CN106116260B - A kind of granolith plank and preparation method thereof - Google Patents
A kind of granolith plank and preparation method thereof Download PDFInfo
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- CN106116260B CN106116260B CN201610488070.5A CN201610488070A CN106116260B CN 106116260 B CN106116260 B CN 106116260B CN 201610488070 A CN201610488070 A CN 201610488070A CN 106116260 B CN106116260 B CN 106116260B
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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
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/12—Waste materials; Refuse from quarries, mining or the like
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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
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Mining & Mineral Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of granolith plank and preparation method thereof, the granolith plank is 100 by mass ratio:5 10 granite powder and DAHTM type resins composition.Preparation method includes the following steps：Epoxy resin and 4, after 4 " hydroxyl triphenylmenthane hybrid reaction of 4' diamino; latent curing agent LRC30 and liquid acid anhydrides is added; be uniformly mixed; obtain DAHTM type resins, then mixed with granite powder, is put into stainless steel flat plate frame; pressing is preforming, heat-pressure curing molding.Raw material sources of the present invention are convenient, simple production process, it is solvent-free, it is environmental-friendly, product comprehensive performance is superior, it can be widely applied to building materials field, including high-grade hotel, airport lounge, high ferro wait building and platform, family kitchen and bath, office business building etc., have good market application prospect.
Description
Technical field
The invention belongs to organic/inorganic composite material field, more particularly to a kind of granolith plank and its preparation side
Method.
Background technology
Granite plates are a kind of good construction materials, are largely used to high-grade luxurious hotel, airport lounge, high ferro
It waits building and platform, family kitchen and bath, office business building etc..As the improvement of people's living standards, to granite plates
Demand is growing day by day, to further promote exploitation, the processing in granite mine, scale amounts more and more huger.And it opens at it
Adopt, process necessarily leads to a large amount of stone slurry, granite powder scrap etc., cause serious ring to river, mountains and rivers, stockyard etc.
Border is polluted, while the secondary disasters such as also easily cave in, and larger potential threat is caused to the people's lives and property.
For this purpose, people start actively to study the technology that the waste residue in granite stone pit is utilized again.Chinese invention is special
Sharp CN1037042A discloses a kind of inorganic artificial granite production technology, is primarily characterized in that：High alumina cement, stone are used first
Sand, inorganic pigment powder, glycerine and water mixing are tuned into thin pulp shape mill base, pour into shaping frame, after initial set, use high silicon water
Mud, quartz sand, quartz, inorganic pigment powder, glycerine and water, mixing is tuned into thin pulp shape coat of colo(u)r, irregularly on color paste layer
Portion, then after adding water to stir evenly with high alumina cement, river sand, rubble, be cast in shaping frame, as reinforcing after machinery shakes
Layer is finally putting into pond and impregnates maintenance molding in 72 hours, and using ageing-resistant pickling processes, product can be become by oiling.
Chinese invention patent CN1035812A disclose a kind of high intensity, it is indeformable, be not cracked, best bright finish, performance it is steady
The manufacturing method of fixed, high quality full-inorganic artificial marble, is primarily characterized in that：Using cement as raw material, it is added a small amount of inorganic
Auxiliary agent forms ontology, with it is pre-fabricated have a special component vibration is added in ontology into flower at flower agent, conserve and crystallize into water
Product.
Chinese invention patent CN1088146A discloses a kind of high alumina cement artificial granite, marble and its production work
Skill is primarily characterized in that：Using diffusant, alum, the concentrated sulfuric acid, magnesium sulfate, rosin, ferrous sulfate, oxalic acid, boric acid and
Triethanolamine and water are configured to fabric water and bottom material water, then go to mix cement and silica flour with fabric water and bottom material water, make respectively
At face layer and bottom, have between face layer and bottom one stirred with cement, silica flour and fabric water after spread out and put on face layer top
Base, maintenance is carried out using wet saw end.
It is well known that epoxy resin has many excellent performances：(1) good adhesive property：Adhesive strength is high, bonding
Wide, it is with many metals (such as iron, steel, copper, aluminium, metal alloy) or nonmetallic materials (such as glass, ceramics, timber, plastics
Deng) adhesive strength it is very high, some, which is even more than, is glued the intensity of material itself, therefore can be used for many stress members
In, it is one of main component of structural adhesive；(2) good processing performance：The flexibility of Formulaion of epoxy resin, processing work
The diversity of skill and product properties is the most outstanding in high molecular material；(3) good stability：The solidification of epoxy resin
The ring opening polyaddition of epoxy group is mainly relied on, therefore does not generate low-molecular material in solidification process, cure shrinkage is heat
Minimum one of kind, generally 1%-2% in thermosetting resin, if filler appropriate is selected shrinking percentage can be made to be down to 0.2%
Left and right；Epoxy main chains after solidification are ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore have excellent resistance to acid and alkali.
Therefore, epoxy resin is widely used in the every field of national economy：Either high-technology field is still
Its trace can be seen in field of general technology, either defence and military or civilian industry or even daily life.
Related high-temperature resistant epoxy oxygen system is reported：Chinese patent CN101148656A discloses a kind of high temperature resistant without molten
The preparation method of agent epoxy adhesive, is primarily characterized in that：TGDDM epoxy resin, toughener, hydrogenated bisphenol A, curing agent,
Accelerating agent is uniformly mixed, and heat-resistant solvent-free epoxy adhesive has been made.But its high temperature resistance still has larger limitation,
Fail to meet the practical application under many hot environments.
Chinese patent CN101397486A discloses a kind of preparation method of bi-component solvent-free epoxy resin adhesive,
It is characterized mainly in that：It includes component A and B component, and wherein component A contains novolac epoxy resin, alicyclic type epoxy resin and end
Carboxy nitrile rubber；B component is bis- (2,4- diamino phenoxies) the benzene aromatic polyvalent amine hardeners of 1,4-.Alicyclic ring type asphalt mixtures modified by epoxy resin
The additive amount of fat and nbr carboxyl terminal is respectively the 20-35% and 12% (mass percent) of novolac epoxy resin.1,4-
The additive amount of bis- (2,4- diamino phenoxies) benzene aromatic polyvalent amine hardeners is the 15-20% (quality of novolac epoxy resin
Percentage), gained adhesive system good manufacturability.But its heat resistance is ideal not enough.
Chinese invention patent CN101962436A discloses a kind of heat resist modification multi-functional epoxy used for advanced composite material
Matrix resin and preparation method thereof is primarily characterized in that：Using bis- (the 2,4- dimaleimides phenoxyl) benzene of 1,4-
The novel fire resistant of high tenacity is obtained by the reaction with polyfunctional epoxy resin, nbr carboxyl terminal CTBN for four maleimide resins
Organic solvent is added in resin, and stirring and dissolving is uniform, obtains the viscous liquid of homogeneous phase transparent, i.e. component A；Curing agent with it is organic
Solvent mixes, and stirring and dissolving is uniformly to get B component；A, B component are mixed, stirred evenly to get used for advanced composite material
Heat resist modification multi-functional epoxy's substrate resin solution.
Seas Yu Xin et al.【Development [J] of high-temperature resistant single-component epoxy adhesive is bonded, 2008,29 (12)：16-19】It is public
A kind of preparation method of high-temperature resistant single-component epoxy adhesive has been opened, has been primarily characterized in that：It is sealing end with maleic anhydride (MA)
Agent, with bis- (3- amino-4-hydroxylphenyls) hexafluoropropane (BAHPFP) of 2,2-, 2,2- bis- [4- (4- amino-benzene oxygens) phenyl] third
Bis- [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides (BPADA) of alkane (BAPOPP), 2,2- are that main Material synthesis obtains
Phenolic hydroxy group polyetherimide resin (HPEI)；With synthesized obtained HPEI for resistant, toughened dose, with N, N, N', N'- tetra-
Glycidyl -4,4'- diaminodiphenylmethane (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent
Deng, preparation obtained the high-temperature resistant single-component epoxy adhesive of excellent combination property.
Invention content
Technical problem to be solved by the invention is to provide a kind of granolith plank and preparation method thereof, the plank is former
Expect convenient sources, simple production process is solvent-free, environmental-friendly, and product comprehensive performance is superior, can be widely applied to building materials neck
Domain, including high-grade hotel, airport lounge, high ferro wait building and platform, family kitchen and bath, office business building etc., tool
There is good market application prospect.In addition, granite powder derives from the waste in granite stone pit, through the invention technology
It can turn waste into wealth, very important realistic meaning is all had to comprehensive environmental improvement etc..
A kind of granolith plank of the present invention is 100 by mass ratio:The granite powder of 5-10 and DAHTM type trees
Fat forms；Wherein, DAHTM types resin is 100 by mass ratio:5-10:5-10:Epoxy resin, the 4,4'- diamino-of 40-80
4 "-hydroxyl triphenylmenthane DAHTM, latent curing agent LRC30 and liquid acid anhydrides composition.
The epoxy resin is selected from E-51 epoxy resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 asphalt mixtures modified by epoxy resin
Fat, CE793 epoxy resin, glycidyl amine type epoxy resin, diglycidyl ether type epoxy resin, alicyclic type epoxy resin, phenol
One or more of aldehyde type epoxy resin, glycidyl ester type epoxy resin.
The glycidyl amine type epoxy resin is selected from N, N, N ', N '-four glycidyl groups -4,4 '-diamino hexichol first
Alkane epoxy resin, N, N, N ', N '-four glycidyl groups -3,3 '-dimethyl -4,4 '-diaminodiphenylmethane epoxy resin, N,
N, N ', N '-four glycidyl groups 3,3 '-diethyl -4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four shrinks
3,3 '-two chloro- 4,4 '-diaminodiphenylmethane epoxy resin of glyceryl, N, N, N ', N '-four glycidyl groups -4,4 '-diamino
Yl diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-diaminodiphenylsulfone epoxy resin, N, N, N ', N ' -
Four glycidyl group -3,4 '-diaminodiphenyl ether epoxy resin, N, N, N ', N '-four glycidyl groups -3,3 '-diamino hexichol
Sulfone epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-benzidine epoxy resin, N, N, N ', N '-four shrinks sweet
Oil base p-phenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group m-phenylene diamine (MPD)s epoxy resin, N, N, N ', N '-four shrinks
Bis- (4- amino-benzene oxygens) the benzene epoxy resin of glyceryl -1,4-, N, N, N ', bis- (the 3- aminobenzenes of N '-four glycidyl groups -1,4-
Oxygroup) benzene epoxy resin, N, N, N ', bis- (4- amino-benzene oxygens) the benzene epoxy resin of N '-four glycidyl groups -1,3-, N, N, N ',
Bis- (3- amino-benzene oxygens) the benzene epoxy resin of N '-four glycidyl groups -1,3-, N, N, N ', N '-four glycidyl groups -1,4- is double
(2- trifluoromethyl-4-aminophenoxyls) benzene epoxy resin, N, N, N ', bis- (the 2- trifluoromethyls-of N '-four glycidyl groups -1,3-
4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N ', O- five glycidyls -4,4 '-diamino -4 "-hydroxyl triphenylmenthane
Epoxy resin, N, N, N ', bis- [4- (4- amino-benzene oxygens) phenyl] the propane epoxy resin of N '-four glycidyl groups -2,2-, N, N,
Bis- [4- (4- amino-benzene oxygens) phenyl] the hexafluoropropane epoxy resin of N ', N '-four glycidyl group -2,2-, N, N, N ', N '-four
Bis- [4- (3- amino-benzene oxygens) phenyl] the propane epoxy resin of glycidyl -2,2-, N, N, N ', four glycidyl group -2 N ' -,
Bis- [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] the propane epoxy resin of 2-, N, N, N ', N '-four glycidyl groups -2,2-
Bis- [4- (3- amino-benzene oxygens) phenyl] hexafluoropropane epoxy resin, N, N, N ', the bis- [4- (2- of N '-four glycidyl groups -2,2-
Trifluoromethyl-4-aminophenoxyl) phenyl] hexafluoropropane epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4-
Amino-benzene oxygen) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyl -4- aminobenzenes
Oxygroup) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS) asphalt mixtures modified by epoxy resin
Fat, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N,
Bis- (4- amino-benzene oxygens) the diphenyl sulfide epoxy resin of N ', N '-four glycidyl group -4,4 ' -, N, N, N ',-four glycidols of N '
Bis- (2- trifluoromethyl-4-aminophenoxyls) the diphenyl sulfide epoxy resin of base -4,4 ' -, N, N, N ', four glycidyl group -4 N ' -,
4 '-bis- (4- amino-benzene oxygens) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- fluoroforms
Base -4- amino-benzene oxygens) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino-benzene oxygens)
Benzophenone epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) hexichol
Ketone epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino-benzene oxygens) biphenyl epoxy resin, N, N, N ',
N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl epoxy resin, N, N, N ', N ', O, O ' -
Bis- (3- amino-4-hydroxylphenyls) the hexafluoropropane epoxy resin of six glycidyl -2,2-, N, N, O-triglycidyl group is to ammonia
Base phenol epoxy resin, N, one or more of N, O-triglycidyl meta-aminophenol epoxy resin.
The diglycidyl ether type epoxy resin is selected from 1,3- diglycidyls resorcinol, 1,4- diglycidyls
Bis- (4- glycidyl phenyls) hexafluoropropane of hydroquinone, 4,4 '-diglycidyl bisphenol Ss, 2,2-, 2,2- are bis-, and (4- contracts
Water glycerine butylcyclohexyl) propane, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol-A 2-glycidyl
One or more of ether, fatty alcohol polyglycidyl ether.
The alicyclic type epoxy resin is selected from sour -3 ', the 4 '-epoxycyclohexyethylSiOi methyl esters of 3,4- epoxycyclohexyethylSiOis, 3,4- epoxies
Sour-3 ', 4 '-epoxy groups-the 6 '-methyl cyclohexane methyl esters of base-6- methyl cyclohexanes, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two shrink
One or more of glyceride, Dipentenedioxide.
The phenol aldehyde type epoxy resin is selected from phenol-formaldehyde phenolic resin type epoxy resin, o-cresol-formaldehyde novolac tree
Epoxy-type epoxy resin, resorcinol-formaldehyde phenolic resin type epoxy resin, m-cresol-formaldehyde phenolic resin type epoxy resin,
Catechol-formaldehyde phenolic resin type epoxy resin, bisphenol A-formaldehyde phenolic resin type epoxy resin, bisphenol S-formaldehyde novolac tree
Epoxy-type epoxy resin, bisphenol AF-formaldehyde phenolic resin type epoxy resin, '-biphenyl diphenol-formaldehyde phenolic resin type epoxy resin, neighbour
One or more of phenylphenol-formaldehyde phenolic resin type epoxy resin, naphthols-formaldehyde phenolic resin type epoxy resin.
The glycidyl ester type epoxy resin is selected from terephthalic acid diglycidyl ester epoxy resin, M-phthalic acid
2-glycidyl ester epoxy resin, o-phthalic acid diglycidyl ester epoxy resin, interior methine tetrahydrophthalic acid two
Ethylene oxidic ester epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters epoxy resin, two octanoic acid two of adjacent benzene
One or more of polyglycidyl epoxy resin.
The liquid acid anhydrides is selected from tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride, tung oil
Acid anhydrides, with one or more of liquid acid anhydrides made of turpentine oil and maleic acid anhydride reactant.
The granite powder derives from the waste in granite stone pit, through removing mud, except iron, silane coupling agent surface
Treated dried powder.
A kind of preparation method of granolith plank of the present invention, includes the following steps：
(1) by epoxy resin and 4,4'- diamino -4 "-hydroxyl triphenylmenthane DAHTM is put into reaction kettle, is stirred,
After 90 DEG C -110 DEG C are reacted 0.5-1 hours, 60 DEG C are cooled to hereinafter, addition latent curing agent LRC30 and liquid acid anhydrides, are stirred
It mixes uniformly mixed, obtains DAHTM type resins；
(2) after mixing by DAHTM types resin and granite powder, it is put into stainless steel flat plate frame, pressing is preforming
(being in tabular), heat-pressure curing molding；Wherein, the temperature range of heating is room temperature to 180 DEG C；The pressure limit of pressurization is
0.5MPa to 5MPa；Hardening time is 2-5 hours.
Advantageous effect
(1) preparation process of the invention is simple, at low cost, easy to operate, and raw material sources are convenient, can be in common apparatus
Preparation process is completed, industrialized production is advantageously implemented；
(2) the DAHTM type resins have good comprehensive performance；
(3) present invention is solvent-free, and environmental-friendly, product comprehensive performance is superior, can be widely applied to building materials field, including
High-grade hotel, airport lounge, high ferro wait building and platform, family kitchen and bath, office business building etc., have good
Market application prospect.In addition, the granite powder of the present invention derives from the waste in granite stone pit, through the invention technology
It can turn waste into wealth, very important realistic meaning is all had to comprehensive environmental improvement etc..
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
By 500 grams of E-51 epoxy resin, 250 grams of 1,3- diglycidyls resorcinol type epoxies, 250 grams of 3,4- rings
Oxygroup cyclohexylenedinitrilotetraacetic acid -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters epoxy resin are added in reaction kettle, after being uniformly mixed, are added 50 gram 4,
4'- diamino -4 "-hydroxyl triphenylmenthane (DAHTM), is stirred, in 90 DEG C reaction 1 hour after, be cooled to 60 DEG C hereinafter, plus
Enter 100 grams of latent curing agent LRC30, add 300 grams of methyl tetrahydro phthalic anhydrides and 100 grams of dodecyl succinic anhydrides, stirs
It is uniformly mixed, obtains 1550 grams of DAHTM type resins, be denoted as DAHTM-1.
Embodiment 2
By 100 grams of CE793 epoxy resin, 300 grams of N, N, N ', N '-four glycidyl groups -4,4 '-diaminodiphenylmethane
Epoxy resin, 600 grams of Diglycidyl M-phthalate epoxy resin are added in reaction kettle, after being uniformly mixed, are added
80 grams of 4,4'- diamino -4 "-hydroxyl triphenylmenthane (DAHTM), are stirred, and after 100 DEG C are reacted 1 hour, are cooled to 60 DEG C
Hereinafter, 70 grams of latent curing agent LRC30 are added, 600 grams of hexahydrophthalic anhydride are added, are uniformly mixed, obtain 1750 grams
DAHTM type resins, are denoted as DAHTM-2.
Embodiment 3
By 300 grams of N, N, O-triglycidyl group para-aminophenol epoxy resin, 100 grams of phenol-formaldehyde phenolic resin types
Epoxy resin, sour -3 ', the 4 '-epoxycyclohexyethylSiOi methyl esters epoxy resin of 600 grams of 3,4- epoxycyclohexyethylSiOis are added in reaction kettle, stirring
After mixing, 100 grams of 4,4'- diamino -4 are added "-hydroxyl triphenylmenthane (DAHTM), it is stirred, reacts 1 in 110 DEG C
After hour, 60 DEG C are cooled to hereinafter, 50 grams of latent curing agent LRC30 of addition, add 100 grams of hexahydrophthalic anhydride, 600 grams of tung oil
Acid anhydrides and 100 grams of dodecyl succinic anhydrides, are uniformly mixed, and obtain 1950 grams of DAHTM type resins, are denoted as DAHTM-3.
Embodiment 4
DAHTM-1~DAHTM-3 resins of appropriate 1~embodiment of above-described embodiment 3 are taken, and difference even application is in standard
Stainless steel test piece and glass cloth on piece, overlap after hanging 1 hour at room temperature, clamp (glass pieces of cloth 2 standard stainless steel substrates it
Between, only lap-joint is resinous), it is put into convection oven and is cured：It is heated to from room temperature to 100 DEG C, keeps the temperature 1 hour, after
It is continuous to be warming up to 160 DEG C, 1 hour is kept the temperature, is continuously heating to 180 DEG C, keeps the temperature 1 hour, cooled to room temperature.Measure tensile shear
Intensity is as shown in table 1.
DAHTM-1~DAHTM-3 the resins for taking appropriate 1~embodiment of above-described embodiment 3, pour into the stainless of a diameter of 10cm
(disk coats releasing agent in advance), heat cure in steel disk：It is heated to from room temperature to 100 DEG C, keeps the temperature 1 hour, be continuously heating to
160 DEG C, 1 hour is kept the temperature, is continuously heating to 180 DEG C, keeps the temperature 1 hour, cooled to room temperature.Obtain thickness about 1mm, diameter
The circular specimen of 10cm surveys its water absorption rate, the results are shown in Table 1 after distilled water immersion 72 hours.
DAHTM-1~DAHTM-3 resins of appropriate 1~embodiment of above-described embodiment 3 are taken, and difference even application is in standard
Plate glass on piece overlaps after hanging 1 hour at room temperature, clamps, is put into convection oven and is cured：From room temperature be heated to
100 DEG C, 1 hour is kept the temperature, is continuously heating to 160 DEG C, keeps the temperature 1 hour, is continuously heating to 180 DEG C, keeps the temperature 1 hour, natural cooling
To room temperature.It is as shown in table 1 to measure tensile shear strength.
The tensile shear strength and water absorption rate of table 1DAHTM type resins
Embodiment 5
After mixing by 10 grams of DAHTM-1 resins and 200 grams of granite powder, it is put into stainless steel flat plate frame, presses
It is preforming, it is in tabular, heat-pressure curing molding；Wherein, heating temperature is 120 DEG C；Pressure is 0.5MPa；Hardening time is
2 hours.Obtained plank is denoted as BC-1, surveys its performance, as shown in table 2.
After mixing by 16 grams of DAHTM-2 resins and 200 grams of granite powder, it is put into stainless steel flat plate frame, presses
It is preforming, it is in tabular, heat-pressure curing molding；Wherein, heating temperature is 140 DEG C；Pressure is 2MPa；Hardening time is 3
Hour.Obtained plank is denoted as BC-2, surveys its performance, as shown in table 2.
After mixing by 6 grams of DAHTM-1 resins, 6 grams of DAHTM-3 resins and 200 grams of granite powder, it is put into stainless steel
In tablet frame, pressing is preforming, is in tabular, heat-pressure curing molding；Wherein, heating temperature is 160 DEG C；Pressure is
4MPa；Hardening time is 4 hours.Obtained plank is denoted as BC-3, surveys its performance, as shown in table 2.
10 grams of DAHTM-3 resins, 6 grams of DAHTM-1 resins, 6 grams of DAHTM-2 resins are mixed with 200 grams of granite powder
It after uniformly, is put into stainless steel flat plate frame, pressing is preforming, is in tabular, heat-pressure curing molding；Wherein, heating temperature
It is 180 DEG C；Pressure is 5MPa；Hardening time is 5 hours.Obtained plank is denoted as BC-4, surveys its performance, as shown in table 2.
The performance of 2 granolith plate of table
Claims (10)
1. a kind of granolith plank, it is characterised in that：It is 100 by mass ratio:The granite powder of 5-10 and DAHTM type trees
Fat forms；Wherein, DAHTM types resin is 100 by mass ratio:5-10:5-10:Epoxy resin, the 4,4'- diamino-of 40-80
4 "-hydroxyl triphenylmenthane DAHTM, latent curing agent LRC30 and liquid acid anhydrides composition.
2. a kind of granolith plank according to claim 1, it is characterised in that：The epoxy resin is selected from E-51 rings
Oxygen resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 epoxy resin, CE793 epoxy resin, glycidyl amine type ring
Oxygen resin, diglycidyl ether type epoxy resin, alicyclic type epoxy resin, phenol aldehyde type epoxy resin, glycidyl ester type epoxy tree
One or more of fat.
3. a kind of granolith plank according to claim 2, it is characterised in that：The glycidyl amine epoxy tree
Fat is selected from N, N, N ', N '-four glycidyl groups -4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ',-four glycidols of N '
Base -3,3 '-dimethyl -4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ', 3,3 '-diethyl of N '-four glycidyl groups -
4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ', 3,3 '-two chloro- 4,4 '-diamino hexichol first of N '-four glycidyl groups
Alkane epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-diaminodiphenyl ether epoxy resin, N, N, N ', N '-four shrinks
Glyceryl -4,4 '-diaminodiphenylsulfone epoxy resin, N, N, N ', N '-four glycidyl groups -3,4 '-diaminodiphenyl ether epoxy
Resin, N, N, N ', N '-four glycidyl groups -3,3 '-diaminodiphenylsulfone epoxy resin, N, N, N ', N '-four glycidyl groups -
4,4 '-benzidine epoxy resin, N, N, N ', N '-four glycidyl group p-phenylenediamine epoxy resin, N, N, N ', N '-four contracts
Water glyceryl m-phenylene diamine (MPD) epoxy resin, N, N, N ', bis- (4- amino-benzene oxygens) the benzene asphalt mixtures modified by epoxy resin of N '-four glycidyl groups -1,4-
Fat, N, N, N ', bis- (3- amino-benzene oxygens) the benzene epoxy resin of N '-four glycidyl groups -1,4-, N, N, N ',-four glycidols of N '
Bis- (4- amino-benzene oxygens) the benzene epoxy resin of base -1,3-, N, N, N ', N '-four glycidyl groups -1,3- bis- (3- amino-benzene oxygens)
Benzene epoxy resin, N, N, N ', bis- (2- trifluoromethyl-4-aminophenoxyls) the benzene epoxy resin of N '-four glycidyl groups -1,4-,
N, N, N ', bis- (2- trifluoromethyl-4-aminophenoxyls) the benzene epoxy resin of N '-four glycidyl groups -1,3-, N, N, N ', N ', O-
Five glycidyls -4,4 '-diamino -4 "-hydroxyl triphenylmenthane epoxy resin, N, N, N ', N '-four glycidyl groups -2,2-
Bis- [4- (4- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', bis- [4- (the 4- amino of N '-four glycidyl groups -2,2-
Phenoxy group) phenyl] hexafluoropropane epoxy resin, N, N, N ', bis- [4- (3- amino-benzene oxygens) benzene of N '-four glycidyl groups -2,2-
Base] propane epoxy resin, N, N, N ', bis- [4- (2- trifluoromethyl-4-aminophenoxyls) benzene of N '-four glycidyl groups -2,2-
Base] propane epoxy resin, N, N, N ', bis- [4- (3- amino-benzene oxygens) phenyl] the hexafluoropropane rings of N '-four glycidyl groups -2,2-
Oxygen resin, N, N, N ', bis- [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] hexafluoropropane of N '-four glycidyl groups -2,2-
Epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino-benzene oxygens) diphenyl ether epoxy resin, N, N, N ',
N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether epoxy resin, N, N, N ', N '-four contracts
Water glyceryl -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis-
(2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino
Phenoxy group) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyl -4- aminobenzene oxygen
Base) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino-benzene oxygens) diphenyl-methane epoxy
Resin, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl-methane epoxy resin,
N, N, N ', N '-four glycidyl groups -4,4 '-bis- (4- amino-benzene oxygens) benzophenone epoxy resin, N, N, N ', N '-four shrinks
Bis- (2- trifluoromethyl-4-aminophenoxyls) the benzophenone epoxy resin of glyceryl -4,4 ' -, N, N, N ',-four glycidols of N '
Bis- (4- amino-benzene oxygens) biphenyl epoxy resins of base -4,4 ' -, N, N, N ', N '-four glycidyl groups -4,4 '-bis- (2- fluoroforms
Base -4- amino-benzene oxygens) biphenyl epoxy resin, N, N, N ', bis- (the 3- amino-4-hydroxies of N ', O, the O glycidyl of '-six -2,2-
Phenyl) hexafluoropropane epoxy resin, N, N, O-triglycidyl group para-aminophenol epoxy resin, N, N, O-triglycidyl group
One or more of m-aminophenol epoxy resin.
4. a kind of granolith plank according to claim 2, it is characterised in that：The diglycidyl ether type epoxy tree
Fat is selected from 1,3- diglycidyls resorcinol, 1,4- diglycidyls hydroquinone, 4,4 '-diglycidyl bis-phenols
S, bis- (4- glycidyl phenyls) hexafluoropropane of 2,2-, bis- (4- glycidyl cyclohexyls) propane of 2,2-, Bisphenol F two are shunk
Glycerin ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, one kind in fatty alcohol polyglycidyl ether or several
Kind.
5. a kind of granolith plank according to claim 2, it is characterised in that：The alicyclic type epoxy resin is selected from
Sour -3 ', the 4 '-epoxycyclohexyethylSiOi methyl esters of 3,4- epoxycyclohexyethylSiOis, sour -3 ', the 4 '-epoxy groups-of 3,4- epoxy group -6- methyl cyclohexanes
6 '-methyl cyclohexane methyl esters, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, one kind in Dipentenedioxide or
It is several.
6. a kind of granolith plank according to claim 2, it is characterised in that：The phenol aldehyde type epoxy resin is selected from
Phenol-formaldehyde phenolic resin type epoxy resin, o-cresol-formaldehyde phenolic resin type epoxy resin, resorcinol-formaldehyde phenolic aldehyde
Resin type epoxy resins, m-cresol-formaldehyde phenolic resin type epoxy resin, catechol-formaldehyde phenolic resin type asphalt mixtures modified by epoxy resin
Fat, bisphenol A-formaldehyde phenolic resin type epoxy resin, bisphenol S-formaldehyde phenolic resin type epoxy resin, bisphenol AF-formaldehyde novolac
Resin type epoxy resins, '-biphenyl diphenol-formaldehyde phenolic resin type epoxy resin, o-phenyl phenol-formaldehyde phenolic resin type ring oxygen
One or more of resin, naphthols-formaldehyde phenolic resin type epoxy resin.
7. a kind of granolith plank according to claim 2, it is characterised in that：The glycidyl ester type epoxy tree
Fat is selected from terephthalic acid diglycidyl ester epoxy resin, Diglycidyl M-phthalate epoxy resin, O-phthalic
Sour 2-glycidyl ester epoxy resin, interior methine tetrahydrophthalic acid 2-glycidyl ester epoxy resin, 4,5- epoxide rings
One kind or several in hexane -1,2- dicarboxylic acid diglycidyl esters epoxy resin, two sad diglycidyl ether epoxy resin of adjacent benzene
Kind.
8. a kind of granolith plank according to claim 1, it is characterised in that：The liquid acid anhydrides is selected from tetrahydrochysene benzene
Acid anhydride, methyl tetrahydro phthalic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride, tung oil acid anhydride, with turpentine oil and maleic acid anhydride reactant
Made of one or more of liquid acid anhydrides.
9. a kind of granolith plank according to claim 1, it is characterised in that：The granite powder is flower hilllock
The waste in rock stone pit, through removing mud, except the dried powder after iron, silane coupling agent surface treatment.
10. a kind of preparation method of granolith plank as described in claim 1, includes the following steps：
(1) by epoxy resin and 4,4'- diamino -4 "-hydroxyl triphenylmenthane DAHTM is put into reaction kettle, is stirred, in 90
After DEG C of -110 DEG C reactions 0.5-1 hour, 60 DEG C are cooled to hereinafter, latent curing agent LRC30 and liquid acid anhydrides is added, stirring mixes
It closes uniformly, obtains DAHTM type resins；
(2) after mixing by DAHTM types resin and granite powder, it is put into stainless steel flat plate frame, pressing is preforming, heating
Cure under pressure is molded；Wherein, the temperature range of heating is room temperature to 180 DEG C；The pressure limit of pressurization is 0.5MPa to 5MPa；Gu
It is 2-5 hours to change the time.
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| CN108863252A (en) * | 2018-08-07 | 2018-11-23 | 枣庄鑫金山智能机械股份有限公司 | A kind of preparation method of artificial granite plate |
| WO2020118572A1 (en) * | 2018-12-12 | 2020-06-18 | Mflgh Inc. D/B/A Mgroup | Engineered stone product and methods of making the same |
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| CN101629062A (en) * | 2009-08-20 | 2010-01-20 | 东华大学 | Polyimide-epoxy resin adhesive and preparation method and application thereof |
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