Type epoxy resin, diglycidyl ether type epoxy resin, alicyclic type epoxy resin, phenol aldehyde type epoxy resin, glycidyl ester type ring At least one in epoxy resins.
A kind of BAPP type granolith sheet material the most according to claim 2, it is characterised in that described glycidic amine type Epoxy resin is N, N, N ', N '-four glycidyl group-4,4 '-MDA epoxy resin, N, N, N ', N '-four shrinks Glyceryl-3,3 '-dimethyl-4,4 '-MDA epoxy resin, N, N, N ', N '-four glycidyl group-3,3 '-two Ethyl-4,4 '-MDA epoxy resin, N, N, N ', N '-chloro-4,4 '-diaminourea of four glycidyl group-3,3 '-two 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 hexichol Ether ring epoxy resins, N, N, N ', N '-four glycidyl group-3,3 '-DADPS epoxy resin, N, N, N ', N '-four shrinks Glyceryl-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 (4-amino-benzene oxygen) benzene of N '-four glycidyl group-1,4- Epoxy resin, N, N, N ', N '-four glycidyl group-1,4-double (3-amino-benzene oxygen) phenyl ring epoxy resins, N, N, N ', N '-four contracts Water glyceryl-1,3-double (4-amino-benzene oxygen) phenyl ring epoxy resins, N, N, N ', double (the 3-amino of N '-four glycidyl group-1,3- Phenoxy group) phenyl ring epoxy resins, N, N, N ', double (2-trifluoromethyl-4-aminophenoxyl) phenyl ring of N '-four glycidyl group-1,4- Epoxy resins, N, N, N ', N '-four glycidyl group-1,3-double (2-trifluoromethyl-4-aminophenoxyl) phenyl ring epoxy resins, N, N, N ', N ', O-five glycidyl-4,4 '-diaminourea-4 "-hydroxyl tritan. epoxy resin, N, N, N ', N '-four (+)-2,3-Epoxy-1-propanol Base-2,2-double [4-(4-amino-benzene oxygen) phenyl] propane epoxy resin, N, N, N ', the double [4-of N '-four glycidyl group-2,2- (4-amino-benzene oxygen) phenyl] HFC-236fa epoxy resin, N, N, N ', double [4-(the 3-aminobenzene of N '-four glycidyl group-2,2- Epoxide) phenyl] propane epoxy resin, N, N, N ', the double [4-(2-trifluoromethyl-4-aminobenzene oxygen of N '-four glycidyl group-2,2- Base) phenyl] propane epoxy resin, N, N, N ', double [4-(3-amino-benzene oxygen) phenyl] hexafluoro of N '-four glycidyl group-2,2- Propane epoxy resin, N, N, N ', double [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] six of N '-four glycidyl group-2,2- Fluoro-propane 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-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 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 glycidyl group-4,4 ' and-bis-(2-trifluoromethyl-4-ammonia Phenoxyl) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4,4 '-bis-(4-amino-benzene oxygen) hexichol first Alkane epoxy resin, N, N, N ', N '-four glycidyl group-4,4 ' and-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl-methane ring 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-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 ', double (the 3-ammonia of N ', O, O '-six glycidyl-2,2- Base-4-hydroxy phenyl) HFC-236fa epoxy resin, N, N, O triglycidyl group para-aminophenol epoxy resin, N, N, O tri- At least one in glycidyl m-aminophenol epoxy resin.
A kind of BAPP type granolith sheet material the most according to claim 2, it is characterised in that described diglycidyl ether type Epoxy resin is 1,3-diglycidyl resorcinol, 1,4-diglycidyl hydroquinone, 4,4 '-diglycidyl Double (4-glycidyl phenyl) HFC-236fa of bisphenol S, 2,2-, 2,2-double (4-glycidyl cyclohexyl) propane, Bisphenol F two In glycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, fatty alcohol polyglycidyl ether at least A kind of.
A kind of BAPP type granolith sheet material the most according to claim 2, it is characterised in that described alicyclic ring type asphalt mixtures modified by epoxy resin Fat is 3,4-epoxycyclohexyethylSiOi acid-3 ', 4 '-epoxycyclohexyethylSiOi methyl ester, 3,4-epoxy radicals-6-methyl cyclohexane acid-3 ', 4 '-epoxy Base-6 '-methyl cyclohexane methyl ester, 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl ester, in Dipentenedioxide at least A kind of.
A kind of BAPP type granolith sheet material the most according to claim 2, it is characterised in that described phenolic epoxy tree Fat 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, catechol-formaldehyde phenolic resin type ring Epoxy resins, 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, o-phenyl phenol-formaldehyde phenolic resin type At least one in epoxy resin, naphthols-formaldehyde phenolic resin type epoxy resin.
A kind of BAPP type granolith sheet material the most according to claim 2, it is characterised in that described glycidyl ester type Epoxy resin is terephthalic acid diglycidyl ester epoxy resin, Diglycidyl M-phthalate epoxy resin, adjacent benzene Dioctyl phthalate 2-glycidyl ester epoxy resin, interior methine tetrahydrophthalic acid 2-glycidyl ester epoxy resin, 4,5-ring In oxygen hexamethylene-1,2-dioctyl phthalate 2-glycidyl ester epoxy resin, adjacent benzene two octanoic acid diglycidyl ether epoxy resin at least A kind of.
A kind of BAPP type granolith sheet material the most according to claim 1, it is characterised in that described liquid anhydride is four Hydrogen phthalic anhydride, methyl tetrahydro phthalic anhydride, HHPA, dodecyl succinic anhydride, tung oil acid anhydride, with Oleum Terebinthinae and maleic anhydride At least one in the liquid anhydride of reaction.
A kind of BAPP type granolith sheet material the most according to claim 1, it is characterised in that described granite powder is The garbage in granite stone pit, the dried powder obtained after removing mud, processing except ferrum, silane coupler surface.
10. a BAPP type granolith preparation of plates method, including:
(1) by epoxy resin and 2, double [4-(4-amino-benzene oxygen) phenyl] the propane BAPP of 2-stirs mixing, and 115 DEG C-125 DEG C anti- Answer 0.5-1 hour, be cooled to less than 60 DEG C, add latent curing agent LRC30 and liquid anhydride, stirring, obtain BAPP type tree Fat；Wherein, epoxy resin, 2, double [4-(4-amino-benzene oxygen) phenyl] propane BAPP, the latent curing agent LRC30 of 2-and liquid The mass ratio of anhydride is 100:2-4:10-20:10-30；
(2) being mixed homogeneously with granite powder by the BAPP 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 BAPP type resin is 100:5-10.
CN201610578936.1A 2016-07-21 2016-07-21 A kind of BAPP type granolith sheet material and preparation method thereof Pending CN106277931A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62158152A (en) * 1985-12-30 1987-07-14 武居　二郎 Composition for protective coating
CN103131370A (en) * 2013-03-11 2013-06-05 东华大学 1,3-bis(2,4-diamidophenoxy)benzene high-temperature-resistant epoxy adhesive and preparation method thereof
CN103214793A (en) * 2013-04-22 2013-07-24 东华大学 Advanced composite material matrix resin and preparation method thereof
CN103483553A (en) * 2013-09-17 2014-01-01 东华大学 TGDADPE type epoxy matrix resin for advanced composite material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62158152A (en) * 1985-12-30 1987-07-14 武居　二郎 Composition for protective coating
CN103131370A (en) * 2013-03-11 2013-06-05 东华大学 1,3-bis(2,4-diamidophenoxy)benzene high-temperature-resistant epoxy adhesive and preparation method thereof
CN103214793A (en) * 2013-04-22 2013-07-24 东华大学 Advanced composite material matrix resin and preparation method thereof
CN103483553A (en) * 2013-09-17 2014-01-01 东华大学 TGDADPE type epoxy matrix resin for advanced composite material and preparation method thereof

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* Cited by examiner, † Cited by third party
Title
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Application publication date: 20170104