CN106186826A - A kind of 14BDAPB type granolith sheet material and preparation method thereof - Google Patents
A kind of 14BDAPB type granolith sheet material and preparation method thereof Download PDFInfo
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- CN106186826A CN106186826A CN201610578997.8A CN201610578997A CN106186826A CN 106186826 A CN106186826 A CN 106186826A CN 201610578997 A CN201610578997 A CN 201610578997A CN 106186826 A CN106186826 A CN 106186826A
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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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- Polymers & Plastics (AREA)
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Abstract
The present invention relates to a kind of 14BDAPB 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 14BDAPB type resin.Preparation method includes: mixed with 14BDAPB 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 14BDAPB type resin;14BDAPB 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 14BDAPB type artificial flower hilllock
Rock beam 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: TG14BDAPB 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 (TG14BDAPB), 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 14BDAPB type granolith sheet material and preparation side thereof
Method, 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, can
To be widely used in building materials field, including high-grade hotel, airport lounge, high ferro wait building and platform, family kitchen guarding,
Office business buildings etc., have good market application foreground.Additionally, granite powder derives from the discarded of granite stone pit
Thing, 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 14BDAPB type granolith sheet material of the present invention, described granite plates is 100:5-10 by mass ratio
Granite powder and 14BDAPB type resin composition;Wherein, 14BDAPB type resin is 100:2-4:10-20:10-by mass ratio
Epoxy resin, 1,4-double (2,4-diamino phenoxy) benzene 14BDAPB, latent curing agent LRC30 and the liquid anhydride group of 30
Become.
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 14BDAPB type granolith preparation of plates method of the present invention, including:
(1) putting in reactor by epoxy resin and Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene, stirring mixing, in 115
After DEG C of-125 DEG C reactions 0.5-1 hour, being cooled to less than 60 DEG C, add latent curing agent LRC30 and liquid anhydride, stirring is mixed
Close uniformly, obtain 14BDAPB type resin;Wherein, epoxy resin, Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene 14BDAPB, hide
The mass ratio of property firming agent LRC30 and liquid anhydride is 100:2-4:10-20:10-30;
(2), after 14BDAPB 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 14BDAPB 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 14BDAPB 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 200 grams of 3,4-epoxy radicals-6-methyl cyclohexane acid-3 ', 4 '-epoxy radicals-6 '-methyl cyclohexane methyl ester epoxy resin,
300 grams of E-51 epoxy resin, 240 grams of 1,3-diglycidyl resorcinol type epoxy, 260 grams of N, N, O three-glycidyl
Base para-aminophenol epoxy resin adds in reactor, after being uniformly mixed, adds 20 grams of Isosorbide-5-Nitraes-bis-(2,4-diaminobenzene oxygen
Base) benzene (14BDAPB), stirring mixing, after 115 DEG C of reactions 1 hour, it is cooled to less than 60 DEG C, adds 150 grams of latent curings
Agent LRC30, adds 200 grams of dodecyl succinic anhydrides, is uniformly mixed, and obtains the 14BDAPB type resin of 1370 grams, note
Make 14BDAPB-1.
Embodiment 2
By 180 grams of 3,4-epoxy radicals-6-methyl cyclohexane acid-3 ', 4 '-epoxy radicals-6 '-methyl cyclohexane methyl ester epoxy resin,
120 grams of CE793 epoxy resin, 100 grams of N, N, N ', N '-four glycidyl group-4,4 '-MDA epoxy resin,
200 grams of E-44 epoxy resin, 400 grams of o-phthalic acid diglycidyl ester epoxy resin add in reactor, and stirring mixing is all
After even, adding 30 grams of Isosorbide-5-Nitraes-bis-(2,4-diamino phenoxy) benzene (14BDAPB), stirring mixes, after 120 DEG C of reactions 1 hour,
It is cooled to less than 60 DEG C, adds 100 grams of latent curing agent LRC30, add 100 grams of HHPAs and 200 grams of methyl tetrahydrochysenes
The liquid anhydride of phthalic anhydride, is uniformly mixed, and obtains the 14BDAPB type resin of 1430 grams, is denoted as 14BDAPB-2.
Embodiment 3
', N '-four glycidyl group-4,4 '-MDA epoxy resin, 50 grams of 1,3-bis-by 100 grams of N, N, N
Glycidyl resorcinol type epoxy, 150 grams of N, N, O triglycidyl meta-aminophenol epoxy resin, 100 grams of neighbours
Cresols-formaldehyde phenolic resin type epoxy resin, 500 grams of 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl esters, 100
Grams 3,4-epoxycyclohexyethylSiOi acid-3 ', 4 '-epoxycyclohexyethylSiOi methyl ester epoxy resin adds in reactor, after being uniformly mixed, adds
Enter 40 grams of Isosorbide-5-Nitraes-bis-(2,4-diamino phenoxy) benzene (14BDAPB), stirring mixing, after 125 DEG C of reactions 0.5 hour, cool down
To less than 60 DEG C, add 200 grams of latent curing agent LRC30, add 20 grams of methyl tetrahydro phthalic anhydrides, 20 grams of tung oil acid anhydrides and 60
Gram dodecyl succinic anhydride, is uniformly mixed, obtains the 14BDAPB type resin of 1340 grams, be denoted as 14BDAPB-3.
Embodiment 4
Take 14BDAPB-1~the 14BDAPB-3 resin of appropriate above-described embodiment 1~embodiment 3, and respectively even application in
In standard 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 rustless steels in clamping
Between sheet, only lap-joint is resinous), put in convection oven and solidify: be heated to 110 DEG C from room temperature, be incubated 1 hour,
It is continuously heating to 150 DEG C, is incubated 1 hour, is continuously heating to 180 DEG C, be incubated 2 hours, naturally cool to room temperature.Record stretching to cut
Shearing stress is as shown in table 1.
Take 14BDAPB-1~the 14BDAPB-3 resin of appropriate above-described embodiment 1~embodiment 3, pour a diameter of 10cm's into
In rustless steel disk (disk coats releasing agent in advance), heat cure: be heated to 110 DEG C from room temperature, it is incubated 1 hour, continues 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.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 14BDAPB-1~the 14BDAPB-3 resin of appropriate above-described embodiment 1~embodiment 3, and respectively even application in
On dressing plate sheet glass, overlap after hanging under room temperature 1 hour, clamping, put in convection oven and solidify: heat from room temperature
To 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, the coldest
But to room temperature.Record tensile shear strength as shown in table 1.
The tensile shear strength of table 1 14BDAPB type resin and water absorption rate
Embodiment 5
After 10 grams of 14BDAPB-1 resins and 200 grams of granite powder mix homogeneously, put in stainless steel flat plate frame, pressure
Close 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
Power 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 14BDAPB-2 resins and 200 grams of granite powder mix homogeneously, put in stainless steel flat plate frame, pressure
Close 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
Power 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 14BDAPB-1 resins, 9 grams of 14BDAPB-3 resins and 200 grams of granite powder mix homogeneously, put into not
In rust 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.
By 5 grams of 14BDAPB-3 resins, 10 grams of 14BDAPB-1 resins, 5 grams of 14BDAPB-2 resins and 200 grams of granite powders
After the mix homogeneously of end, put in stainless steel flat plate frame, pressing preforming, in tabular, heat-pressure curing molding;Wherein, add
The temperature range of heat 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, obtains
Sheet material be denoted as BC-4, survey 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) | 304 | 307 | 303 | 309 |
Water absorption rate, MPa (/ 25 DEG C) | 0.17 | 0.19 | 0.15 | 0.16 |
Bending strength, MPa (/ 25 DEG C) | 25.7 | 26.2 | 25.9 | 26.7 |
Bending strength, MPa (/ 170 DEG C) | 22.1 | 23.0 | 22.2 | 22.4 |
Bulk density, g/cm3(/25℃) | 2.79 | 2.82 | 2.81 | 2.81 |
Claims (10)
1. a 14BDAPB type granolith sheet material, it is characterised in that described granite plates is 100:5-10 by mass ratio
Granite powder and 14BDAPB type resin composition;Wherein, 14BDAPB type resin is 100:2-4:10-20:10-by mass ratio
Epoxy resin, 1,4-double (2,4-diamino phenoxy) benzene 14BDAPB, latent curing agent LRC30 and the liquid anhydride group of 30
Become.
A kind of 14BDAPB type granolith sheet material the most according to claim 1, it is characterised in that described epoxy resin
For E-51 epoxy resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 epoxy resin, CE793 epoxy resin, shrink sweet
Oleyl amine type epoxy resin, diglycidyl ether type epoxy resin, alicyclic type epoxy resin, phenol aldehyde type epoxy resin, ethylene oxidic ester
At least one in type epoxy resin.
A kind of 14BDAPB type granolith sheet material the most according to claim 2, it is characterised in that described (+)-2,3-Epoxy-1-propanol
Amine type epoxy resin is N, N, N ', N '-four glycidyl group-4,4 '-MDA epoxy resin, N, N, N ', N '-four
Glycidyl-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 glycidyl group-3,3 '-two are chloro-4,4 '-
MDA 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 ' and-diamino
Yl diphenyl 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 glycidyl group p-phenylenediamine epoxy resin,
N, N, N ', N '-four glycidyl group m-diaminobenzene. epoxy resin, N, N, N ', double (the 4-aminobenzene of N '-four glycidyl group-1,4-
Epoxide) 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 14BDAPB type granolith sheet material the most according to claim 2, it is characterised in that described (+)-2,3-Epoxy-1-propanol
Ether type epoxy be 1,3-diglycidyl resorcinol, 1,4-diglycidyl hydroquinone, 4,4 '-two shrink sweet
Double (4-glycidyl cyclohexyl) propane of double (4-glycidyl phenyl) HFC-236fa of oil base bisphenol S, 2,2-, 2,2-, double
In phenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, fatty alcohol polyglycidyl ether
At least one.
A kind of 14BDAPB type granolith sheet material the most according to claim 2, it is characterised in that described alicyclic ring type ring
Epoxy resins 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 ester, in Dipentenedioxide
At least one.
A kind of 14BDAPB type granolith sheet material the most according to claim 2, it is characterised in that described phenol aldehyde type ring
Epoxy resins be 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 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, o-phenyl phenol-formaldehyde novolac tree
At least one in epoxy-type epoxy resin, naphthols-formaldehyde phenolic resin type epoxy resin.
A kind of 14BDAPB type granolith sheet material the most according to claim 2, it is characterised in that described (+)-2,3-Epoxy-1-propanol
Ester type epoxy resin be terephthalic acid diglycidyl ester epoxy resin, Diglycidyl M-phthalate epoxy resin,
O-phthalic acid diglycidyl ester epoxy resin, interior methine tetrahydrophthalic acid 2-glycidyl ester epoxy resin, 4,
In 5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl ester epoxy resin, adjacent benzene two octanoic acid diglycidyl ether epoxy resin
At least one.
A kind of 14BDAPB type granolith sheet material the most according to claim 1, it is characterised in that described liquid anhydride
For THPA, methyl tetrahydro phthalic anhydride, HHPA, dodecyl succinic anhydride, tung oil acid anhydride, with Oleum Terebinthinae and maleic two
At least one in the liquid anhydride of anhydride reaction.
A kind of 14BDAPB type granolith sheet material the most according to claim 1, it is characterised in that described granite powder
End is the garbage in granite stone pit, the dried powder obtained after removing mud, processing except ferrum, silane coupler surface.
10. a 14BDAPB type granolith preparation of plates method, including:
(1) epoxy resin is stirred mixing, 115 DEG C-125 DEG C reactions with Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene 14BDAPB
0.5-1 hour, it is cooled to less than 60 DEG C, adds latent curing agent LRC30 and liquid anhydride, stirring, obtain 14BDAPB type tree
Fat;Wherein, epoxy resin, Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene 14BDAPB, latent curing agent LRC30 and liquid acid
The mass ratio of acid anhydride is 100:2-4:10-20:10-30;
(2) the 14BDAPB 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 14BDAPB type resin is 100:5-10.
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---|---|---|---|---|
EP0362884A2 (en) * | 1988-10-07 | 1990-04-11 | Nippon Shokubai Co., Ltd. | Granite-like artificial stone |
CN103113841A (en) * | 2012-12-07 | 2013-05-22 | 北京航天试验技术研究所 | Preparation method of strong-acid-resistant epoxy resin quick plugging agent |
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 |
CN104002372A (en) * | 2014-06-09 | 2014-08-27 | 山东大学 | Variable-temperature maintenance method for resin mineral composite material |
-
2016
- 2016-07-21 CN CN201610578997.8A patent/CN106186826A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0362884A2 (en) * | 1988-10-07 | 1990-04-11 | Nippon Shokubai Co., Ltd. | Granite-like artificial stone |
CN103113841A (en) * | 2012-12-07 | 2013-05-22 | 北京航天试验技术研究所 | Preparation method of strong-acid-resistant epoxy resin quick plugging agent |
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 |
CN104002372A (en) * | 2014-06-09 | 2014-08-27 | 山东大学 | Variable-temperature maintenance method for resin mineral composite material |
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Title |
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