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CN104312398A - Polyurea-polysiloxane organic-inorganic hybridized concrete biological pollution protection material and preparation method thereof - Google Patents

Polyurea-polysiloxane organic-inorganic hybridized concrete biological pollution protection material and preparation method thereof Download PDF

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Publication number
CN104312398A
CN104312398A CN201410566514.3A CN201410566514A CN104312398A CN 104312398 A CN104312398 A CN 104312398A CN 201410566514 A CN201410566514 A CN 201410566514A CN 104312398 A CN104312398 A CN 104312398A
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polysiloxane
acid ester
polyurea
epoxy resin
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CN104312398B (en
Inventor
韩炜
李珍
邵晓妹
汪在芹
甘国权
尹作仿
景锋
苏强
刘校
郑卫
邝亚力
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WUHAN CHANGJIANG KECHUANG TECHNOLOGY DEVELOPMENT Co Ltd
Changjiang River Scientific Research Institute Changjiang Water Resources Commission
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WUHAN CHANGJIANG KECHUANG TECHNOLOGY DEVELOPMENT Co Ltd
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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    • C08K5/00—Use of organic ingredients
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    • C08K5/00—Use of organic ingredients
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Abstract

The invention discloses a polyurea-polysiloxane organic-inorganic hybridized concrete biological pollution protection material and a preparation method thereof. The pollution protection material is composed of a surface protection material and a base protection material, wherein the surface protection material is composed of the following raw materials in parts by weight: polyaspartic acid ester modified polysiloxane, modified isocyanate, a biological growth inhibitor, a catalyst, a coupling agent, an anti-ageing agent, a filler and pigment; the base protection material is composed of the following raw materials in parts by weight: modified epoxy resin, an epoxy curing agent, an reactive diluent, a coupling agent, an anti-ageing agent and a filler. The pollution protection material is excellent in biological pollution imitation performance, has the characteristic of low surface energy and can prevent biofouling. Special elements in structure interior of the material can inhibit growth of ocean and fresh water creatures, thereby achieving the aim of preventing biological pollution.

Description

Polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material and preparation method thereof
Technical Field
The invention relates to the field of biological pollution protection materials, in particular to a polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material and a preparation method thereof.
Background
According to statistics, 31 pumped storage power stations and 23 pumped storage power stations under construction are built in China by 2012. Particularly southern power stations, which are a significant percentage of the diversion tunnels of pumped storage power stations, Ca (OH)2Subjected to HCO in reservoir water3CO produced by decomposition2Corrosion of cement hydrate, decomposition of cement hydrate, surface strength reduction, exfoliation under pressure of pressurized water and CO2Secondary erosion is performed on the aggregate of the exfoliated concrete. In addition, a large amount of limnoperna lacustris is generated on the surface of the concrete in the tunnel, the propagation is fast, the distribution is wide, the inhabitation characteristic and the growth characteristic of the limnoperna lacustris not only have erosion influence on the concrete, but also increase the inner wall of the tunnelThe roughness affects the water delivery efficiency and power generation of the tunnel. In order to effectively protect the concrete in the tunnel from CO2And the erosion of limnoperna lacustris, a novel surface coating material which can protect concrete from various loss erosion and effectively prevent the attachment of limnoperna lacustris, has high construction efficiency and excellent durability needs to be developed, so that the long-term, efficient and stable operation of a power plant is ensured.
At present, most of the concrete anti-corrosion materials in China are epoxy resin, polyurethane, polyurea, cement permeable crystallization type, organosilicon, vinyl resin, fluorocarbon, silane and the like, and the materials have certain effect on concrete anti-corrosion protection, but the materials do not have the function of effectively preventing limnoperna lacustris. The prevention method of the limnoperna lacustris comprises a physical method, a chemical method, a biological method and the like, wherein the physical method comprises the modes of physical interception, water temperature control, light ray control, water flow velocity control, engineering operation mode optimization, mechanical and manual cleaning, dehydration and drying and the like, the chemical method comprises the modes of byssus dissolution, chemical agent killing and the like, and the biological method mainly comprises a biological inhibition method. Most physical methods are complex in operation, more in factor limitation, and poor in controllability and feasibility. Compared with a physical method, the chemical killing method has the characteristics of strong controllability, quick response and the like, but has certain hidden danger on water supply safety due to the problems of chemical components, structures and the like. When the killing effect is examined, the long-term influence of the killing effect is also considered. The application of the biological inhibition method has great limitation, can only be used in an open water body area, and is suitable for the growth environment of the fishes predating the limnoperna lacustris.
In summary, at present, no simple, effective and environment-friendly material and preparation method capable of effectively preventing concrete corrosion and inhibiting the growth of the limnoperna lacustris thereon exist at home and abroad.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material and a preparation method thereof.
In order to solve the technical problems, the invention provides a polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material, which comprises a surface layer protection material and a base layer protection material, and is characterized in that: the surface layer protective material comprises the following raw materials in parts by weight: 45-60 parts of polyaspartic acid ester modified polysiloxane, 20-50 parts of modified isocyanate, 5-10 parts of biological growth inhibitor, 0.5-3 parts of catalyst, 0.5-3 parts of coupling agent, 0.5-1 part of anti-aging agent, 5-10 parts of filler and 1-5 parts of pigment;
the base layer protective material comprises the following raw materials in parts by weight: 30-40 parts of modified epoxy resin, 20-40 parts of epoxy resin curing agent, 20-50 parts of reactive diluent, 1-5 parts of coupling agent, 0.5-1 part of anti-aging agent and 1-5 parts of filler.
Further, the polyaspartic acid ester modified polysiloxane comprises the following raw materials in parts by weight: 30-50 parts of polyamine, 20-40 parts of maleic acid ester and 30-50 parts of polysiloxane; wherein,
the polyamine is any one of difunctional primary amine, difunctional polyether amine and difunctional heterocyclic diamine with low molecular weight;
the difunctional primary amines are preferably hexamethylenediamine, isophoronediamine, dicyclohexylmethanediamine and 3,3 '-dimethyl-4, 4' -dicyclohexylmethanediamine;
the difunctional polyether amines preferably include polypropylene glycol diamine and polyethylene glycol diamine;
the difunctional heterocyclic diamines are preferably 4, 7-dioxadecane-1, 10-diamine, 4, 9-dioxadodecane-1, 12-diamine and 4, 7, 10-trioxatridecane-1, 13-diamine;
the maleate is any one of diethyl maleate, dimethyl maleate, dipropyl maleate, dibutyl maleate and methyl propyl maleate;
the polysiloxane is one or more of polydimethylsiloxane, amino-terminated polydimethylsiloxane, epoxy-terminated polysiloxane, polymethylphenylsiloxane, propylamino-terminated polysiloxane, aminopropyl-terminated polydimethyldiphenylsiloxane, aminopropyl-terminated polycyanopropyl methylsiloxane, siloxane containing Si-H bonds, carboxyl-terminated polydimethylsiloxane, tetramethyldisiloxane and poly-side aminopropyl-methylsiloxane.
Still further, the preparation method of the polyaspartic ester modified polysiloxane comprises the following steps: the method comprises the following steps:
1) weighing polyamine, maleic acid ester and polysiloxane according to the weight part ratio for later use;
2) adding polyamine into a reaction kettle, stirring and introducing nitrogen;
3) slowly dropwise adding maleic acid ester into the reaction kettle, and keeping the temperature at 30-40 ℃; after the dropwise adding, heating to 90-100 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester;
4) putting the mixture into a reaction kettle filled with polyaspartic acid ester; continuously and slowly dripping polysiloxane, and keeping the temperature at 30-40 ℃; after the dropwise addition, heating to 60-120 ℃, and reacting for 8-20 h to obtain the polyaspartic acid ester modified polysiloxane.
Still further, the modified isocyanate is any one of toluene diisocyanate and a modified adduct thereof, diphenylmethane diisocyanate and a modified adduct thereof, toluene diisocyanate, n-butyl isocyanate, polyisocyanate, p-chlorophenyl isocyanate, chlorosulfonyl isocyanate, p-toluenesulfonyl isocyanate, methyl isocyanate, isopropyl isocyanate, diphenylmethane diisocyanate, and 1, 6-hexamethylene diisocyanate.
The biological growth inhibitor is any one of fluorine-containing silane and nano-scale silver additives;
the fluorine-containing silane is preferably trimethyl fluoro silane, triethyl fluoro silane, trifluoromethyl trimethyl silane, triethyl trifluoromethyl silane, tridecafluorooctyl trimethoxysilane, tridecafluorooctyl triethoxysilane and heptadecafluorodecyl trimethoxysilane; the nano-sized silver-based additive preferably includes organically modified silver particles and a silver antibacterial solution. (ii) a
Still further, the catalyst is N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethylpiperazine, triethanolamine, DME, and aromatic amines such as pyridine, N, N' -dimethylpyridine, dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecylthio) and dibutyltin diacetate.
Still further, the modified epoxy resin is any one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin, amino epoxy resin and glycidyl ester type epoxy resin.
Still further, the epoxy resin curing agent is any one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, m-xylylenediamine, triethanolamine, tetramethylguanidine, N' -dimethylpiperazine, and triethylenediamine.
Still further, the reactive diluent is butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, butylphenyl glycidyl ether and propylene oxide butyl ether.
Still further, the silane coupling agent is one or more of amino functional silane (KH550), methacryloxy functional silane (KH570), vinyltriethoxysilane (A-151), (vinyltrimethoxysilane) A-171, diamino functional silane (KH792), phenyltrimethoxysilane, phenyltriethoxysilane and methyltriethoxysilane;
the filler is talcum powder and TiO2、SiO2、BaSO4、ZnO、Al2O3And CaCO3Any one or more of the above, wherein the particle size of the filler is 5-50 nm;
the pigment is any one or more of titanium dioxide, iron black and carbon black;
the anti-aging agent is Chinox245, Chinox1010, ChinoxB225, UV-234, UV-328, SUV, 2-hydroxy-4-N-octoxybenzophenone (UV-531), 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole (UV327), KY-1010 and GW-628.
The invention also provides a preparation method of the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution prevention material, which is characterized by comprising the following steps: the method comprises the following steps:
1) weighing 30-50 parts of polyamine, 20-40 parts of maleic acid ester and 30-50 parts of polysiloxane for later use;
2) adding polyamine into a reaction kettle, stirring and introducing nitrogen;
3) slowly dropwise adding maleic acid ester into the reaction kettle, and keeping the temperature at 30-40 ℃; after the dropwise adding, heating to 90-100 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester;
4) putting the mixture into a reaction kettle filled with polyaspartic acid ester; continuously and slowly dripping polysiloxane, and keeping the temperature at 30-40 ℃; after the dropwise addition, heating to 60-120 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester modified polysiloxane;
5) weighing 45-60 parts of polyaspartic acid ester modified polysiloxane, 20-50 parts of modified isocyanate, 5-10 parts of biological growth inhibitor, 0.5-3 parts of catalyst, 0.5-3 parts of coupling agent, 0.5-1 part of anti-aging agent, 5-10 parts of filler and 1-5 parts of pigment according to the weight part ratio of the raw materials of the surface layer protective material for later use;
6) adding a biological growth inhibitor, a catalyst, a coupling agent, an anti-aging agent, a filler and a pigment into the polyaspartic acid ester modified polysiloxane, and uniformly mixing; adding modified isocyanate and mixing uniformly to obtain a surface layer protective material;
7) weighing 30-40 parts of modified epoxy resin, 20-40 parts of epoxy resin curing agent, 20-50 parts of reactive diluent, 1-5 parts of coupling agent, 0.5-1 part of anti-aging agent and 1-5 parts of filler according to the weight part ratio of the raw materials of the base protective material for later use.
8) Uniformly mixing the modified epoxy resin, the reactive diluent, the coupling agent, the anti-aging agent and the filler, and adding the epoxy resin curing agent to obtain a base protective material;
9) when in use, the base layer protective material is paved, and after the base layer material is cured, the surface layer protective material is paved, so that the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material is obtained.
The invention has the beneficial effects that:
1) has excellent biological pollution simulating performance, low surface energy and capacity of preventing attachment of organism. Meanwhile, special elements contained in the material structure can inhibit the growth of marine and freshwater organisms, so that the aim of preventing biological pollution is fulfilled;
2) the material system has excellent mechanical property, durability, green environmental protection performance, good matching performance with concrete, and anti-leakage, anti-cracking, anti-carbonization and anti-degradation performances.
3) The material system prepared by the invention not only can meet the biological pollution protection requirement of hydraulic concrete, but also can be applied to the concrete erosion protection field of marine environment, and has wide application prospect.
Detailed Description
In order to better explain the invention, the following further illustrate the main content of the invention in connection with specific examples, but the content of the invention is not limited to the following examples.
Example 1
1) Weighing 30 parts of dicyclohexylmethanediamine (HMDA), 40 parts of diethyl maleate and 30 parts of epoxy-terminated polysiloxane according to the weight part ratio for later use;
2) adding dicyclohexylmethane diamine (HMDA) into a reaction kettle, stirring and introducing nitrogen;
3) slowly dripping diethyl maleate into the reaction kettle, and keeping the temperature at 35 ℃; after the dropwise addition, heating to 90-100 ℃, and reacting for 12 hours to obtain polyaspartic acid ester;
4) putting the mixture into a reaction kettle filled with polyaspartic acid ester; continuously and slowly dripping epoxy-terminated polysiloxane, and keeping the temperature at 30-40 ℃; after the dropwise addition, heating to 60-120 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester modified polysiloxane;
5) weighing 50 parts of polyaspartic acid ester modified polysiloxane, 20 parts of 1, 6-hexamethylene diisocyanate, 5 parts of tridecafluorooctyltrimethoxysilane, 5 parts of nano-silver particles, 1 part of dibutyltin didodecylsulfate, 3 parts of coupling agent KH550, 0.5 part of age resister Chinox245, 0.5 part of age resister UV-234 and 5 parts of particle size 1 according to the weight part ratio of the raw materials of the surface layer protective material0nm SiO24 parts of titanium dioxide, 0.8 part of iron black and 0.2 part of carbon black for later use;
6) adding tridecafluorooctyltrimethoxysilane, nano-silver particles, dibutyltin didodecylsulfide, a silane coupling agent KH550, an age resister Chinox245, an age resister UV-234 and SiO with the particle size of 10nm into the polyaspartic acid ester modified polysiloxane2Mixing the titanium dioxide, the iron black and the carbon black uniformly; adding 1, 6-hexamethylene diisocyanate, and uniformly mixing to obtain a surface layer protective material;
7) weighing 35 parts of bisphenol A epoxy resin E51, 30 parts of diethylenetriamine, 30 parts of butyl glycidyl ether, 3 parts of silane coupling agent KH550, 1 part of anti-aging agent UV-531 and 1 part of CaCO with the particle size of 10nm according to the weight part ratio of the raw materials of the base protective material3And then standby.
8) Bisphenol A epoxy resin E51, butyl glycidyl ether, silane coupling agent KH550, anti-aging agent UV-531 and CaCO with particle diameter of 10nm3Uniformly mixing, and adding diethylenetriamine to obtain a base layer protective material;
9) when in use, the base layer protective material is paved, and after the base layer material is cured, the surface layer protective material is paved, so that the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 1 is obtained.
The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution prevention material 1 has the following basic properties:
main performance indexes of base protection material of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 1
Main performance indexes of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material surface layer protection material
Example 2
1) Weighing 50 parts of 3,3 '-dimethyl 4, 4' -dicyclohexylmethane diamine, 20 parts of dimethyl maleate, 20 parts of aminopropyl-terminated polycyanopropyl methyl siloxane and 30 parts of epoxy-terminated polysiloxane according to the parts by weight for later use;
2) adding 3,3 '-dimethyl 4, 4' -dicyclohexylmethane diamine into a reaction kettle, stirring and introducing nitrogen;
3) slowly dropwise adding dimethyl maleate into the reaction kettle, and keeping the temperature at 35 ℃; after the dropwise adding, heating to 90-100 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester;
4) putting the mixture into a reaction kettle filled with polyaspartic acid ester; continuously and slowly dropwise adding aminopropyl-terminated polycyanopropyl methyl siloxane and epoxy-terminated polysiloxane, and keeping the temperature at 30-40 ℃; after the dropwise addition, heating to 60-120 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester modified polysiloxane;
5) weighing 45 parts of polyaspartic acid ester modified polysiloxane, 30 parts of 1, 6-hexamethylene diisocyanate, 5 parts of trifluoromethyl trimethylsilane, 5 parts of nano silver particles, 1 part of dibutyltin dilaurate, 3 parts of silane coupling agent KH570, 0.5 part of age resister Chinox1010, 0.5 part of age resister SUV and 5 parts of SiO with the particle size of 10nm according to the weight part ratio of the raw materials of the surface layer protective material24 parts of titanium dioxide, 0.8 part of iron black and 0.2 part of carbon black for later use;
6) adding trifluoromethyl trimethylsilane, nano silver particles, dibutyltin dilaurate, a silane coupling agent KH570 and anti-aging into the polyaspartic acid ester modified polysiloxaneChinox1010 oxidant, anti-aging agent SUV, SiO with particle size of 10nm2Mixing the titanium dioxide, the iron black and the carbon black uniformly; adding 1, 6-hexamethylene diisocyanate, and uniformly mixing to obtain a surface layer protective material;
7) weighing 35 parts of bisphenol F type epoxy resin DER354, 30 parts of m-xylylenediamine, 30 parts of glycerol triglycidyl ether, 3 parts of silane coupling agent KH550, 1 part of anti-aging agent KY-1010 and 1 part of CaCO with the particle size of 10nm according to the weight part ratio of the raw materials of the base protective material3And then standby.
8) Bisphenol F type epoxy resin DER354, glycerol triglycidyl ether, silane coupling agent KH550, anti-aging agent KY-1010 and CaCO with particle diameter of 10nm3Uniformly mixing, and adding m-xylylenediamine to obtain a base layer protective material;
9) when in use, the base layer protective material is paved, and after the base layer material is cured, the surface layer protective material is paved, so that the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 2 is obtained.
The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution prevention material 2 has the following basic properties:
polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 2-base protective material main performance index
Polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 2 surface protective material main performance index
Example 3
1) Weighing 40 parts of 3,3 '-dimethyl 4, 4' -dicyclohexylmethane diamine, 30 parts of dimethyl maleate, 20 parts of aminopropyl-terminated polycyanopropyl methyl siloxane and 20 parts of epoxy-terminated polysiloxane according to the weight parts for later use;
2) adding 3,3 '-dimethyl 4, 4' -dicyclohexylmethane diamine into a reaction kettle, stirring and introducing nitrogen;
3) slowly dropwise adding dimethyl maleate into the reaction kettle, and keeping the temperature at 30-40 ℃; after the dropwise adding, heating to 90-100 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester;
4) putting the mixture into a reaction kettle filled with polyaspartic acid ester; continuously and slowly dropwise adding aminopropyl-terminated polycyanopropyl methyl siloxane and epoxy-terminated polysiloxane, and keeping the temperature at 35 ℃; after the dropwise addition, heating to 60-120 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester modified polysiloxane;
5) weighing 45 parts of polyaspartic acid ester modified polysiloxane, 30 parts of 1, 6-hexamethylene diisocyanate, 5 parts of trifluoromethyl trimethylsilane, 5 parts of nano silver particles, 1 part of dibutyltin dilaurate, 3 parts of silane coupling agent KH570, 0.5 part of age resister Chinox1010, 0.5 part of age resister SUV and 5 parts of SiO with the particle size of 10nm according to the weight part ratio of the raw materials of the surface layer protective material24 parts of titanium dioxide, 0.8 part of iron black and 0.2 part of carbon black for later use;
6) adding trifluoromethyl trimethylsilane, nano silver particles, dibutyltin dilaurate, silane coupling agent KH570, age resister Chinox1010 age resister SUV, and SiO with particle size of 10nm into polyaspartic acid ester modified polysiloxane2Mixing the titanium dioxide, the iron black and the carbon black uniformly; adding 1, 6-hexamethylene diisocyanate, and uniformly mixing to obtain a surface layer protective material;
7) weighing 35 parts by weight of raw materials of the base layer protective materialThe bisphenol F epoxy resin DER354, 20-40 parts of m-xylylenediamine, 30 parts of glycerol triglycidyl ether, 3 parts of coupling agent KH550, 1 part of age resister KY-1010 and 1 part of CaCO with the particle size of 10nm3And then standby.
8) The bisphenol F type epoxy resin DER354, glycerol triglycidyl ether, a coupling agent KH550, an anti-aging agent KY-1010 and CaCO with the particle size of 10nm3Uniformly mixing the active diluent, the coupling agent, the anti-aging agent and the filler, and adding m-xylylenediamine to obtain a base layer protective material;
9) when in use, the base layer protective material is paved, and after the base layer material is cured, the surface layer protective material is paved, so that the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 3 is obtained.
The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution prevention material 3 has the following basic properties:
polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 3-base protective material main performance index
Polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 3 surface protective material main performance index
Example 4
1) Weighing 45 parts of 4, 7-dioxadecane-1, 10-diamine, 35 parts of methylpropyl maleate and 35 parts of tetramethyldisiloxane in parts by weight for later use;
2) adding 4, 7-dioxadecane-1, 10-diamine into a reaction kettle, stirring and introducing nitrogen;
3) slowly dropwise adding methyl propyl maleate into the reaction kettle, and keeping the temperature at 35 ℃; after the dropwise adding, heating to 90-100 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester;
4) putting the mixture into a reaction kettle filled with polyaspartic acid ester; continuously and slowly dripping tetramethyldisiloxane, and keeping the temperature at 30-40 ℃; after the dropwise addition, heating to 60-120 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester modified polysiloxane;
5) weighing 60 parts of polyaspartic acid ester modified polysiloxane, 50 parts of p-chlorophenyl isocyanate, 5 parts of trifluoromethyl trimethylsilane, 0.5 part of bis (2-dimethylaminoethyl) ether, 0.5 part of phenyltrimethoxysilane, 1 part of an anti-aging agent ChinoxB225, 5 parts of ZnO with the particle size of 50nm and 1 part of titanium dioxide according to the weight part ratio of the raw materials of the surface layer protective material for later use;
6) adding trifluoromethyl trimethylsilane, bis (2-dimethylaminoethyl) ether, a coupling agent, an anti-aging agent, a filler and a pigment into the polyaspartic ester modified polysiloxane, and uniformly mixing; adding p-chlorophenyl isocyanate, and mixing uniformly to obtain a surface layer protective material;
7) weighing 40 parts of novolac epoxy resin, 20 parts of hexamethylenediamine, 50 parts of phenyl glycidyl ether, 5 parts of silane coupling agent KH171, 1 part of age resister GW-628 and 3 parts of CaCO with the particle size of 50nm according to the weight part ratio of the raw materials of the base protective material3And then standby.
8) Phenolic epoxy resin, phenyl glycidyl ether, silane coupling agent KH171, age resister GW-628 and CaCO with particle size of 50nm3Uniformly mixing, and adding hexamethylene diamine to obtain a base protective material;
9) when in use, the base layer protective material is paved, and after the base layer material is cured, the surface layer protective material is paved, so that the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 4 is obtained.
The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution prevention material 4 has the following basic properties:
polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 4-base protective material main performance index
Polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 4 surface protective material main performance index
Example 5
1) Weighing 45 parts of 4, 7-dioxadecane-1, 25 parts of diethyl maleate and 30 parts of poly side aminopropyl methyl siloxane according to the weight part ratio for later use;
2) adding 4, 7-dioxadecane-1 into a reaction kettle, stirring and introducing nitrogen;
3) slowly dropwise adding diethyl maleate into the reaction kettle, and keeping the temperature at 30-40 ℃; after the dropwise adding, heating to 90-100 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester;
4) putting the mixture into a reaction kettle filled with polyaspartic acid ester; continuously slowly dripping poly-lateral aminopropyl methyl siloxane, and keeping the temperature at 35 ℃; after the dropwise addition, heating to 60-120 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester modified polysiloxane;
5) weighing 55 parts of polyaspartic acid according to the weight part ratio of the raw materials of the surface layer protective materialAcid ester modified polysiloxane, 20 parts of N-butyl isocyanate, 7 parts of heptadecafluorodecyltrimethoxysilane, 1 part of triethylamine, N-dimethylbenzylamine, 2 parts of silane coupling agent KH171, 0.5 part of anti-aging agent UV-328, and 7 parts of Al with the particle size of 20nm2O3And 2 parts of iron oxide black for later use;
6) adding heptadecafluorodecyltrimethoxysilane, triethylamine, N-dimethylbenzylamine, silane coupling agent KH171, anti-aging agent UV-328 and Al with particle size of 20nm into polyaspartic acid ester modified polysiloxane2O3Mixing with iron black; adding modified isocyanate and mixing uniformly to obtain a surface layer protective material;
7) weighing 30 parts of amino epoxy resin, 20 parts of tetraethylenepentamine, 40 parts of cresyl glycidyl ether, 5 parts of phenyltriethoxysilane, 1 part of anti-aging agent UV327 and 2 parts of BaSO with the particle size of 20nm according to the weight part ratio of the raw materials of the base layer protective material4And then standby.
8) Amino epoxy resin, cresyl glycidyl ether, phenyl triethoxysilane, anti-aging agent UV327 and BaSO with particle size of 20nm4Uniformly mixing, and adding tetraethylenepentamine to obtain a base layer protective material;
9) when in use, the base layer protective material is paved, and after the base layer material is cured, the surface layer protective material is paved, so that the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 5 is obtained.
The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution prevention material 5 has the following basic properties:
polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 5-base protective material main performance index
Polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material 5 surface layer protective material main performance index
Other parts not described in detail are prior art. Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims (10)

1. The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material comprises a surface layer protection material and a base layer protection material, and is characterized in that: the surface layer protective material comprises the following raw materials in parts by weight: 45-60 parts of polyaspartic acid ester modified polysiloxane, 20-50 parts of modified isocyanate, 5-10 parts of biological growth inhibitor, 0.5-3 parts of catalyst, 0.5-3 parts of coupling agent, 0.5-1 part of anti-aging agent, 5-10 parts of filler and 1-5 parts of pigment;
the base layer protective material comprises the following raw materials in parts by weight: 30-40 parts of modified epoxy resin, 20-40 parts of epoxy resin curing agent, 20-50 parts of reactive diluent, 1-5 parts of coupling agent, 0.5-1 part of anti-aging agent and 1-5 parts of filler.
2. The polyurea-polysiloxane organic-inorganic hybrid concrete biological contamination prevention material according to claim 1, characterized in that: the polyaspartic acid ester modified polysiloxane comprises the following raw materials in parts by weight: 30-50 parts of polyamine, 20-40 parts of maleic acid ester and 30-50 parts of polysiloxane; wherein,
the polyamine is any one of difunctional primary amine, difunctional polyether amine and difunctional heterocyclic diamine with low molecular weight;
the low molecular weight difunctional primary amine is any one of hexamethylene diamine, isophorone diamine, dicyclohexyl methane diamine and 3,3 '-dimethyl 4, 4' -dicyclohexyl methane diamine, and the difunctional polyether amine is polypropylene glycol diamine or polyethylene glycol diamine;
the difunctional heterocyclic diamine is any one of 4, 7-dioxadecane-1, 10-diamine, 4, 9-dioxadodecane-1, 12-diamine and 4, 7, 10-trioxatridecane-1, 13-diamine;
the maleate is any one of diethyl maleate, dimethyl maleate, dipropyl maleate, dibutyl maleate and methyl propyl maleate;
the polysiloxane is one or more of polydimethylsiloxane, amino-terminated polydimethylsiloxane, epoxy-terminated polysiloxane, polymethylphenylsiloxane, propylamino-terminated polysiloxane, aminopropyl-terminated polydimethyldiphenylsiloxane, aminopropyl-terminated polycyanopropyl methylsiloxane, siloxane containing Si-H bonds, carboxyl-terminated polydimethylsiloxane, tetramethyldisiloxane and poly-side aminopropyl-methylsiloxane.
3. The polyurea-polysiloxane organic-inorganic hybrid concrete biological contamination prevention material according to claim 2, characterized in that: the preparation method of the polyaspartic acid ester modified polysiloxane comprises the following steps: the method comprises the following steps:
1) weighing polyamine, maleic acid ester and polysiloxane according to the weight part ratio for later use;
2) adding polyamine into a reaction kettle, stirring and introducing nitrogen;
3) slowly dropwise adding maleic acid ester into the reaction kettle, and keeping the temperature at 30-40 ℃; after the dropwise adding, heating to 90-100 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester;
4) putting the mixture into a reaction kettle filled with polyaspartic acid ester; continuously and slowly dripping polysiloxane, and keeping the temperature at 30-40 ℃; after the dropwise addition, heating to 60-120 ℃, and reacting for 8-20 h to obtain the polyaspartic acid ester modified polysiloxane.
4. The polyurea-polysiloxane organic-inorganic hybrid concrete biological contamination prevention material according to claim 1 or 2, characterized in that: the modified isocyanate is any one of toluene diisocyanate and modified addition products thereof, diphenylmethane diisocyanate and modified addition products thereof, toluene diisocyanate, n-butyl isocyanate, polyisocyanate, p-chlorophenyl isocyanate, chlorosulfonyl isocyanate, p-toluenesulfonyl isocyanate, methyl isocyanate, isopropyl isocyanate, diphenylmethane diisocyanate and 1, 6-hexamethylene diisocyanate.
5. The polyurea-polysiloxane organic-inorganic hybrid concrete biological contamination prevention material according to claim 1 or 2, characterized in that: the biological growth inhibitor is one or more of fluorine-containing silane and nano-scale silver additives.
6. The polyurea-polysiloxane organic-inorganic hybrid concrete biological contamination prevention material according to claim 1 or 2, characterized in that: the catalyst is N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethylpiperazine, triethanolamine, DME, and aromatic amines such as pyridine, N, N' -dimethylpyridine, dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfide) and dibutyltin diacetate.
7. The polyurea-polysiloxane organic-inorganic hybrid concrete biological contamination prevention material according to claim 1 or 2, characterized in that: the modified epoxy resin is any one of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, amino epoxy resin and glycidyl ester epoxy resin.
8. The polyurea-polysiloxane organic-inorganic hybrid concrete biological contamination prevention material according to claim 1 or 2, characterized in that: the epoxy resin curing agent is any one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, m-xylylenediamine, triethanolamine, tetramethylguanidine, N' -dimethylpiperazine and triethylenediamine.
The active diluent is butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, butyl phenyl glycidyl ether and epoxypropane butyl ether.
9. The polyurea-polysiloxane organic-inorganic hybrid concrete biological contamination prevention material according to claim 1 or 2, characterized in that:
the coupling agent is a silane coupling agent, and the silane coupling agent is any one of amino functional group silane, methacryloxy functional group silane, vinyl triethoxysilane, vinyl trimethoxysilane, diamino functional group silane, phenyl trimethoxysilane, phenyl triethoxysilane and methyl triethoxysilane;
the filler is talcum powder and TiO2、SiO2、BaSO4、ZnO、Al2O3And CaCO3Any one or more of the above, wherein the particle size of the filler is 5-50 nm;
the pigment is any one or more of titanium dioxide, iron black and carbon black;
the anti-aging agent is Chinox245, Chinox1010, ChinoxB225, UV-234, UV-328, SUV, 2-hydroxy-4-N-octoxybenzophenone, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, KY-1010 and GW-628.
10. A preparation method of a polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution prevention material is characterized by comprising the following steps: the method comprises the following steps:
1) weighing 30-50 parts of polyamine, 20-40 parts of maleic acid ester and 30-50 parts of polysiloxane for later use;
2) adding polyamine into a reaction kettle, stirring and introducing nitrogen;
3) slowly dropwise adding maleic acid ester into the reaction kettle, and keeping the temperature at 30-40 ℃; after the dropwise adding, heating to 90-100 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester;
4) putting the mixture into a reaction kettle filled with polyaspartic acid ester; continuously and slowly dripping polysiloxane, and keeping the temperature at 30-40 ℃; after the dropwise addition, heating to 60-120 ℃, and reacting for 8-20 h to obtain polyaspartic acid ester modified polysiloxane;
5) weighing 45-60 parts of polyaspartic acid ester modified polysiloxane, 20-50 parts of modified isocyanate, 5-10 parts of biological growth inhibitor, 0.5-3 parts of catalyst, 0.5-3 parts of coupling agent, 0.5-1 part of anti-aging agent, 5-10 parts of filler and 1-5 parts of pigment according to the weight part ratio of the raw materials of the surface layer protective material for later use;
6) adding a biological growth inhibitor, a catalyst, a coupling agent, an anti-aging agent, a filler and a pigment into the polyaspartic acid ester modified polysiloxane, and uniformly mixing; adding modified isocyanate and mixing uniformly to obtain a surface layer protective material;
7) weighing 30-40 parts of modified epoxy resin, 20-40 parts of epoxy resin curing agent, 20-50 parts of reactive diluent, 1-5 parts of coupling agent, 0.5-1 part of anti-aging agent and 1-5 parts of filler according to the weight part ratio of the raw materials of the base protective material for later use.
8) Uniformly mixing the modified epoxy resin, the reactive diluent, the coupling agent, the anti-aging agent and the filler, and adding the epoxy resin curing agent to obtain a base protective material;
9) when in use, the base layer protective material is paved, and after the base layer material is cured, the surface layer protective material is paved, so that the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protective material is obtained.
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JP7440500B2 (en) 2018-10-19 2024-02-28 モメンティブ パフォーマンス マテリアルズ ゲーエムベーハー Aspartate functional polysiloxanes, their preparation and their uses
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