CN106277929A - A kind of BDATHQ type granolith sheet material and preparation method thereof - Google Patents
A kind of BDATHQ type granolith sheet material and preparation method thereof Download PDFInfo
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- CN106277929A CN106277929A CN201610578264.4A CN201610578264A CN106277929A CN 106277929 A CN106277929 A CN 106277929A CN 201610578264 A CN201610578264 A CN 201610578264A CN 106277929 A CN106277929 A CN 106277929A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—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
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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
- 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
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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
- 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
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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
- 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 BDATHQ 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 BDATHQ type resin.Preparation method includes: mixed with BDATHQ 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 BDATHQ type resin;BDATHQ 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
Technical field
The invention belongs to organic/inorganic composite material and preparation field thereof, particularly to a kind of BDATHQ 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: TGBDATHQ 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 (TGBDATHQ), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing
Agent etc., 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 BDATHQ 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 BDATHQ type granolith sheet material of the present invention, described granite plates is 100:5-10's by mass ratio
Granite powder and BDATHQ type resin composition;Wherein, BDATHQ type resin is 100:2-4:10-20:10-30's by mass ratio
Epoxy resin, 2,5-double (2,4-diamino phenoxy) toluene BDATHQ, latent curing agent LRC30 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 BDATHQ type granolith preparation of plates method of the present invention, including:
(1) by epoxy resin and 2, double (2,4-diamino phenoxy) the toluene BDATHQ of 5-puts in reactor, and stirring is mixed
Close, after 115 DEG C-125 DEG C reactions 0.5-1 hour, be cooled to less than 60 DEG C, add latent curing agent LRC30 and liquid acid
Acid anhydride, is uniformly mixed, and obtains BDATHQ type resin;Wherein, epoxy resin, 2, double (2, the 4-diamino phenoxy) toluene of 5-
The mass ratio of BDATHQ, latent curing agent LRC30 and liquid anhydride is 100:2-4:10-20:10-30;
(2), after BDATHQ type resin being mixed homogeneously with granite powder, put in stainless steel flat plate frame, pressing preformation
Type, 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 BDATHQ 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 BDATHQ 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 ', O-five glycidyl-4,4 '-diaminourea-4 by 200 grams of N, N, N "-hydroxyl tritan. epoxy resin,
150 grams of 3,4-epoxy radicals-6-methyl cyclohexanes acid-3 ', 4 '-epoxy radicals-6 '-methyl cyclohexane methyl ester epoxy resin, 150 grams of E-51 rings
Epoxy resins, 220 grams of 1,3-diglycidyl resorcinol type epoxy, 280 grams of N, N, O triglycidyl group p-aminophenyl
Phenol epoxy resin adds in reactor, after being uniformly mixed, adds 20 gram 2, double (2, the 4-diamino phenoxy) toluene of 5-
(BDATHQ), 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 agents
LRC30, adds 200 grams of dodecyl succinic anhydrides, is uniformly mixed, and obtains the BDATHQ type resin of 1370 grams, is denoted as
BDATHQ-1。
Embodiment 2
', N ', O-five glycidyl-4,4 '-diaminourea-4 by 120 grams of N, N, N "-hydroxyl tritan. epoxy resin,
80 grams of 3,4-epoxy radicals-6-methyl cyclohexanes acid-3 ', 4 '-epoxy radicals-6 '-methyl cyclohexane methyl ester epoxy resin, 100 grams of CE793 rings
Epoxy resins, 400 grams of N, N, N ', N '-four glycidyl group-4,4 '-MDA epoxy resin, 100 grams of E-44 epoxies
Resin, 200 grams of o-phthalic acid diglycidyl ester epoxy resin add in reactor, after being uniformly mixed, add 30 grams
2,5-double (2,4-diamino phenoxy) toluene (BDATHQ), stirring mixing, after 120 DEG C of reactions 1 hour, be cooled to 60 DEG C with
Under, add 100 grams of latent curing agent LRC30, add 150 grams of HHPAs and the liquid acid of 150 grams of methyl tetrahydro phthalic anhydrides
Acid anhydride, is uniformly mixed, and obtains the BDATHQ type resin of 1430 grams, is denoted as BDATHQ-2.
Embodiment 3
', N ', O-five glycidyl-4,4 '-diaminourea-4 by 80 grams of N, N, N "-hydroxyl tritan. epoxy resin,
120 grams of N, N, N ', N '-four glycidyl group-4,4 '-MDA epoxy resin, 90 grams of 1,3-diglycidyl
Resorcinol type epoxy, 110 grams of N, N, O triglycidyl group para-aminophenol epoxy resin, 120 grams of o-cresol-formaldehyde
Phenolic resin type epoxy resin, 300 grams of 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl esters, 180 grams of 3,4-epoxy radicals
Cyclohexylenedinitrilotetraacetic acid-3 ', 4 '-epoxycyclohexyethylSiOi methyl ester epoxy resin adds in reactor, after being uniformly mixed, adds 40 gram 2, and 5-is double
(2,4-diamino phenoxy) toluene (BDATHQ), stirring mixing, after 125 DEG C of reactions 0.5 hour, it is cooled to less than 60 DEG C,
Add 200 grams of latent curing agent LRC30, add 35 grams of methyl tetrahydro phthalic anhydrides, 10 grams of tung oil acid anhydrides and 55 grams of dodecyls
Succinic anhydrides, is uniformly mixed, and obtains the BDATHQ type resin of 1340 grams, is denoted as BDATHQ-3.
Embodiment 4
Take BDATHQ-1~the BDATHQ-3 resin of appropriate above-described embodiment 1~embodiment 3, and difference even application is in mark
In quasi-rustless steel test piece and glass pieces of cloth, overlapping after hanging 1 hour under room temperature, (glass pieces of cloth are at 2 standard stainless steel substrates in clamping
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
Continue and be warming up 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
Intensity is as shown in table 1.
Take BDATHQ-1~the BDATHQ-3 resin of appropriate above-described embodiment 1~embodiment 3, pour a diameter of 10cm into not
In rust 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
The circular specimen of 10cm, after distilled water immersion 72 hours, surveys its water absorption rate, and result is as shown in table 1.
Take BDATHQ-1~the BDATHQ-3 resin of appropriate above-described embodiment 1~embodiment 3, and difference even application is in mark
On quasi-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 BDATHQ type resin and water absorption rate
Embodiment 5
After 10 grams of BDATHQ-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 BDATHQ-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 BDATHQ-1 resins, 9 grams of BDATHQ-3 resins and 200 grams of granite powder mix homogeneously, put into stainless
In steel flat board frame, pressing preforming, in tabular, heat-pressure curing molding;Wherein, the temperature range of heating be room temperature extremely
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 it
Performance, as shown in table 2.
5 grams of BDATHQ-3 resins, 10 grams of BDATHQ-1 resins, 5 grams of BDATHQ-2 resins and 200 grams of granite powder are mixed
After closing uniformly, put in stainless steel flat plate frame, pressing preforming, in tabular, heat-pressure curing molding;Wherein, heating
Temperature range 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 plate obtained
Material 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 | 309 | 315 | 314 |
Water absorption rate, MPa/25 DEG C) | 0.15 | 0.13 | 0.12 | 0.13 |
Bending strength, MPa (/ 25 DEG C) | 27.3 | 27.9 | 27.2 | 28.1 |
Bending strength, MPa (/ 170 DEG C) | 24.4 | 24.7 | 25.1 | 25.5 |
Bulk density, g/cm3(/25℃) | 2.89 | 2.88 | 2.87 | 2.89 |
Claims (10)
1. a BDATHQ type granolith sheet material, it is characterised in that described granite plates is 100:5-10 by mass ratio
Granite powder and BDATHQ type resin composition;Wherein, BDATHQ type resin is 100:2-4:10-20:10-30 by mass ratio
Epoxy resin, 2,5-double (2,4-diamino phenoxy) toluene BDATHQ, latent curing agent LRC30 and liquid anhydride group
Become.
A kind of BDATHQ 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 BDATHQ 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 BDATHQ 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 BDATHQ 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 BDATHQ 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 BDATHQ 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 BDATHQ 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 BDATHQ 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 BDATHQ type granolith preparation of plates method, including:
(1) by epoxy resin and 2, double (2,4-diamino phenoxy) the toluene BDATHQ of 5-stirs mixing, 115 DEG C-125 DEG C reactions
0.5-1 hour, it is cooled to less than 60 DEG C, adds latent curing agent LRC30 and liquid anhydride, stirring, obtain BDATHQ type tree
Fat;Wherein, epoxy resin, 2,5-double (2,4-diamino phenoxy) toluene BDATHQ, latent curing agent LRC30 and liquid acid
The mass ratio of acid anhydride is 100:2-4:10-20:10-30;
(2) the BDATHQ type resin in step (1) is mixed homogeneously with granite powder, pressing preforming, heat-pressure curing
Molding;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;
The mass ratio of granite powder and BDATHQ type resin is 100:5-10.
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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 |
-
2016
- 2016-07-21 CN CN201610578264.4A patent/CN106277929A/en active Pending
Patent Citations (4)
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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Title |
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