CN105176343A - Waterproof polyurea coating and preparation method thereof - Google Patents
Waterproof polyurea coating and preparation method thereof Download PDFInfo
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- CN105176343A CN105176343A CN201510591712.XA CN201510591712A CN105176343A CN 105176343 A CN105176343 A CN 105176343A CN 201510591712 A CN201510591712 A CN 201510591712A CN 105176343 A CN105176343 A CN 105176343A
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- silane
- component
- zinc sulfide
- coating
- sulfide white
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- 238000000576 coating method Methods 0.000 title claims abstract description 72
- 239000011248 coating agent Substances 0.000 title claims abstract description 70
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000570 polyether Polymers 0.000 claims abstract description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 25
- 239000004970 Chain extender Substances 0.000 claims abstract description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 47
- 239000005083 Zinc sulfide Substances 0.000 claims description 36
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 26
- 150000001412 amines Chemical group 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 230000006837 decompression Effects 0.000 claims description 14
- 230000018044 dehydration Effects 0.000 claims description 14
- 238000006297 dehydration reaction Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000004902 Softening Agent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 12
- OIWXXOQGYSGOIN-UHFFFAOYSA-N [diethoxy(hexadecyl)silyl] prop-2-enoate Chemical group C(CCCCCCCCCCCCCCC)[Si](OCC)(OCC)OC(C=C)=O OIWXXOQGYSGOIN-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- HRFBRMUMYWGLEQ-UHFFFAOYSA-N 2-(2-phenylethenyl)benzene-1,4-diamine Chemical group NC1=CC=C(N)C(C=CC=2C=CC=CC=2)=C1 HRFBRMUMYWGLEQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 229940059574 pentaerithrityl Drugs 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical group CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 17
- 230000032683 aging Effects 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 125000003277 amino group Chemical group 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- 150000001491 aromatic compounds Chemical class 0.000 abstract 1
- 238000013032 photocatalytic reaction Methods 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000007921 spray Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 238000005507 spraying Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- LXODQLXKQIJVNK-UHFFFAOYSA-N 2-(2-benzoyloxypropoxy)propyl benzoate Chemical class C=1C=CC=CC=1C(=O)OC(C)COC(C)COC(=O)C1=CC=CC=C1 LXODQLXKQIJVNK-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- -1 hydroxy group compound Chemical group 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3036—Sulfides of zinc
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a waterproof polyurea coating and a preparation method thereof. The waterproof polyurea coating comprises a component A and a component B, wherein the component A comprises 3,3-dimethyl- 4,4-diisocyanatodicyclohexylmethane, polyether glycol and a solvent; and the component B comprises aminopolyether, an amine chain extender, a plasticizer and silane-modified nanometer lithopone. According to the waterproof polyurea coating, 3,3-dimethyl-4,4-diisocyanatodicyclohexylmethane is used as the raw material, so that the light stability and weather resistance of the waterproof polyurea coating are improved, the problem that a coating prepared by taking an aromatic compound as a raw material is easily aged is solved, the coating is kept to have long enough gelling time and curing time, and the coating is relatively good in permeation and combination with a substrate. The silane-modified nanometer lithopone is adopted, so that the corrosion resistance and ageing resistance of the coating are improved; and ultraviolet is effectively absorbed, and a photocatalytic reaction is carried out, so that the coating has antibacterial property, and the pollution resistibility of the coating is improved.
Description
Technical field
The present invention relates to technical field of coatings, particularly relate to a kind of polyurea waterproof coating material and preparation method thereof.
Background technology
Spray Polyurea Elastomer Technology is abroad over nearly 10 years, after the low stain application techniques such as high solid coating, water-borne coatings, radiation curable coating, powder coating, in order to adapt to, ecological requirements is developed, a kind of Novel solvent-free developed, free of contamination green construction technology, in anticorrosion, waterproof, the engineering such as wear-resisting, have good application prospect.
Two component spray polyurea waterproof coating material utilizes isocyanate component and aminated compounds to react a kind of elastomer substances generated, and isocyanic ester both can be aromatic, also can be aliphatic.For two component spray polyurea waterproof coating material, first component is wherein monomer, polymer, the derivative of isocyanic ester, prepolymer and semi prepolymer, prepolymer and semi prepolymer are obtained by Amino End Group or terminal hydroxy group compound and isocyanate reaction, described terminal hydroxy group compound usually adopt oligopolymer dibasic alcohol, trivalent alcohol or between mixture; Second component is made up of Amino End Group resin, Amino End Group chainextender, pigment, filler and auxiliary agent etc.Two kinds of mixed speed of response of component are exceedingly fast, and need to be mixed by shock mode under certain temperature, pressure with specific equipment, carry out spraying or pour into a mould formation polyurea elastomer.
Based on aromatic series Spray Polyurea Elastomer in existing pair of component polyurea waterproof coating material, namely with aromatic isocyanate (TDI, MDI, PAPI) for main raw material synthesizing isocyanate performed polymer or hemipolymer, take aromatic amine as chainextender.Because aromatics can decompose under action of ultraviolet radiation, there is chemical instability, coating ageing-resistant performance is reduced.In prior art, application publication number is that the Chinese patent literature of CN101531861A discloses a kind of two-component spraying polyurea waterproof coating material, utilize aliphatic spray polyurea elastomer for raw material is to improve the ageing-resistant performance of coating products, but fundamentally do not solve ultraviolet to the solarization of carbamide paint, its ageing-resistant performance needs to be improved further.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of polyurea waterproof coating material and preparation method thereof, and this polyurea waterproof coating material has good corrosion-resistant, anti-aging and anti-microbial property.
In view of this, the invention provides a kind of polyurea waterproof coating material, comprise component A and B component, in mass fraction, described component A comprises:
50-65 part 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanate,
30-40 part polyether glycol,
5-10 part solvent;
Described B component comprises:
40-50 part amino-polyether,
30-40 part amine chain extender,
10-15 part softening agent,
The silane-modified nanometer zinc sulfide white of 5-10 part.
Preferably, described polyether glycol is tetramethylolmethane polyethers.
Preferably, described amino-polyether is diaminodiphenyl oxide.
Preferably, described amine chain extender is 2,5-diaminostilbene, 3,3-3-methyl cyclohexanol methylamine.
Preferably, described softening agent is dipropylene glycol dibenzoate.
Preferably, the granularity of silane-modified nanometer zinc sulfide white meets D
90be less than 50nm, whiteness is greater than 90%, and described silane is acryloxy hexadecyl diethoxy silane.
Preferably, described silane-modified nanometer zinc sulfide white is prepared as follows:
Be the hydrochloric acid soln adding 0.1M in the aqueous ethanolic solution of 1: 1 to volume ratio, adjust ph to 4.0, obtains mixing solutions;
In described mixing solutions, add nanometer zinc sulfide white, under the rotating speed of 500r/min stirs in the water-bath of 40 DEG C, dropwise add acryloxy hexadecyl diethoxy silane, continue to stir 3h, suction filtration, washing, obtain silane-modified zinc sulfide white after fully dry, pulverize at 80 DEG C.
Accordingly, the present invention also provides a kind of preparation method of polyurea waterproof coating material, in mass fraction, comprises the following steps:
30-40 part polyether glycol and 5-10 part solvent are placed in the first reactor, under agitation be warming up to 125 DEG C, pass into nitrogen and carry out atmosphere protection, decompression dehydration 3h, is cooled to 80 DEG C, then adds 50-65 part 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanate, reacts 3h after stirring, and obtains component A;
40-50 part amino-polyether, 30-40 part amine chain extender and 10-15 part softening agent are placed in the second reactor; pass into nitrogen and carry out atmosphere protection; decompression dehydration 3h at 120 DEG C; then silane-modified for 5-10 part nanometer zinc sulfide white is added described second reactor high speed to stir, obtain B component.
Preferably, described amine chain extender is 2,5-diaminostilbene, 3,3-3-methyl cyclohexanol methylamine.
Preferably, described silane-modified nanometer zinc sulfide white is prepared as follows: be the hydrochloric acid soln adding 0.1M in the aqueous ethanolic solution of 1: 1 to volume ratio, adjust ph to 4.0, obtains mixing solutions; In described mixing solutions, add nanometer zinc sulfide white, under the rotating speed of 500r/min stirs in the water-bath of 40 DEG C, dropwise add acryloxy hexadecyl diethoxy silane, continue to stir 3h, suction filtration, washing, obtain silane-modified zinc sulfide white after fully dry, pulverize at 80 DEG C.
The invention provides a kind of polyurea waterproof coating material and preparation method thereof, comprise component A and B component, in mass fraction, described component A comprises: 50-65 part 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanate, 30-40 part polyether glycol, 5-10 part solvent; Described B component comprises: 40-50 part amino-polyether, 30-40 part amine chain extender, 10-15 part softening agent, the silane-modified nanometer zinc sulfide white of 5-10 part.Compared with prior art, on the one hand, the present invention adopts 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanate to be raw material, it belongs to saturated fatty hydrocarbon compound, simultaneously with methyl chains, improve light stability and the weathering resistance of polyurea waterproof coating material, overcoming with aromatics is the problem that raw material dope is easily aging, guarantee that coating has enough gels and set time, coating and base material infiltration combine better simultaneously.On the other hand, the present invention adopts silane-modified nanometer zinc sulfide white to carry out modification to coating, not only increases the corrosion-resistant of coating and ageing resistance, and nanoparticle effectively can absorb the concurrent third contact of a total solar or lunar eclipse catalyzed reaction of ultraviolet simultaneously, give coating antibiosis performance, add the durability against pollution of coating.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of polyurea waterproof coating material, comprise component A and B component, in mass fraction, described component A comprises:
50-65 part 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanate,
30-40 part polyether glycol,
5-10 part solvent;
Described B component comprises:
40-50 part amino-polyether,
30-40 part amine chain extender,
10-15 part softening agent,
The silane-modified nanometer zinc sulfide white of 5-10 part.
The present invention adopts saturated fatty hydrocarbon compound to substitute arene raw material, to be with the cyclohexyl six-ring isocyanic ester-3 of methyl chains, 3-dimethyl-4,4-dicyclohexyl methane diisocyanate is raw material, this raw material belongs to saturated fatty hydrocarbon compound, simultaneously with methyl chains, screened raw material is made to have excellent light stability and weathering resistance.The present invention selects to have more SA aliphatic spray polyurea elastomer 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanate is raw material, not only overcome with aromatics is the problem that raw material dope is easily aging, guarantee that coating has enough gels and set time simultaneously, coating and base material infiltration are combined better.
Preferably, described polyether glycol is tetramethylolmethane polyethers; Described solvent is preferably vinyldimethicone.
In B component, described amino-polyether is preferably diaminodiphenyl oxide; Described amine chain extender is preferably 2,5-diaminostilbene, 3,3-3-methyl cyclohexanol methylamine; Described softening agent is preferably dipropylene glycol dibenzoate.
The amido chainextender that the present invention adopts is preferably 2,5-diaminostilbene, 3,3-3-methyl cyclohexanol methylamine, and it is a kind of novel chainextender, containing three Amino End Group groups, has excellent reactive behavior and chemical stability, improves the weather resistance of coating further.
Because general surface of inorganic particles is hydrophilic, not easily mix with traditional polymkeric substance, therefore, the present invention adopts silane-modified nanometer zinc sulfide white, its surface is hydrophobic, adds the consistency of particle and inorganic polymer, improves the dispersing uniformity of silane-modified nanometer zinc sulfide white in coating, making coating can wrap up particle uniformly, avoiding the adhesive property reducing coating because producing macrobead locally.
Preferably, the granularity of described silane-modified nanometer zinc sulfide white preferably meets D
90be less than 50nm, whiteness is greater than 90%, and described silane is preferably acryloxy hexadecyl diethoxy silane.
Preferably, described silane-modified nanometer zinc sulfide white is prepared as follows: be the hydrochloric acid soln adding 0.1M in the aqueous ethanolic solution of 1: 1 to volume ratio, adjust ph to 4.0, obtains mixing solutions; In described mixing solutions, add nanometer zinc sulfide white, under the rotating speed of 500r/min stirs in the water-bath of 40 DEG C, dropwise add acryloxy hexadecyl diethoxy silane, continue to stir 3h, suction filtration, washing, obtain silane-modified zinc sulfide white after fully dry, pulverize at 80 DEG C.
The filler that the present invention adopts is silane-modified nanometer zinc sulfide white, not only increase the corrosion-resistant of coating and ageing resistance, it contains zinc sulfide nano photocatalytic particle, effectively can absorb ultraviolet thus eliminate ultraviolet to the solarization of coating, improving the weathering resistance of coating.Simultaneously nanoparticle issues third contact of a total solar or lunar eclipse catalyzed reaction in action of ultraviolet radiation, gives the effect that coating surface has sterilization, can effectively kill bacteria, mould, maintenance coating top layer bright and clean, adds the durability against pollution of coating.
Preferably, the weight part of the present invention to each component adjusts, and described 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanates are preferably 55-65 part, are more preferably 55-60 part; Polyether glycol is preferably 33-40 part, is more preferably 33-37 part; Described solvent is preferably 5-8 part, is more preferably 7-8 part; Described amino-polyether is preferably 43-50 part, is more preferably 43-46 part; Described amine chain extender is preferably 30-37 part, is more preferably 34-37 part; Described softening agent is preferably 12-15 part, is more preferably 12-13 part; Described silane-modified nanometer zinc sulfide white is preferably 5-8 part, is more preferably 7-8 part.
Accordingly, the present invention also provides a kind of preparation method of polyurea waterproof coating material, in mass fraction, comprise the following steps: 30-40 part polyether glycol and 5-10 part solvent are placed in the first reactor, under agitation be warming up to 125 DEG C, pass into nitrogen and carry out atmosphere protection, decompression dehydration 3h, be cooled to 80 DEG C, then 50-65 part 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanate is added, react 3h after stirring, obtain component A; 40-50 part amino-polyether, 30-40 part amine chain extender, 10-15 part softening agent are placed in the second reactor; pass into nitrogen and carry out atmosphere protection; decompression dehydration 3h at 120 DEG C, then adds the second reactor high speed by silane-modified for 5-10 part nanometer zinc sulfide white and stirs, obtain B component.
Preferably, described amine chain extender is 2,5-diaminostilbene, 3,3-3-methyl cyclohexanol methylamine, it is a kind of novel chainextender, containing three Amino End Group groups, there is more excellent reactive behavior and chemical stability, improve the weather resistance of coating further.
Described silane-modified nanometer zinc sulfide white is preferably prepared as follows: be the hydrochloric acid soln adding 0.1M in the aqueous ethanolic solution of 1: 1 to volume ratio, adjust ph to 4.0, obtains mixing solutions; In described mixing solutions, add nanometer zinc sulfide white, under the rotating speed of 500r/min stirs in the water-bath of 40 DEG C, dropwise add acryloxy hexadecyl diethoxy silane, continue to stir 3h, suction filtration, washing, obtain silane-modified zinc sulfide white stopping composition at 80 DEG C after fully dry, pulverize.
The granularity of described silane-modified nanometer zinc sulfide white preferably meets D
90be less than 50nm, whiteness is greater than 90%, and described silane is preferably acryloxy hexadecyl diethoxy silane.
Described silane-modified nanometer zinc sulfide white not only increases the corrosion-resistant of coating and ageing resistance, and it contains zinc sulfide nano photocatalytic particle, effectively can absorb ultraviolet thus eliminate ultraviolet to the solarization of coating, improving the weathering resistance of coating.Simultaneously nanoparticle issues third contact of a total solar or lunar eclipse catalyzed reaction in action of ultraviolet radiation, gives the effect that coating surface has sterilization, can effectively kill bacteria, mould, maintenance coating top layer bright and clean, adds the durability against pollution of coating.
Preferably, the weight part of the present invention to each raw material adjusts, and 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanate is preferably 55-65 part, is more preferably 55-60 part; Polyether glycol is preferably 33-40 part, is more preferably 33-37 part; Solvent is preferably 5-8 part, is more preferably 7-8 part; Amino-polyether is preferably 43-50 part, is more preferably 43-46 part; Amine chain extender is preferably 30-37 part, is more preferably 34-37 part; Softening agent is preferably 12-15 part, is more preferably 12-13 part; Silane-modified nanometer zinc sulfide white is preferably 5-8 part, is more preferably 7-8 part.
Accordingly, the present invention also provides a kind of constructional method of polyurea waterproof coating material of above-mentioned preparation, comprising: by the component A of above-mentioned preparation and B component according to volume ratio 1: 1 with the use of, utilize high-pressure spray gun to make A and B component atomizing spraying film forming.
As can be seen from above scheme, 1, present invention employs the cyclohexyl six-ring isocyanic ester-3 of band methyl chains, 3-dimethyl-4,4-dicyclohexyl methane diisocyanate is raw material, this raw material belongs to saturated fatty hydrocarbon compound, simultaneously with methyl chains, screened raw material is made to have excellent light stability and weathering resistance.2, amido chainextender preferably adopts 2,5-diaminostilbene, 3,3-3-methyl cyclohexanol methylamine, and it contains three Amino End Group groups, has more excellent reactive behavior and chemical stability, improves the weather resistance of coating further.3, selected filler is silane-modified nanometer zinc sulfide white, containing zinc sulfide nano photocatalytic particle, effectively can absorb ultraviolet thus eliminate ultraviolet to the solarization of coating, improving the weathering resistance of coating.Simultaneously nanoparticle issues third contact of a total solar or lunar eclipse catalyzed reaction in action of ultraviolet radiation, gives the effect that coating surface has sterilization, can effectively kill bacteria, mould, maintenance coating top layer bright and clean.
In order to understand the present invention further, be described in detail to technical scheme provided by the invention below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
The raw material that the embodiment of the present invention adopts and chemical reagent are commercial.
Embodiment 1
First dose volume ratio is the aqueous ethanolic solution of 1: 1, by the hydrochloric acid soln adjust ph to 4.0 of 0.1M, nanometer zinc sulfide white is dispersed in above-mentioned solution, under in the water-bath of 40 DEG C, the rotating speed of 500r/min stirs, dropwise add acryloxy hexadecyl diethoxy silane, continue after completing to stir 3h, eventually pass suction filtration, washing, fully dry at 80 DEG C, pulverize, obtain silane-modified zinc sulfide white, the size composition of described nanometer zinc sulfide white meets D90 and is less than 50nm, and whiteness is greater than 90%.
Embodiment 2
(1), routine in mass ratio; take the tetramethylolmethane polyethers of 40 parts and 10 parts of vinyldimethicone in reactor; under agitation raised temperature to 125 DEG C; pass into nitrogen simultaneously and carry out atmosphere protection, above-mentioned substance is carried out decompression dehydration 3h, after completing, make temperature be reduced to 80 DEG C; then 50 parts 3 are added; 3-dimethyl-4,4-dicyclohexyl methane diisocyanate, keeps reaction 3h to obtain component A after stirring.
(2), according to mass ratio; take 40 parts of diaminodiphenyl oxides, 40 part 2; 5-diaminostilbene; 3; 3-3-methyl cyclohexanol methylamine, 10 parts of dipropylene glycol dibenzoates are in another reactor; pass into nitrogen protection decompression dehydration 3h at 120 DEG C, the silane-modified zinc sulfide white then adding 10 parts of embodiments 1 preparations stirs in reactor high speed, obtains B component.
(3), by component A and B component according to volume ratio 1: 1 with the use of, utilize high-pressure spray gun to make A and B component atomizing spraying film forming.
Embodiment 3
(1), routine in mass ratio; take the tetramethylolmethane polyethers of 37 parts and 8 parts of vinyldimethicone in reactor; under agitation raised temperature to 125 DEG C; pass into nitrogen simultaneously and carry out atmosphere protection, above-mentioned substance is carried out decompression dehydration 3h, after completing, make temperature be reduced to 80 DEG C; then 55 parts 3 are added; 3-dimethyl-4,4-dicyclohexyl methane diisocyanate, keeps reaction 3h to obtain component A after stirring.
(2), according to mass ratio; take 43 parts of diaminodiphenyl oxides, 37 part 2; 5-diaminostilbene; 3; 3-3-methyl cyclohexanol methylamine, 12 parts of dipropylene glycol dibenzoates are in another reactor; pass into nitrogen protection decompression dehydration 3h at 120 DEG C, the silane-modified zinc sulfide white then adding 8 parts of embodiments 1 preparations stirs in reactor high speed, obtains B component.
(3), by component A and B component according to volume ratio 1: 1 with the use of, utilize high-pressure spray gun to make A and B component atomizing spraying film forming.
Embodiment 4
(1), routine in mass ratio; take the tetramethylolmethane polyethers of 33 parts and 7 parts of vinyldimethicone in reactor; under agitation raised temperature to 125 DEG C; pass into nitrogen simultaneously and carry out atmosphere protection, above-mentioned substance is carried out decompression dehydration 3h, after completing, make temperature be reduced to 80 DEG C; then 60 parts 3 are added; 3-dimethyl-4,4-dicyclohexyl methane diisocyanate, keeps reaction 3h to obtain component A after stirring.
(2), according to mass ratio; take 46 parts of diaminodiphenyl oxides, 34 part 2; 5-diaminostilbene; 3; 3-3-methyl cyclohexanol methylamine, 13 parts of dipropylene glycol dibenzoates are in another reactor; pass into nitrogen protection decompression dehydration 3h at 120 DEG C, the silane-modified zinc sulfide white then adding 7 parts of embodiments 1 preparations stirs in reactor high speed, obtains B component.
(3), by component A and B component according to volume ratio 1: 1 with the use of, utilize high-pressure spray gun to make A and B component atomizing spraying film forming.
Embodiment 5
(1), routine in mass ratio; take the tetramethylolmethane polyethers of 30 parts and 5 parts of vinyldimethicone in reactor; under agitation raised temperature to 125 DEG C; pass into nitrogen simultaneously and carry out atmosphere protection, above-mentioned substance is carried out decompression dehydration 3h, after completing, make temperature be reduced to 80 DEG C; then 65 parts 3 are added; 3-dimethyl-4,4-dicyclohexyl methane diisocyanate, keeps reaction 3h to obtain component A after stirring.
(2), according to mass ratio; take 50 parts of diaminodiphenyl oxides, 30 part 2; 5-diaminostilbene; 3; 3-3-methyl cyclohexanol methylamine, 15 parts of dipropylene glycol dibenzoates are in another reactor; pass into nitrogen protection decompression dehydration 3h at 120 DEG C, the silane-modified zinc sulfide white then adding 5 parts of embodiments 1 preparations stirs in reactor high speed, obtains B component.
(3), by component A and B component according to volume ratio 1: 1 with the use of, utilize high-pressure spray gun to make A and B component atomizing spraying film forming.
Detect according to GB/T23446-2009 standard the leading indicator with the polyurea waterproof coating material of anti-microbial property prepared by embodiment of the present invention 2-5, its test result is as shown in table 1.As seen from table, the main performance index of the waterproof paint of each embodiment gained all meets national standard requirement.
The main performance index of table 1, each embodiment waterproof paint
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a polyurea waterproof coating material, is characterized in that, comprises component A and B component, and in mass fraction, described component A comprises:
50-65 part 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanate,
30-40 part polyether glycol,
5-10 part solvent;
Described B component comprises:
40-50 part amino-polyether,
30-40 part amine chain extender,
10-15 part softening agent,
The silane-modified nanometer zinc sulfide white of 5-10 part.
2. polyurea waterproof coating material according to claim 1, is characterized in that, described polyether glycol is tetramethylolmethane polyethers.
3. polyurea waterproof coating material according to claim 1, is characterized in that, described amino-polyether is diaminodiphenyl oxide.
4. polyurea waterproof coating material according to claim 1, is characterized in that, described amine chain extender is 2,5-diaminostilbene, 3,3-3-methyl cyclohexanol methylamine.
5. polyurea waterproof coating material according to claim 1, is characterized in that, described softening agent is dipropylene glycol dibenzoate.
6. the polyurea waterproof coating material according to claim 1-5 any one, is characterized in that, the granularity of silane-modified nanometer zinc sulfide white meets D
90be less than 50nm, whiteness is greater than 90%, and described silane is acryloxy hexadecyl diethoxy silane.
7. the polyurea waterproof coating material according to claim 1-5 any one, is characterized in that, described silane-modified nanometer zinc sulfide white is prepared as follows:
Be the hydrochloric acid soln adding 0.1M in the aqueous ethanolic solution of 1: 1 to volume ratio, adjust ph to 4.0, obtains mixing solutions;
In described mixing solutions, add nanometer zinc sulfide white, under the rotating speed of 500r/min stirs in the water-bath of 40 DEG C, dropwise add acryloxy hexadecyl diethoxy silane, continue to stir 3h, suction filtration, washing, obtain silane-modified zinc sulfide white after fully dry, pulverize at 80 DEG C.
8. a preparation method for polyurea waterproof coating material, is characterized in that, in mass fraction, comprises the following steps:
30-40 part polyether glycol and 5-10 part solvent are placed in the first reactor, under agitation be warming up to 125 DEG C, pass into nitrogen and carry out atmosphere protection, decompression dehydration 3h, is cooled to 80 DEG C, then adds 50-65 part 3,3-dimethyl-4,4-dicyclohexyl methane diisocyanate, reacts 3h after stirring, and obtains component A;
40-50 part amino-polyether, 30-40 part amine chain extender and 10-15 part softening agent are placed in the second reactor; pass into nitrogen and carry out atmosphere protection; decompression dehydration 3h at 120 DEG C; then silane-modified for 5-10 part nanometer zinc sulfide white is added described second reactor high speed to stir, obtain B component.
9. preparation method according to claim 8, is characterized in that, described amine chain extender is 2,5-diaminostilbene, 3,3-3-methyl cyclohexanol methylamine.
10. preparation method according to claim 8, is characterized in that, described silane-modified nanometer zinc sulfide white is prepared as follows:
Be the hydrochloric acid soln adding 0.1M in the aqueous ethanolic solution of 1: 1 to volume ratio, adjust ph to 4.0, obtains mixing solutions;
In described mixing solutions, add nanometer zinc sulfide white, under the rotating speed of 500r/min stirs in the water-bath of 40 DEG C, dropwise add acryloxy hexadecyl diethoxy silane, continue to stir 3h, suction filtration, washing, obtain silane-modified zinc sulfide white after fully dry, pulverize at 80 DEG C.
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| CN201510591712.XA CN105176343B (en) | 2015-09-12 | 2015-09-12 | A kind of polyurea waterproof coating material and preparation method thereof |
| CN201711091434.7A CN107641444A (en) | 2015-09-12 | 2015-09-12 | A kind of polyurea waterproof coating material and preparation method thereof |
| CN201711091424.3A CN107779065A (en) | 2015-09-12 | 2015-09-12 | A kind of polyurea waterproof coating material and preparation method thereof |
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| CN201711091424.3A Division CN107779065A (en) | 2015-09-12 | 2015-09-12 | A kind of polyurea waterproof coating material and preparation method thereof |
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| CN201711091434.7A Withdrawn CN107641444A (en) | 2015-09-12 | 2015-09-12 | A kind of polyurea waterproof coating material and preparation method thereof |
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| CN106118431A (en) * | 2016-07-29 | 2016-11-16 | 上海基典防水科技有限公司 | High intensity high ferro waterproof material and preparation method thereof |
| CN106243971A (en) * | 2016-07-29 | 2016-12-21 | 上海基典防水科技有限公司 | NEW TYPE OF COMPOSITE high ferro waterproof material and preparation method thereof |
| CN107286309A (en) * | 2016-04-01 | 2017-10-24 | 新疆科能防水防护技术股份有限公司 | Low VOC and high performance bi-component hand scratch-type polyurea waterproof coating material and preparation method thereof |
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Also Published As
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| CN107779065A (en) | 2018-03-09 |
| CN107641444A (en) | 2018-01-30 |
| CN105176343B (en) | 2018-05-11 |
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