CN106242369A - A kind of DDS type granolith sheet material and preparation method thereof - Google Patents
A kind of DDS type granolith sheet material and preparation method thereof Download PDFInfo
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- CN106242369A CN106242369A CN201610579000.0A CN201610579000A CN106242369A CN 106242369 A CN106242369 A CN 106242369A CN 201610579000 A CN201610579000 A CN 201610579000A CN 106242369 A CN106242369 A CN 106242369A
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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
- C08G59/40—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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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
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- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of DDS 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 DDS type resin.Preparation method includes: mixed with DDS 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 DDS type resin；DDS 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 DDS 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: TGDDS 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 (TGDDS), 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 DDS 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 DDS 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 DDS type resin form；Wherein, DDS type resin is the asphalt mixtures modified by epoxy resin of 100:2-4:10-20:10-30 by mass ratio
Fat, 4,4' diaminodiphenyl sulfone DDS, 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 DDS type granolith preparation of plates method of the present invention, including:
(1) by epoxy resin and 4,4'-DADPS is put in reactor, stirring mixing, anti-in 115 DEG C-125 DEG C
After answering 0.5-1 hour, it is cooled to less than 60 DEG C, adds latent curing agent LRC30 and liquid anhydride, be uniformly mixed,
To DDS type resin；Wherein, epoxy resin, 4,4'-DADPS DDS, latent curing agent LRC30 and liquid anhydride
Mass ratio is 100:2-4:10-20:10-30；
(2), after DDS type resin being mixed homogeneously with granite powder, put in stainless steel flat plate frame, pressing preforming, add
Hot cure under pressure 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；The mass ratio of granite powder and DDS 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 DDS 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 500 grams of E-44 epoxy resin, 250 grams of 1,3-diglycidyl resorcinol type epoxy, 250 grams of N, N, O
Triglycidyl group para-aminophenol epoxy resin adds in reactor, after being uniformly mixed, adds 20 gram 4,4'-diaminourea
Diphenyl sulphone (DPS) (DDS), 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 DDS type resin of 1370 grams, is denoted as DDS-
1。
Embodiment 2
By 200 grams of CE793 epoxy resin, 200 grams of N, N, N ', N '-four glycidyl group-4,4 '-MDA
Epoxy resin, 300 grams of E-44 epoxy resin, 300 grams of o-phthalic acid diglycidyl ester epoxy resin add in reactor, stir
After mixing mix homogeneously, add 30 gram 4,4'-DADPS (DDS), stirring mixing, after 120 DEG C of reactions 1 hour, cooling
To less than 60 DEG C, add 100 grams of latent curing agent LRC30, add 100 grams of HHPAs and 200 grams of methyl tetrahydro phthalic anhydrides
Liquid anhydride, be uniformly mixed, obtain the DDS type resin of 1430 grams, be denoted as DDS-2.
Embodiment 3
By 100 grams of 1,3-diglycidyl resorcinol type epoxy, 200 grams of N, amino between N, O triglycidyl group
Phenol epoxy resin, 200 grams of o-cresol-formaldehyde phenolic resin type epoxy resin, 300 grams of 4,5-7-oxa-bicyclo[4.1.0-1,2-two
Formic acid 2-glycidyl ester, 200 grams of 3,4-epoxycyclohexyethylSiOi acid-3 ', 4 '-epoxycyclohexyethylSiOi methyl ester epoxy resin adds reactor
In, after being uniformly mixed, add 40 gram 4,4'-DADPS (DDS), stirring mixing, react 0.5 hour in 125 DEG C
After, it is cooled to less than 60 DEG C, adds 200 grams of latent curing agent LRC30, add 20 grams of methyl tetrahydro phthalic anhydrides, 20 grams of Oleum Verniciae fordii
Anhydride and 60 grams of dodecyl succinic anhydrides, be uniformly mixed, and obtains the DDS type resin of 1340 grams, is denoted as DDS-3.
Embodiment 4
Take DDS-1～the DDS-3 resin of appropriate above-described embodiment 1～embodiment 3, and even application is stainless in standard respectively
In steel test piece and glass pieces of cloth, overlap after hanging under room temperature 1 hour, clamping (glass pieces of cloth between 2 standard stainless steel substrates,
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 to heat up
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.Record tensile shear strength such as
Shown in table 1.
Take DDS-1～the DDS-3 resin of appropriate above-described embodiment 1～embodiment 3, pour the rustless steel circle of a diameter of 10cm into
In dish (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, the circle of diameter 10cm
Shape sample, after distilled water immersion 72 hours, surveys its water absorption rate, and result is as shown in table 1.
Take DDS-1～the DDS-3 resin of appropriate above-described embodiment 1～embodiment 3, and difference even application is in dressing plate
On sheet glass, overlap after hanging under room temperature 1 hour, clamping, put in convection oven and solidify: be heated to 110 DEG C from room temperature,
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 1 DDS type resin and water absorption rate
| Sample | DDS-1 | DDS-2 | DDS-3 |
| Water absorption rate, % | 0.33 | 0.42 | 0.23 |
| Tensile shear strength (rustless steel test piece and glass pieces of cloth), MPa (/ 25 DEG C) | 27.3 | 27.6 | 28.7 |
| Hot strength (rustless steel test piece and glass pieces of cloth), MPa (/ 170 DEG C) | 24.4 | 24.1 | 24.2 |
| Tensile shear strength (flat glass film), MPa (/ 25 DEG C) | 20.1 | 21.3 | 20.4 |
| Hot strength (flat glass film), MPa (/ 170 DEG C) | 19.3 | 19.7 | 19.2 |
Embodiment 5
After 10 grams of DDS-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 DDS-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 DDS-1 resins, 9 grams of DDS-3 resins and 200 grams of granite powder mix homogeneously, put into stainless steel flat plate
In frame, pressing preforming, in tabular, heat-pressure curing molding；Wherein, the temperature range of heating is that room temperature is to 180 DEG C；Add
The pressure limit of pressure is 0.5MPa to 5MPa；Hardening time is 2-5 hour, and the sheet material obtained is denoted as BC-3, surveys its performance, such as table
Shown in 2.
After 5 grams of DDS-3 resins, 10 grams of DDS-1 resins, 5 grams of DDS-2 resins and 200 grams of granite powder mix homogeneously,
Putting in stainless steel flat plate frame, pressing preforming, in tabular, 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-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) | 301 | 312 | 301 | 299 |
| Water absorption rate, MPa/25 DEG C) | 0.15 | 0.17 | 0.12 | 0.18 |
| Bending strength, MPa (/ 25 DEG C) | 28.1 | 28.7 | 28.2 | 27.7 |
| Bending strength, MPa (/ 170 DEG C) | 23.4 | 22.7 | 22.4 | 23.5 |
| Bulk density, g/cm3(/25℃) | 2.88 | 2.89 | 2.86 | 2.85 |
Claims (10)
1. a DDS type granolith sheet material, it is characterised in that described granite plates is the flower of 100:5-10 by mass ratio
Rock dust end, hilllock and DDS type resin form；Wherein, DDS type resin is the asphalt mixtures modified by epoxy resin of 100:2-4:10-20:10-30 by mass ratio
Fat, 4,4' diaminodiphenyl sulfone DDS, latent curing agent LRC30 and liquid anhydride composition.
A kind of DDS 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 DDS 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 DDS 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 DDS 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 DDS 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 DDS 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 DDS 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 DDS 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 DDS type granolith preparation of plates method, including:
(1) by epoxy resin and 4,4'-DADPS DDS stirs mixing, and 115 DEG C-125 DEG C are reacted 0.5-1 hour, cooling
To less than 60 DEG C, add latent curing agent LRC30 and liquid anhydride, stirring, obtain DDS type resin；Wherein, epoxy resin,
The mass ratio of 4,4' diaminodiphenyl sulfone DDS, latent curing agent LRC30 and liquid anhydride is 100:2-4:10-20:10-
30；
(2) being mixed homogeneously with granite powder by the DDS 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 DDS type resin is 100:5-10.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805493A (en) * | 2010-03-10 | 2010-08-18 | 中山大学 | High-temperature resistance carbon fiber/epoxy resin composite material, preparation method and use |
| CN103122232A (en) * | 2013-03-11 | 2013-05-29 | 东华大学 | 2,2-di[4-(2,4-diamino phenoxy) phenyl] propane form high-temperature epoxy adhesive and preparation method thereof |
| CN103122231A (en) * | 2013-03-11 | 2013-05-29 | 东华大学 | 1,4-di(2,4-diamino phenoxy) benzenoid form high-temperature epoxy adhesive and preparation method thereof |
| CN103131369A (en) * | 2013-03-11 | 2013-06-05 | 东华大学 | 4,4'-bis(2,4-diamidophenoxy)diphenylsulphone high-temperature-resistant epoxy adhesive and preparation method thereof |
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2016
- 2016-07-21 CN CN201610579000.0A patent/CN106242369A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805493A (en) * | 2010-03-10 | 2010-08-18 | 中山大学 | High-temperature resistance carbon fiber/epoxy resin composite material, preparation method and use |
| CN103122232A (en) * | 2013-03-11 | 2013-05-29 | 东华大学 | 2,2-di[4-(2,4-diamino phenoxy) phenyl] propane form high-temperature epoxy adhesive and preparation method thereof |
| CN103122231A (en) * | 2013-03-11 | 2013-05-29 | 东华大学 | 1,4-di(2,4-diamino phenoxy) benzenoid form high-temperature epoxy adhesive and preparation method thereof |
| CN103131369A (en) * | 2013-03-11 | 2013-06-05 | 东华大学 | 4,4'-bis(2,4-diamidophenoxy)diphenylsulphone high-temperature-resistant epoxy adhesive and preparation method thereof |
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