CN113462338A - Stone binder and preparation method thereof - Google Patents
Stone binder and preparation method thereof Download PDFInfo
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- CN113462338A CN113462338A CN202110780989.2A CN202110780989A CN113462338A CN 113462338 A CN113462338 A CN 113462338A CN 202110780989 A CN202110780989 A CN 202110780989A CN 113462338 A CN113462338 A CN 113462338A
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- 239000004575 stone Substances 0.000 title claims abstract description 61
- 239000011230 binding agent Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 122
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 84
- 150000001412 amines Chemical class 0.000 claims abstract description 68
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 48
- 229920000570 polyether Polymers 0.000 claims abstract description 48
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 75
- 239000003822 epoxy resin Substances 0.000 claims description 73
- 229920000647 polyepoxide Polymers 0.000 claims description 73
- 238000003756 stirring Methods 0.000 claims description 55
- -1 polyoxypropylene Polymers 0.000 claims description 52
- 239000006229 carbon black Substances 0.000 claims description 48
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 40
- 239000012745 toughening agent Substances 0.000 claims description 37
- 238000009775 high-speed stirring Methods 0.000 claims description 36
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 35
- 239000013008 thixotropic agent Substances 0.000 claims description 30
- 230000001070 adhesive effect Effects 0.000 claims description 29
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 28
- 150000004985 diamines Chemical class 0.000 claims description 28
- 229920001451 polypropylene glycol Polymers 0.000 claims description 28
- 239000000853 adhesive Substances 0.000 claims description 27
- 229910021485 fumed silica Inorganic materials 0.000 claims description 27
- 239000003085 diluting agent Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 21
- 239000002518 antifoaming agent Substances 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 19
- 239000004359 castor oil Substances 0.000 claims description 18
- 235000019438 castor oil Nutrition 0.000 claims description 18
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- CNSGPAMLXMBLNA-UHFFFAOYSA-N 2-amino-3,4,5,6-tetrafluorobenzoic acid Chemical compound NC1=C(F)C(F)=C(F)C(F)=C1C(O)=O CNSGPAMLXMBLNA-UHFFFAOYSA-N 0.000 claims description 14
- WTNSXWSOTDBWOR-UHFFFAOYSA-N 4-amino-2,3,5,6-tetrafluorobenzoic acid Chemical compound NC1=C(F)C(F)=C(C(O)=O)C(F)=C1F WTNSXWSOTDBWOR-UHFFFAOYSA-N 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 14
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 14
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 14
- 229920002635 polyurethane Polymers 0.000 claims description 14
- 239000004814 polyurethane Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- CYCBPQPFMHUATH-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound OCCCCOCC1CO1 CYCBPQPFMHUATH-UHFFFAOYSA-N 0.000 claims description 11
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 11
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- UXMYUFHUUYBDLL-UHFFFAOYSA-N 2,2-dimethyl-3-(oxiran-2-ylmethoxy)propan-1-ol Chemical compound OCC(C)(C)COCC1CO1 UXMYUFHUUYBDLL-UHFFFAOYSA-N 0.000 claims description 7
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 7
- WNISWKAEAPQCJQ-UHFFFAOYSA-N 2-[(2-nonylphenoxy)methyl]oxirane Chemical compound CCCCCCCCCC1=CC=CC=C1OCC1OC1 WNISWKAEAPQCJQ-UHFFFAOYSA-N 0.000 claims description 7
- SSLDKXORXLCJBF-UHFFFAOYSA-N 2-amino-3,4,5-trifluorobenzoic acid Chemical compound NC1=C(F)C(F)=C(F)C=C1C(O)=O SSLDKXORXLCJBF-UHFFFAOYSA-N 0.000 claims description 7
- FXEMCOVVTSYFRJ-UHFFFAOYSA-N 3-amino-2,5,6-trifluorobenzoic acid Chemical compound NC1=CC(F)=C(F)C(C(O)=O)=C1F FXEMCOVVTSYFRJ-UHFFFAOYSA-N 0.000 claims description 7
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 claims description 7
- NPOKVVQMFRQBAO-UHFFFAOYSA-N 6-amino-2,3,4-trifluorobenzoic acid Chemical compound NC1=CC(F)=C(F)C(F)=C1C(O)=O NPOKVVQMFRQBAO-UHFFFAOYSA-N 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 7
- 229960001124 trientine Drugs 0.000 claims description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007767 bonding agent Substances 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 6
- 229940083037 simethicone Drugs 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical class CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims 2
- 229920006332 epoxy adhesive Polymers 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 7
- 230000035882 stress Effects 0.000 description 6
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical class CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- OQILSTRGJVCFAG-UHFFFAOYSA-N 1-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound CCCC(O)OCC1CO1 OQILSTRGJVCFAG-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000004579 marble Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000004823 Reactive adhesive Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C08G59/60—Amines together with other curing agents with amides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C08G2170/00—Compositions for adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a stone binder and a preparation method thereof, the stone binder adopts a mixed curing agent composed of a polyether amine modified curing agent and an aliphatic amine modified curing agent, has excellent adhesion and a certain stress relaxation function, and improves the dispersion effect of modified calcium carbonate in resin by modifying the modified calcium carbonate, thereby greatly improving the adhesion performance of an epoxy adhesive. The preparation method and operation of the epoxy adhesive are relatively simple and convenient, the utilization rate of raw materials is high, the bonded stone has high strength, and secondary cracking in the later period can be effectively avoided.
Description
Technical Field
The invention relates to a stone adhesive, in particular to a stone binder and a preparation method thereof, and belongs to the technical field of building material adhesion.
Background
The natural stone slab has elegant texture and unique and beautiful texture, and is often used as a facing material for inner and outer walls, floors, ceilings, windowsills, table tops and sanitary wares of buildings. With the development of economy, the living standard of people is improved and the culture is improved, and the quantity of the decorative materials is increased. With the wide application of stone in the construction industry, the market demand of the stone bonding adhesive is continuously expanded, which is particularly embodied in the bonding and reinforcing operation of repairing, installing and positioning the stone, and the bonding and reinforcing material for repairing, installing and positioning the stone at the present stage mainly adopts unsaturated polyester adhesive (marble adhesive); it has a lot of not enoughly when the location of stone material is consolidated, if: the volatilization is serious, the volatile matter is toxic, the unsaturated polyester adhesive contains 20-30% of styrene monomer, and is volatile at room temperature, the styrene has larger toxicity and irritation, the industrial sanitation and labor protection are influenced, and the leukemia can be caused by long-term contact; the shrinkage rate is large, and large stress is generated by curing shrinkage; high brittleness, poor ageing resistance and the like. After the epoxy adhesive is cured, the epoxy adhesive has excellent adhesiveness and mechanical strength, excellent aging resistance, environmental protection, small shrinkage rate and good toughness after modification, accelerates the curing speed on the basis of common epoxy adhesive, can completely replace unsaturated polyester adhesive (marble adhesive), and meets the requirement of quick positioning and bonding of stone dry hanging in the building industry.
The epoxy resin contains various polar groups and epoxy groups with high activity, so that the epoxy resin has high adhesive force with materials with high surface activity, and the epoxy cured material has high cohesive strength, so that the adhesive strength is high, the curing shrinkage is small, the size stability of the cured product is good, the hardness of the cured product is high, and the polishing processing is easy. Therefore, in the stone processing industry at present, the adhesive prepared by taking the epoxy resin as the raw material gradually occupies the leading position of the market.
Although the epoxy resin material is widely used, the epoxy resin material has a plurality of defects when used as a stone adhesive, and the stone adhesive has relatively small adhesive area in the repairing, installing and positioning processes, so that the adhesive is relatively large in stress, and the performance requirements on the adhesive are high, especially the adhesive strength, stability, wear resistance, stain resistance and the like of the adhesive.
Disclosure of Invention
The invention provides a stone binder which is a reactive adhesive, has few volatile matters and low shrinkage rate in the curing process, and simultaneously adopts two modified curing agent compositions, thereby having excellent adhesion and a certain stress relaxation function. The stone binder also adopts modified calcium carbonate, so that on one hand, the appearance of the cured rubber material is as close as possible to that of the stone, and simultaneously, the bonding strength, wear resistance, aging resistance, stain resistance and other properties of the stone binder can be enhanced.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
according to a first embodiment of the present invention, an adhesive for stone is provided.
An adhesive for stone comprises a component A and a component B, wherein the component A comprises:
the epoxy resin is 35 to 55 parts by weight, preferably 40 to 50 parts by weight, and more preferably 42 to 48 parts by weight.
The reactive diluent is 1 to 7 parts by weight, preferably 2 to 6 parts by weight, and more preferably 3 to 5 parts by weight.
6-20 parts of toughening agent, preferably 8-18 parts of toughening agent, and more preferably 10-15 parts of toughening agent.
The modified calcium carbonate is 15 to 35 parts by weight, preferably 20 to 32 parts by weight, and more preferably 25 to 30 parts by weight.
The thixotropic agent is 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, and more preferably 2 to 4 parts by weight.
The defoaming agent is 0.05 to 1 part by weight, preferably 0.08 to 0.8 part by weight, and more preferably 0.1 to 0.5 part by weight.
1-6 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black.
Wherein the component B comprises:
the modified curing agent is 62 to 88 parts by weight, preferably 65 to 85 parts by weight, and more preferably 68 to 80 parts by weight.
The accelerator is 0.5 to 7 parts by weight, preferably 0.8 to 6 parts by weight, and more preferably 1 to 5 parts by weight.
1 to 10 parts by weight, preferably 2 to 9 parts by weight, and more preferably 3 to 8 parts by weight of a silane coupling agent.
The thixotropic agent is 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight, and more preferably 0.08 to 0.5 part by weight.
0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black.
The modified calcium carbonate is 8 to 25 parts by weight, preferably 10 to 22 parts by weight, and more preferably 12 to 20 parts by weight.
Wherein the modified curing agent is a mixture of polyether amine modified curing agent and fatty amine modified curing agent.
The sum of the components in the component A is 100 parts by weight. The sum of the components in the component B is 100 parts by weight.
Preferably, the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resins. Preferably a mixture of E-51 epoxy and 133L epoxy.
Preferably, the polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an epoxy resin. Preferably, the curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an E-51 epoxy resin and then further treating the modified curing agent with benzyl alcohol.
Preferably, the aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine modified by nonylphenol glycidyl ether.
Preferably, the amount of benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine-modified curing agent.
Preferably, in the mixed modified curing agent consisting of the polyether amine modified curing agent and the fatty amine modified curing agent, the mass ratio of the polyether amine modified curing agent to the fatty amine modified curing agent is 1:0.5-3, and preferably 1: 0.8-2.
Preferably, the reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether. Preferably glycerol triglycidyl ether and/or 1, 4-butanediol glycidyl ether.
Preferably, the toughening agent is an active polyurethane toughening agent.
Preferably, the defoaming agent is one of simethicone, BYK-530 and BYK-088.
Preferably, the modified calcium carbonate is obtained by modifying calcium carbonate with aminobenzoic acid. The aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid and 6-amino-2, 3, 4-trifluorobenzoic acid, and is preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid.
Preferably, the particle size composition of the modified calcium carbonate is as follows: 10-30% of particle size less than 100 meshes, 25-55% of particle size 100-200 meshes, 18-35% of particle size 300-500 meshes and 12-28% of particle size more than 500 meshes.
Preferably, the accelerator is selected from one or more of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), tris- (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine, thiourea. 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) is preferred.
Preferably, the white carbon black is fumed silica.
Preferably, the silane coupling agent is a dialkoxysilane or trialkoxysilane coupling agent containing an amino or hydroxyl functional group. Preferably one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and diethylenetriaminopropyltriethoxysilane.
Preferably, the thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.
According to a second embodiment of the invention, a method for preparing a binder for stone material or a method for preparing a binder for stone material according to the first embodiment is provided.
A method for preparing a binder for stone, comprising the steps of:
s1: preparation of the component A: firstly, mixing epoxy resin, reactive diluent, toughening agent, defoaming agent and white carbon black. Then adding the modified calcium carbonate and the thixotropic agent, and continuously mixing to obtain the component A after uniform mixing.
S2: preparation of the component B: firstly, mixing the modified curing agent and the accelerator. Then adding the thixotropic agent and the silane coupling agent and continuously mixing uniformly. Finally, adding the modified calcium carbonate and the white carbon black, and continuously mixing to obtain the component B after uniform mixing.
S3: preparing a two-component stone binder: bottling the component A and the component B according to the proportion to obtain the double-component stone binder.
Wherein the modified curing agent is a mixed modified curing agent consisting of polyether amine modified curing agent and fatty amine modified curing agent according to the mass ratio of 1:0.5-3 (preferably 1: 0.8-2). The modified calcium carbonate is modified calcium carbonate obtained by modifying calcium carbonate with aminobenzoic acid.
Preferably, the aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid, 6-amino-2, 3, 4-trifluorobenzoic acid, and preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid.
Preferably, the amounts of the components are as follows: wherein the component A is as follows:
the epoxy resin is 35 to 55 parts by weight, preferably 40 to 50 parts by weight, and more preferably 42 to 48 parts by weight.
The reactive diluent is 1 to 7 parts by weight, preferably 2 to 6 parts by weight, and more preferably 3 to 5 parts by weight.
6-20 parts of toughening agent, preferably 8-18 parts of toughening agent, and more preferably 10-15 parts of toughening agent.
The modified calcium carbonate is 15 to 35 parts by weight, preferably 20 to 32 parts by weight, and more preferably 25 to 30 parts by weight.
The thixotropic agent is 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, and more preferably 2 to 4 parts by weight.
The defoaming agent is 0.05 to 1 part by weight, preferably 0.08 to 0.8 part by weight, and more preferably 0.1 to 0.5 part by weight.
1-6 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black.
Wherein the component B is as follows:
the modified curing agent is 62 to 88 parts by weight, preferably 65 to 85 parts by weight, and more preferably 68 to 80 parts by weight.
The accelerator is 0.5 to 7 parts by weight, preferably 0.8 to 6 parts by weight, and more preferably 1 to 5 parts by weight.
1 to 10 parts by weight, preferably 2 to 9 parts by weight, and more preferably 3 to 8 parts by weight of a silane coupling agent.
The thixotropic agent is 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight, and more preferably 0.08 to 0.5 part by weight.
0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black.
The modified calcium carbonate is 8 to 25 parts by weight, preferably 10 to 22 parts by weight, and more preferably 12 to 20 parts by weight.
Preferably, the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resins. Preferably a mixture of E-51 epoxy and 133L epoxy.
Preferably, the polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an epoxy resin. Preferably, the curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an E-51 epoxy resin and then further treating the modified curing agent with benzyl alcohol. The aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine which are modified by nonyl phenol glycidyl ether. Preferably, the amount of benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine-modified curing agent.
Preferably, the reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether.
Preferably, the accelerator is selected from one or more of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), tris- (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine, thiourea.
Preferably, the toughening agent is an active polyurethane toughening agent.
Preferably, the defoaming agent is one of simethicone, BYK-530 and BYK-088.
Preferably, the white carbon black is fumed silica.
Preferably, the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), and diethylenetriaminopropyltriethoxysilane.
Preferably, the thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.
Preferably, S1 is specifically: preparation of the component A: the epoxy resin, the reactive diluent, the toughening agent, the defoaming agent and the fumed silica are uniformly mixed under the condition of raising the temperature (for example, the epoxy resin, the reactive diluent, the toughening agent, the defoaming agent and the fumed silica are uniformly stirred and mixed at 50-95 ℃ and preferably at 60-80 ℃). Then starting high-speed stirring and vacuumizing (for example, vacuumizing to-0.01 MPa to-0.09 MPa), wherein the high-speed stirring time is 10-60 min. And finally, adding the modified calcium carbonate and the thixotropic agent, continuously stirring for 10-40min, cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain the component A.
Preferably, S2 is specifically: preparation of the component B: the modified curing agent is firstly mixed uniformly according to the proportion, and then the accelerant is added to continue mixing uniformly (for example, stirring and mixing for 10-60 min). Then adding the thixotropic agent and the silane coupling agent and mixing uniformly (for example, stirring and mixing). After a period of time, high-speed stirring is started and vacuum is pumped (for example, the vacuum pumping is from-0.01 MPa to-0.09 MPa), and the high-speed stirring time is 10-60 min. And finally, adding the modified calcium carbonate and the fumed silica, continuously stirring (stirring for 10-40min), cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.
Preferably, S3 is specifically: preparing a two-component stone binder: and respectively bottling the component A and the component B according to the mass ratio of 1:1.0-1.5 (preferably 1:1.1-1.3) to obtain the two-component stone binder.
In the present invention, a mixture of E-51 epoxy resin and 133L epoxy resin is preferably used as the epoxy resin. The 133L epoxy resin, the E-51 epoxy resin and the reactive diluent form an IPN interpenetrating polymer network structure, so that the adhesive density of the system is improved, and the toughness is improved without sacrificing the strength. And 133L of epoxy resin can improve the compatibility of the E-51 epoxy resin and the reactive diluent. (E51 epoxy resin and 133L epoxy resin are both from south Asia electronic materials Co., Ltd.)
In the invention, the modified curing agent is a mixture of polyether amine modified curing agent and fatty amine modified curing agent. The polyether amine modified curing agent is self-made and is prepared by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with E-51 epoxy resin. Preferably, the polyether amine modified curing agent is a curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with E-51 epoxy resin to obtain the polyether amine modified curing agent, and then treating the polyether amine modified curing agent with benzyl alcohol. Still preferably, the amount of the benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine-modified curing agent. The aliphatic amine modified curing agent is also self-made, and refers to the aliphatic amine modified curing agent which is prepared by modifying one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine by using nonyl phenol glycidyl ether. Through modification of the polyether amine, the defects of low hardness, small adhesion, poor moisture resistance, long curing time and the like of the polyether amine are overcome; the defects of high normal-temperature volatility, high toxicity and the like of aliphatic amines are overcome by modifying the aliphatic amines; meanwhile, the polyether amine modified curing agent and the fatty amine modified curing agent are compounded according to a certain proportion (for example, the mass ratio of the polyether amine modified curing agent to the fatty amine modified curing agent is 1:0.5-3, preferably 1:0.8-2), so that excellent complementation can be realized, the bonding strength, the tensile strength, the shear strength and the bending strength of the epoxy cured product are greatly improved, the high temperature resistance, the corrosion resistance, the wear resistance and the like are greatly improved, the maximum elongation is improved, the flexibility is good, and the later-stage secondary cracking and stripping can be effectively avoided.
According to the invention, the specific epoxy resin and the specific curing agent are combined for use, so that the curing effect is good, on one hand, a compact film layer is formed, and the internal stress is effectively eliminated after curing. After a long time (e.g., 2 years) has elapsed after the construction, the film layer section is sampled, and the sample is examined by a Scanning Electron Microscope (SEM), and no micro-cracks or micro-pores are found on the sample surface of the film layer.
In the invention, the cracking resistance of the colloid is improved and the stability and the ageing resistance of the material are improved by adding the active polyurethane toughening agent. The toughening agent does not generate chemical reaction when blending epoxy resin and a diluent, but has good physical blending stability, is not layered and can stably exist for a long time. The toughening agent contains terminal epoxy group which is active to amino group and can generate chemical reaction. The elastomer structure with a 'polyurethane-urea' structure is generated by the reaction of the active polyurethane and the amino, meanwhile, the epoxy group and the amino of the epoxy resin react to generate a body type polymer containing a flexible chain, the two reactions are carried out simultaneously to form an IPN polymer interpenetrating network, and finally, the cured product changes the molecular structure of the polymer to increase the elongation and toughness of the polymer, thereby improving the cracking resistance of the colloid, avoiding the phenomenon that the plasticizer migrates to the surface of the colloid along with the time extension in different degrees when the flexibility is increased by simply depending on external plasticization, and further obtaining more effective material stability and aging hard and brittle life compared with the method of simply adding the external plasticizer for plasticization.
In the present invention, the reactive diluent is or includes one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether, and neopentyl glycol glycidyl ether, and preferably one or two selected from glycerol triglycidyl ether and 1,4 butanediol glycidyl ether are used. The reactive diluent can improve the consistency and optimize the construction performance.
In the present invention, the silane coupling agent is a dialkoxysilane-based or trialkoxysilane-based coupling agent containing an amino or hydroxyl functional group. Preferably one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and diethylenetriaminopropyltriethoxysilane. The coupling agent can increase the adhesive property.
In the present invention, the accelerator is selected from one or more of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), tris- (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine, thiourea. 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) is preferred. The accelerator can accelerate the reaction speed.
In the present invention, the modified calcium carbonate is modified calcium carbonate. The grain size composition is as follows: 10-30% of particle size less than 100 meshes, 25-55% of particle size 100-200 meshes, 18-35% of particle size 300-500 meshes and 12-28% of particle size more than 500 meshes. In general, when calcium carbonate is directly used as a filler, since it has a small particle size, a high surface energy, unstable thermodynamic properties, and easy agglomeration of particles affects its filling effect, aminobenzoic acid having both amino and carboxyl groups (e.g., anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid, 6-amino-2, 3, 4-trifluorobenzoic acid, and more preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid) as a modifier to obtain modified calcium carbonate; on one hand, the modified calcium carbonate is in composite bonding with special groups (such as carboxyl) contained in the modifier, so that the van der Waals force among calcium carbonate particles can be effectively reduced, the agglomeration phenomenon among the calcium carbonate particles is avoided, and the dispersibility of the modified calcium carbonate is improved; on the other hand, the calcium carbonate is bonded on the epoxy group through the special group (such as amino group) contained in the modifier and the epoxy resin, so that the adhesive property and the adhesive strength of the epoxy adhesive are greatly improved. When the fluorine-substituted aminobenzoic acid is used as a modifier, the aminobenzoic acid containing the fluorine-substituted group is not only used as a bonding bridge between the filler and the resin, but also can be used as a side chain group on the main chain of the resin after being bonded with an epoxy group of the resin through a chemical bond due to the fluorine-substituted group, so that the epoxy adhesive has better weather resistance, cold resistance, high temperature resistance and corrosion resistance, and also has higher thermal stability and surface self-cleaning performance due to the carbon-fluorine bond length and large bond energy. The modified calcium carbonate is used as the filler, so that the mechanical strength of the colloid can be increased, the curing shrinkage is reduced, the thermal expansion coefficient of a cured material is reduced, and the sensitivity of the rubber material to high and low temperature changes is reduced, so that the internal stress is reduced, and secondary cracking is avoided.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the self-made polyether amine modified curing agent is matched with the polyamide curing agent for use, so that the defect of a single curing agent is overcome, the self-made polyether amine modified curing agent and the polyamide curing agent are complementary and mutually assisted, and the self-made polyether amine modified curing agent has high strength, high maximum elongation and good flexibility; the prepared adhesive has excellent adhesion and certain stress relieving function. The preparation method and operation of the bonding agent are relatively simple and convenient, the material utilization rate is high, the stone material has higher strength after being bonded by the epoxy adhesive, and the secondary cracking in the later period can be effectively avoided.
2. According to the invention, the modified calcium carbonate and the hydrophobic fumed silica are matched for use, so that the paste property of the binder is ensured, the dispersibility of the calcium carbonate in resin is further improved, the binding property of the binder is greatly improved, and meanwhile, the weather resistance, cold resistance, high temperature resistance and corrosion resistance of the binder are further improved by introducing side chain fluorine groups, so that the binder has higher thermal stability, surface self-cleaning property and the like.
3. The binder disclosed by the invention is simple in preparation method, wide in raw material source, simple and convenient in construction method, greatly improves the construction efficiency, and has the advantages of low cost, good binding performance and low curing shrinkage rate.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
An adhesive for stone comprises a component A and a component B, wherein the component A comprises:
the epoxy resin is 35 to 55 parts by weight, preferably 40 to 50 parts by weight, and more preferably 42 to 48 parts by weight.
The reactive diluent is 1 to 7 parts by weight, preferably 2 to 6 parts by weight, and more preferably 3 to 5 parts by weight.
6-20 parts of toughening agent, preferably 8-18 parts of toughening agent, and more preferably 10-15 parts of toughening agent.
The modified calcium carbonate is 15 to 35 parts by weight, preferably 20 to 32 parts by weight, and more preferably 25 to 30 parts by weight.
The thixotropic agent is 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, and more preferably 2 to 4 parts by weight.
The defoaming agent is 0.05 to 1 part by weight, preferably 0.08 to 0.8 part by weight, and more preferably 0.1 to 0.5 part by weight.
1-6 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black.
Wherein the component B comprises:
the modified curing agent is 62 to 88 parts by weight, preferably 65 to 85 parts by weight, and more preferably 68 to 80 parts by weight.
The accelerator is 0.5 to 7 parts by weight, preferably 0.8 to 6 parts by weight, and more preferably 1 to 5 parts by weight.
1 to 10 parts by weight, preferably 2 to 9 parts by weight, and more preferably 3 to 8 parts by weight of a silane coupling agent.
The thixotropic agent is 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight, and more preferably 0.08 to 0.5 part by weight.
0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black.
The modified calcium carbonate is 8 to 25 parts by weight, preferably 10 to 22 parts by weight, and more preferably 12 to 20 parts by weight.
Wherein the modified curing agent is a mixture of polyether amine modified curing agent and fatty amine modified curing agent.
Preferably, the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resins. Preferably a mixture of E-51 epoxy and 133L epoxy.
Preferably, the polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an epoxy resin. Preferably, the curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an E-51 epoxy resin and then further treating the modified curing agent with benzyl alcohol.
Preferably, the aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine modified by nonylphenol glycidyl ether.
Preferably, the amount of benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine-modified curing agent.
Preferably, in the mixed modified curing agent consisting of the polyether amine modified curing agent and the fatty amine modified curing agent, the mass ratio of the polyether amine modified curing agent to the fatty amine modified curing agent is 1:0.5-3, and preferably 1: 0.8-2.
Preferably, the reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether. Preferably glycerol triglycidyl ether and/or 1, 4-butanediol glycidyl ether.
Preferably, the toughening agent is an active polyurethane toughening agent.
Preferably, the defoaming agent is one of simethicone, BYK-530 and BYK-088.
Preferably, the modified calcium carbonate is obtained by modifying calcium carbonate with aminobenzoic acid. The aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid and 6-amino-2, 3, 4-trifluorobenzoic acid, and is preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid.
Preferably, the particle size composition of the modified calcium carbonate is as follows: 10-30% of particle size less than 100 meshes, 25-55% of particle size 100-200 meshes, 18-35% of particle size 300-500 meshes and 12-28% of particle size more than 500 meshes.
Preferably, the accelerator is selected from one or more of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), tris- (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine, thiourea. 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) is preferred.
Preferably, the white carbon black is fumed silica.
Preferably, the silane coupling agent is a dialkoxysilane or trialkoxysilane coupling agent containing an amino or hydroxyl functional group. Preferably one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and diethylenetriaminopropyltriethoxysilane.
Preferably, the thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.
A method for preparing a binder for stone, comprising the steps of:
s1: preparation of the component A: firstly, mixing epoxy resin, reactive diluent, toughening agent, defoaming agent and white carbon black. Then adding the modified calcium carbonate and the thixotropic agent, and continuously mixing to obtain the component A after uniform mixing.
S2: preparation of the component B: firstly, mixing the modified curing agent and the accelerator. Then adding the thixotropic agent and the silane coupling agent and continuously mixing uniformly. Finally, adding the modified calcium carbonate and the white carbon black, and continuously mixing to obtain the component B after uniform mixing.
S3: preparing a two-component stone binder: bottling the component A and the component B according to the proportion to obtain the double-component stone binder.
Wherein the modified curing agent is a mixed modified curing agent consisting of polyether amine modified curing agent and fatty amine modified curing agent according to the mass ratio of 1:0.5-3 (preferably 1: 0.8-2). The modified calcium carbonate is modified calcium carbonate obtained by modifying calcium carbonate with aminobenzoic acid.
Preferably, the aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid, 6-amino-2, 3, 4-trifluorobenzoic acid, and preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid.
Preferably, the amounts of the components are as follows: wherein the component A is as follows:
the epoxy resin is 35 to 55 parts by weight, preferably 40 to 50 parts by weight, and more preferably 42 to 48 parts by weight.
The reactive diluent is 1 to 7 parts by weight, preferably 2 to 6 parts by weight, and more preferably 3 to 5 parts by weight.
6-20 parts of toughening agent, preferably 8-18 parts of toughening agent, and more preferably 10-15 parts of toughening agent.
The modified calcium carbonate is 15 to 35 parts by weight, preferably 20 to 32 parts by weight, and more preferably 25 to 30 parts by weight.
The thixotropic agent is 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, and more preferably 2 to 4 parts by weight.
The defoaming agent is 0.05 to 1 part by weight, preferably 0.08 to 0.8 part by weight, and more preferably 0.1 to 0.5 part by weight.
1-6 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black.
Wherein the component B is as follows:
the modified curing agent is 62 to 88 parts by weight, preferably 65 to 85 parts by weight, and more preferably 68 to 80 parts by weight.
The accelerator is 0.5 to 7 parts by weight, preferably 0.8 to 6 parts by weight, and more preferably 1 to 5 parts by weight.
1 to 10 parts by weight, preferably 2 to 9 parts by weight, and more preferably 3 to 8 parts by weight of a silane coupling agent.
The thixotropic agent is 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight, and more preferably 0.08 to 0.5 part by weight.
0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black.
The modified calcium carbonate is 8 to 25 parts by weight, preferably 10 to 22 parts by weight, and more preferably 12 to 20 parts by weight.
Preferably, the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resins. Preferably a mixture of E-51 epoxy and 133L epoxy.
Preferably, the polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an epoxy resin. Preferably, the curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an E-51 epoxy resin and then further treating the modified curing agent with benzyl alcohol. The aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine which are modified by nonyl phenol glycidyl ether. Preferably, the amount of benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine-modified curing agent.
Preferably, the reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether.
Preferably, the accelerator is selected from one or more of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), tris- (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine, thiourea.
Preferably, the toughening agent is an active polyurethane toughening agent.
Preferably, the defoaming agent is one of simethicone, BYK-530 and BYK-088.
Preferably, the white carbon black is fumed silica.
Preferably, the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), and diethylenetriaminopropyltriethoxysilane.
Preferably, the thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.
Preferably, S1 is specifically: preparation of the component A: the epoxy resin, the reactive diluent, the toughening agent, the defoaming agent and the fumed silica are uniformly mixed under the condition of raising the temperature (for example, the epoxy resin, the reactive diluent, the toughening agent, the defoaming agent and the fumed silica are uniformly stirred and mixed at 50-95 ℃ and preferably at 60-80 ℃). Then starting high-speed stirring and vacuumizing (for example, vacuumizing to-0.01 MPa to-0.09 MPa), wherein the high-speed stirring time is 10-60 min. And finally, adding the modified calcium carbonate and the thixotropic agent, continuously stirring for 10-40min, cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain the component A.
Preferably, S2 is specifically: preparation of the component B: the modified curing agent is firstly mixed uniformly according to the proportion, and then the accelerant is added to continue mixing uniformly (for example, stirring and mixing for 10-60 min). Then adding the thixotropic agent and the silane coupling agent and mixing uniformly (for example, stirring and mixing). After a period of time, high-speed stirring is started and vacuum is pumped (for example, the vacuum pumping is from-0.01 MPa to-0.09 MPa), and the high-speed stirring time is 10-60 min. And finally, adding the modified calcium carbonate and the fumed silica, continuously stirring (stirring for 10-40min), cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.
Preferably, S3 is specifically: preparing a two-component stone binder: and respectively bottling the component A and the component B according to the mass ratio of 1:1.0-1.5 (preferably 1:1.1-1.3) to obtain the two-component stone binder.
Example 1
Preparation of the component A: 38.0g of 38.0g E-51 epoxy resin, 9.0g of 133L epoxy resin, 4.0g of 1, 4g of butanediol glycidyl ether, 13.5g of active polyurethane, 0.3g of BYK-088 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of heating to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 28.0g of modified calcium carbonate and 3.7g of hydrogenated castor oil were added and stirring was continued for 30min, the temperature was reduced to room temperature and stirring was stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.
Preparation of the component B: 32.0g of polyether amine modified curing agent and 43.0g of fatty amine modified curing agent are uniformly mixed, and then 3.0g of DMP-30 is added to continue stirring and mixing for 30 min. Then 0.4g of hydrogenated castor oil and 5.0g of KH-550 are added and mixed uniformly. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. And then adding 14.4g of modified calcium carbonate and 2.2g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.
Preparation of a bonding agent I for stone: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the stone binder I.
Example 2
Preparation of the component A: 47.0g of 47.0g E-51 epoxy resin, 4g of 1, 4g of butanediol glycidyl ether, 13.5g of active polyurethane, 0.3g of BYK-088 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of heating to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 28.0g of modified calcium carbonate and 3.7g of hydrogenated castor oil were added and stirring was continued for 30min, the temperature was reduced to room temperature and stirring was stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.
Preparation of the component B: 32.0g of polyether amine modified curing agent and 43.0g of fatty amine modified curing agent are uniformly mixed, and then 3.0g of DMP-30 is added to continue stirring and mixing for 30 min. Then 0.4g of hydrogenated castor oil and 5.0g of KH-550 are added and mixed uniformly. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. And then adding 14.4g of modified calcium carbonate and 2.2g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.
Preparation of stone binder II: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the stone binder II.
Example 3
Preparation of the component A: 38.0g of 38.0g E-51 epoxy resin, 9.0g of 133L epoxy resin, 4g of benzyl glycidyl ether, 13.5g of active polyurethane, 0.3g of BYK-088 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of heating to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 28.0g of modified calcium carbonate and 3.7g of hydrogenated castor oil were added and stirring was continued for 30min, the temperature was reduced to room temperature and stirring was stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.
Preparation of the component B: 32.0g of polyether amine curing agent and 43.0g of fatty amine curing agent are uniformly mixed, then 3.0g of DMP-30 is added, and the mixture is continuously stirred and mixed for 30 min. Then 0.4g of hydrogenated castor oil and 5.0g of KH-550 are added and mixed uniformly. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. And then adding 14.4g of modified calcium carbonate and 2.2g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.
Preparation of stone binder III: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the stone binder III.
Example 4
Preparation of the component A: 38.0g of 38.0g E-51 epoxy resin, 9.0g of 133L epoxy resin, 4g of benzyl glycidyl ether, 13.5g of active polyurethane, 0.3g of BYK-088 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of heating to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 28.0g of calcium carbonate and 3.7g of hydrogenated castor oil are added and stirring is continued for 30min, the temperature is reduced to room temperature and the stirring is stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.
Preparation of the component B: 32.0g of polyether amine modified curing agent and 43.0g of fatty amine modified curing agent are uniformly mixed, and then 3.0g of DMP-30 is added to continue stirring and mixing for 30 min. Then 0.4g of hydrogenated castor oil and 5.0g of KH-550 are added and mixed uniformly. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. Then adding 14.4g of calcium carbonate and 2.2g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.
Preparation of stone binder IV: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the stone binder IV.
Example 5
Preparation of the component A: 38.0g of 38.0g E-51 epoxy resin, 9.0g of 133L epoxy resin, 4g of glycerol triglycidyl ether, 13.5g of reactive polyurethane, 0.3g of BYK-088 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of raising the temperature to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 28.0g of modified calcium carbonate and 3.7g of hydrogenated castor oil were added and stirring was continued for 30min, the temperature was reduced to room temperature and stirring was stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.
Preparation of the component B: 75.0g of the polyetheramine modified curing agent and 3.0g of DMP-30 were stirred and mixed for 30 min. Then 0.4g of hydrogenated castor oil and 5.0g of KH-550 are added and mixed well. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. And then adding 14.4g of modified calcium carbonate and 2.2g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.
Preparation of stone binder V: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the stone binder V.
Example 6
Preparation of the component A: 38.0g of 38.0g E-51 epoxy resin, 9.0g of 133L epoxy resin, 4g of glycerol triglycidyl ether, 13.5g of reactive polyurethane, 0.3g of BYK-088 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of raising the temperature to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 28.0g of modified calcium carbonate and 3.7g of hydrogenated castor oil were added and stirring was continued for 30min, the temperature was reduced to room temperature and stirring was stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.
Preparation of the component B: 75.0g of fatty amine modified curing agent and 3.0g of DMP-30 are stirred and mixed for 30 min. Then 0.4g of hydrogenated castor oil and 5.0g of KH-550 are added and mixed well. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. And then adding 14.4g of modified calcium carbonate and 2.2g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.
Preparation of stone binder VI: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the stone binder VI.
And (3) effect testing: the stone binders I to VI prepared in examples 1 to 6 were subjected to aging and strength tests, and the results were as follows:
TABLE 1 aging Performance test
Table 2 strength properties testing
Claims (10)
1. The bonding agent for the stone is characterized in that: the adhesive comprises a component A and a component B, wherein the component A comprises:
35-55 parts by weight of epoxy resin, preferably 40-50 parts by weight, more preferably 42-48 parts by weight;
1-7 parts by weight of reactive diluent, preferably 2-6 parts by weight, more preferably 3-5 parts by weight;
6-20 parts of toughening agent, preferably 8-18 parts, more preferably 10-15 parts;
15-35 parts by weight of modified calcium carbonate, preferably 20-32 parts by weight, more preferably 25-30 parts by weight;
1-5 parts by weight of thixotropic agent, preferably 1.5-4.5 parts by weight, more preferably 2-4 parts by weight;
0.05 to 1 part by weight of a defoaming agent, preferably 0.08 to 0.8 part by weight, more preferably 0.1 to 0.5 part by weight;
1-6 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black;
wherein the component B comprises:
62-88 parts of modified curing agent, preferably 65-85 parts, more preferably 68-80 parts;
0.5-7 parts by weight of accelerator, preferably 0.8-6 parts by weight, more preferably 1-5 parts by weight;
1-10 parts by weight of silane coupling agent, preferably 2-9 parts by weight, more preferably 3-8 parts by weight;
0.01 to 1 part by weight of a thixotropic agent, preferably 0.05 to 0.8 part by weight, more preferably 0.08 to 0.5 part by weight;
0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black;
8-25 parts of modified calcium carbonate, preferably 10-22 parts of modified calcium carbonate, and more preferably 12-20 parts of modified calcium carbonate;
wherein the modified curing agent is a mixture of polyether amine modified curing agent and fatty amine modified curing agent.
2. The bonding agent for stone according to claim 1, wherein: the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resin; preferably a mixture of E-51 epoxy resin and 133L epoxy resin; and/or
The polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine by epoxy resin; preferably a polyether amine modified curing agent which is modified by polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine by E-51 epoxy resin and then is further treated by benzyl alcohol;
the aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine which are modified by nonyl phenol glycidyl ether;
preferably, the amount of the benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyether amine modified curing agent; and/or
In the mixed modified curing agent consisting of the polyether amine modified curing agent and the fatty amine modified curing agent, the mass ratio of the polyether amine modified curing agent to the fatty amine modified curing agent is 1:0.5-3, preferably 1: 0.8-2.
3. The bonding agent for stone according to claim 1 or 2, wherein: the reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether; preferably glycerol triglycidyl ether and/or 1, 4-butanediol glycidyl ether; and/or
The toughening agent is an active polyurethane toughening agent; and/or
The defoaming agent is one of simethicone, BYK-530 and BYK-088.
4. An adhesive for stone according to any one of claims 1 to 3, wherein: the modified calcium carbonate is obtained by modifying calcium carbonate by adopting aminobenzoic acid; the aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid and 6-amino-2, 3, 4-trifluorobenzoic acid, preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid;
preferably, the particle size composition of the modified calcium carbonate is as follows: 10-30% of particle size less than 100 meshes, 25-55% of particle size 100-200 meshes, 18-35% of particle size 300-500 meshes and 12-28% of particle size more than 500 meshes.
5. An adhesive for stone according to any one of claims 1 to 4, wherein: the promoter is selected from one or more of 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30), tri- (2-ethylhexanoic acid) salt of 2,4, 6-tri (dimethylaminomethyl) phenol, triethanolamine and thiourea; preferably 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30); and/or
The white carbon black is fumed silica.
6. An adhesive for stone according to any one of claims 1 to 5, wherein: the silane coupling agent is dialkoxysilane or trialkoxysilane coupling agent containing amino or hydroxyl functional groups; preferably one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), and diethylenetriaminopropyltriethoxysilane; and/or
The thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.
7. Method for preparing a bonding agent for stone materials according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
s1: preparation of the component A: firstly, mixing epoxy resin, an active diluent, a toughening agent, a defoaming agent and white carbon black; then adding the modified calcium carbonate and the thixotropic agent, and continuously mixing to obtain a component A after uniform mixing;
s2: preparation of the component B: firstly, mixing a modified curing agent and an accelerant; then adding a thixotropic agent and a silane coupling agent and continuously mixing uniformly; finally, adding the modified calcium carbonate and the white carbon black, and continuously mixing to obtain a component B after uniform mixing;
s3: preparing a two-component stone binder: bottling the component A and the component B according to a proportion to obtain the double-component stone binder;
wherein the modified curing agent is a mixed modified curing agent consisting of a polyether amine modified curing agent and a fatty amine modified curing agent according to the mass ratio of 1:0.5-3 (preferably 1: 0.8-2); the modified calcium carbonate is modified calcium carbonate obtained by modifying calcium carbonate with aminobenzoic acid;
preferably, the aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid, 6-amino-2, 3, 4-trifluorobenzoic acid, and preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid.
8. The method of claim 7, wherein: the dosage of each component is as follows: wherein the component A is as follows:
35-55 parts by weight of epoxy resin, preferably 40-50 parts by weight, more preferably 42-48 parts by weight;
1-7 parts by weight of reactive diluent, preferably 2-6 parts by weight, more preferably 3-5 parts by weight;
6-20 parts of toughening agent, preferably 8-18 parts, more preferably 10-15 parts;
15-35 parts by weight of modified calcium carbonate, preferably 20-32 parts by weight, more preferably 25-30 parts by weight;
1-5 parts by weight of thixotropic agent, preferably 1.5-4.5 parts by weight, more preferably 2-4 parts by weight;
0.05 to 1 part by weight of a defoaming agent, preferably 0.08 to 0.8 part by weight, more preferably 0.1 to 0.5 part by weight;
1-6 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black;
wherein the component B is as follows:
62-88 parts of modified curing agent, preferably 65-85 parts, more preferably 68-80 parts;
0.5-7 parts by weight of accelerator, preferably 0.8-6 parts by weight, more preferably 1-5 parts by weight;
1-10 parts by weight of silane coupling agent, preferably 2-9 parts by weight, more preferably 3-8 parts by weight;
0.01 to 1 part by weight of a thixotropic agent, preferably 0.05 to 0.8 part by weight, more preferably 0.08 to 0.5 part by weight;
0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black;
the modified calcium carbonate is 8 to 25 parts by weight, preferably 10 to 22 parts by weight, and more preferably 12 to 20 parts by weight.
9. The method according to claim 7 or 8, characterized in that: the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resin; preferably a mixture of E-51 epoxy resin and 133L epoxy resin; and/or
The polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine by epoxy resin; preferably a polyether amine modified curing agent which is modified by polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine by E-51 epoxy resin and then is further treated by benzyl alcohol; the aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine which are modified by nonyl phenol glycidyl ether; preferably, the amount of benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine modified curing agent; and/or
The reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether; and/or
The promoter is selected from one or more of 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30), tri- (2-ethylhexanoic acid) salt of 2,4, 6-tri (dimethylaminomethyl) phenol, triethanolamine and thiourea; and/or
The toughening agent is an active polyurethane toughening agent; and/or
The defoaming agent is one of simethicone, BYK-530 and BYK-088; and/or
The white carbon black is fumed silica; and/or
The silane coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and diethylenetriaminopropyltriethoxysilane; and/or
The thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.
10. The method of claim 9, wherein: s1 specifically includes: preparation of the component A: firstly, uniformly mixing the epoxy resin, the reactive diluent, the toughening agent, the defoaming agent and the fumed silica under the condition of heating (for example, uniformly stirring and mixing at 50-95 ℃, preferably 60-80 ℃); then starting high-speed stirring and vacuumizing (for example, vacuumizing to-0.01 MPa to-0.09 MPa), wherein the high-speed stirring time is 10-60 min; finally, adding the modified calcium carbonate and the thixotropic agent, continuing stirring for 10-40min, cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain a component A; and/or
S2 specifically includes: preparation of the component B: firstly, uniformly mixing the modified curing agent according to the proportion, then adding the accelerant and continuously uniformly mixing (for example, stirring and mixing for 10-60 min); then adding the thixotropic agent and the silane coupling agent and uniformly mixing (for example, stirring and mixing); after a period of time, starting high-speed stirring and vacuumizing (for example, vacuumizing to-0.01 MPa to-0.09 MPa), wherein the high-speed stirring time is 10-60 min; finally, adding the modified calcium carbonate and the fumed silica, continuously stirring (stirring for 10-40min), cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain a component B; and/or
S3 specifically includes: preparing a two-component stone binder: and respectively bottling the component A and the component B according to the mass ratio of 1:1.0-1.5 (preferably 1:1.1-1.3) to obtain the two-component stone binder.
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| CN114149776A (en) * | 2021-12-10 | 2022-03-08 | 武汉市科达云石护理材料有限公司 | Internal toughening type epoxy structural adhesive and preparation method thereof |
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