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

Abstract

The invention discloses a polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material and a preparation method thereof. The pollution protection material is composed of a surface layer protection material and a base layer protection material. The surface layer protection material The raw materials include: polyaspartic acid ester modified polysiloxane, modified isocyanate, biological growth inhibitor, catalyst, coupling agent, anti-aging agent, filler and pigment; The raw materials of the material include: modified epoxy resin, epoxy resin curing agent, reactive diluent, coupling agent, antiaging agent and filler in terms of parts by weight. The invention has excellent performance of imitating biological pollution, has low surface energy characteristics, and can prevent biological adhesion. At the same time, the special elements contained in the material structure can inhibit the growth of marine and freshwater organisms, thereby achieving the purpose 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 technique

According to statistics, by the end of 2012, my country had built 31 pumped storage power stations and 23 pumped storage power stations under construction. In particular, the southern power station accounts for a considerable part. The Ca(OH) ₂ in the concrete in the diversion tunnel of these pumped storage power stations is eroded by the CO ₂ produced by the decomposition of HCO ₃ in the reservoir water, causing the decomposition of cement hydration products. The surface strength is reduced, and spalling occurs under the action of pressure dynamic water, and CO ₂ conducts secondary erosion on the aggregate of spalled concrete. In addition, a large amount of freshwater shellfish is produced on the surface of the concrete in the tunnel, which reproduces quickly and is widely distributed. Its group habitat and growth characteristics not only have an impact on the erosion of the concrete, but also increase the roughness of the inner wall of the tunnel, affecting the efficiency of water delivery and power generation of the tunnel. . In order to effectively protect the concrete inside the tunnel from the erosion of _CO2 and freshwater shellfish, it is necessary to develop a new surface coating material that can protect the concrete from various loss, dissolution and erosion, effectively prevent the adhesion of freshwater shellfish, high construction efficiency, and excellent durability. , so as to ensure the long-term efficient and stable operation of the power plant.

At present, domestic concrete anti-corrosion materials are mostly epoxy resins, polyurethanes, polyureas, cement permeable crystals, silicones, vinyl resins, fluorocarbons, silanes and other materials, which are very important for concrete anti-corrosion protection. Have certain effect, but these materials do not effectively prevent the function of freshwater shellfish. The prevention methods of freshwater shell vegetables include physical methods, chemical methods, biological methods, etc., among which physical methods include physical interception, control of water temperature, control of light, control of water flow rate, control of water flow rate, optimization of project operation mode, mechanical manual cleaning, dehydration and drying The chemical methods include silk dissolving, chemical agent killing, etc., and the biological methods are mainly based on biological inhibition. Most of the physical methods are complicated to operate, have many factors and restrictions, and are poor in controllability and feasibility. Compared with physical methods, chemical methods have the characteristics of strong controllability and quick results, but at the same time, due to their chemical composition and structure, there are certain hidden dangers to the safety of water supply. While examining its killing effect, attention should also be paid to its long-term impact. The application of bioinhibition method has great limitations, and it can only be used in open water body areas, which is suitable for the growth environment of freshwater shellfish that prey on them.

To sum up, at present, there is no simple, effective and environmentally friendly material and preparation method that can effectively prevent concrete erosion and inhibit the growth of freshwater shellfish on it.

Contents of the invention

The technical problem to be solved by the present invention is to provide a polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material and its preparation method. layer protective material and modified epoxy resin protective material, and finally obtained polyurea-polysiloxane organic-inorganic hybrid concrete biofouling protective material with excellent comprehensive performance. The protective material has excellent anti-biological pollution performance, super Strong weather resistance and aging resistance, as well as excellent mechanical properties, it also has the functions of concrete anti-leakage, anti-crack, anti-carbonization, and anti-corrosion.

In order to solve the above-mentioned technical problems, the invention provides a polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material, the pollution protection material is composed of a surface layer protection material and a base layer protection material, and is characterized in that: The raw materials of the surface protection material include: 45-60 parts of polyaspartate 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 raw materials of the basic protective material include: 30-40 parts of modified epoxy resin, 20-40 parts of epoxy resin curing agent, 20-50 parts of active diluent, 1-5 parts Coupling agent, 0.5-1 part of anti-aging agent and 1-5 parts of filler.

Further, the raw materials of the polyaspartic acid ester modified polysiloxane include: 30-50 parts of polyamine, 20-40 parts of maleic acid ester and 30-50 parts of Polysiloxane; where,

The polyamine is any one of low molecular weight difunctional primary amines, difunctional polyetheramines and difunctional heterocyclic diamines;

The difunctional primary amine is preferably hexamethylenediamine, isophoronediamine, dicyclohexylmethanediamine and 3,3'-dimethyl 4,4'-dicyclohexylmethanediamine;

Difunctional polyetheramines preferably include polypropylene glycol diamine and polyethylene glycol diamine;

Difunctional heterocyclic diamines are preferably 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine and 4,7,10-tris Oxatridecane-1,13-diamine;

The maleate is any one of diethyl maleate, dimethyl maleate, dipropyl maleate, dibutyl maleate and methyl propyl maleate;

Polysiloxane is polydimethylsiloxane, amino-terminated polydimethylsiloxane, epoxy-terminated polysiloxane, polymethylphenylsiloxane, propylamino-terminated polysiloxane, Aminopropyl polydimethyldiphenylsiloxane, aminopropyl-terminated polycyanopropylmethylsiloxane, siloxane containing Si-H bonds, carboxy-terminated polydimethylsiloxane, tetra Any one or more of methyldisiloxane and polyaminopropylmethylsiloxane.

Still further, the preparation method of the polyaspartic acid ester modified polysiloxane: comprises the following steps:

1) Take polyamine, maleic acid ester and polysiloxane according to the above-mentioned weight and number ratio, and set aside;

2) Add the polyamine into the reaction kettle, stir and feed nitrogen;

3) Slowly add maleate ester dropwise to the reaction kettle, and keep the temperature at 30-40°C; after the dropwise addition, raise the temperature to 90-100°C, and react for 8-20 hours to obtain polyaspartic acid ester;

4) Into the reaction kettle equipped with polyaspartic acid ester; continue to slowly add polysiloxane dropwise, and keep the temperature at 30-40°C; A polyaspartate-modified polysiloxane was obtained.

Further, the modified isocyanate is toluene diisocyanate and its modified adduct, diphenylmethane diisocyanate and its modified adduct, toluene diisocyanate, n-butyl isocyanate, polyisocyanate, poly Any of isocyanate, 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 or several of fluorine-containing silane and nano-scale silver additives;

The fluorine-containing silane is preferably trimethylfluorosilane, triethylfluorosilane, trifluoromethyltrimethylsilane, triethyltrifluoromethylsilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyl Triethoxysilane and heptadecafluorodecyltrimethoxysilane; the nanoscale silver additives preferably include organically modified silver particles and silver antibacterial solutions. ;

Further, the catalyst is N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl)ether, N,N,N',N'-tetramethylalkylenediamine, triethyl Amine, N,N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N,N'-diethylpiperazine, triethanolamine, DME, aromatic amines include pyridine, N , N'-lutidine, dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide 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 kind.

Further, the epoxy resin curing agent is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, m-xylylenediamine, triethanolamine, tetra Any one of methylguanidine, N,N'-dimethylpiperazine and triethylenediamine.

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.

Further, the silane coupling agent is amino functional silane (KH550), methacryloxy functional silane (KH570), vinyltriethoxysilane (A-151), (vinyltrimethoxysilane ) A-171, any one or more of diamino functional silane (KH792), phenyltrimethoxysilane, phenyltriethoxysilane and methyltriethoxysilane;

The filler is any one or more of talcum powder, TiO ₂ , SiO ₂ , BaSO ₄ , ZnO, Al ₂ O ₃ and CaCO ₃ , and the particle size of the filler is 5-50nm;

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-hydroxyl-4-N-octyloxybenzophenone (UV-531), 2-(2-hydroxyl-3, 5-dibutyl-tert-phenyl)-5-chlorobenzotriazole (UV327), KY-1010, GW-628.

The present invention also provides a preparation method of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material, which is characterized in that: comprising the following steps:

1) Weigh 30-50 parts of polyamine, 20-40 parts of maleic acid ester and 30-50 parts of polysiloxane according to the above weight ratio, and set aside;

2) Add the polyamine into the reaction kettle, stir and feed nitrogen;

3) Slowly add maleate ester dropwise to the reaction kettle, and keep the temperature at 30-40°C; after the dropwise addition, raise the temperature to 90-100°C, and react for 8-20 hours to obtain polyaspartic acid ester;

4) Into the reaction kettle equipped with polyaspartic acid ester; continue to slowly add polysiloxane dropwise, and keep the temperature at 30-40°C; Obtain polyaspartic acid ester modified polysiloxane;

5) Weigh 45-60 parts of polyaspartate-modified polysiloxane, 20-50 parts of modified isocyanate, and 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, set aside;

6) Add biological growth inhibitors, catalysts, coupling agents, anti-aging agents, fillers and pigments to polyaspartic acid ester modified polysiloxane, and mix uniformly; then add modified isocyanate, mix uniformly, and obtain surface protection material;

7) Weigh 30-40 parts of modified epoxy resin, 20-40 parts of epoxy resin curing agent, 20-50 parts of active diluent, 1-5 parts The coupling agent, 0.5-1 part of anti-aging agent and 1-5 parts of filler are used for later use.

8) Mix the modified epoxy resin, reactive diluent, coupling agent, anti-aging agent and filler evenly, and then add epoxy resin curing agent to obtain the base protection material;

9) When in use, lay the base protection material first, and then lay the surface protection material after the base material is solidified, so as to obtain the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material.

The beneficial effects of the present invention are:

1) It has excellent imitation biofouling performance, has low surface energy characteristics, and can prevent biological adhesion. At the same time, the special elements contained in the material structure can inhibit the growth of marine and freshwater organisms, thereby achieving the purpose of preventing biological pollution;

2) The material system has excellent mechanical properties, durability, and environmental protection performance. It has good performance with concrete, and has anti-leakage, anti-crack, anti-carbonization, and anti-corrosion properties.

3) The material system prepared by the present invention can not only meet the biological pollution protection needs of hydraulic concrete, but also can be applied to the field of concrete erosion protection in marine environment, and has broad application prospects.

Detailed ways

In order to better explain the present invention, the main content of the present invention is further clarified below in conjunction with specific examples, but the content of the present invention is not limited to the following examples.

Example 1

1) Take by weighing 30 parts of dicyclohexylmethanediamine (HMDA), 40 parts of diethyl maleate and 30 parts of epoxy-terminated polysiloxane according to the above weight and number ratio, and set aside;

2) Add dicyclohexylmethanediamine (HMDA) into the reactor, stir and feed nitrogen;

3) Slowly add diethyl maleate dropwise into the reaction kettle, and keep the temperature at 35°C; after the dropwise addition, raise the temperature to 90-100°C, and react for 12 hours to obtain polyaspartic acid ester;

4) Into the reaction kettle equipped with polyaspartic acid ester; continue to slowly add epoxy-terminated polysiloxane dropwise, and keep the temperature at 30-40°C; ~20h, to obtain polyaspartic acid ester modified polysiloxane;

5) Take by weighing 50 parts of polyaspartate modified polysiloxane, 20 parts of 1,6-hexamethylene diisocyanate, 5 parts of ten Trifluorooctyltrimethoxysilane, 5 parts of nano-scale silver particles, 1 part of two (dodecyl sulfide) dibutyltin, 3 parts of coupling agent KH550, 0.5 parts of anti-aging agent Chinox245, 0.5 parts of Anti-aging agent UV-234, 5 parts of SiO ₂ with a particle size of 10nm, 4 parts of titanium dioxide, 0.8 part of iron black, and 0.2 part of carbon black, set aside;

6) Add tridecafluorooctyltrimethoxysilane, nanoscale silver particles, dibutyltin di(dodecylsulfide), silane coupling agent KH550, to polyaspartate modified polysiloxane, Anti-aging agent Chinox245, anti-aging agent UV-234, SiO ₂ with a particle size of 10nm, titanium dioxide, iron black and carbon black, mix uniformly; then add 1,6-hexamethylene diisocyanate, mix uniformly, and obtain surface protection material;

7) Take by weighing 35 parts of bisphenol A type epoxy resin E51, 30 parts of diethylenetriamine, 30 parts of butyl glycidyl ether, 3 parts of silane according to the raw material weight ratio of the primary protective material Coupling agent KH550, 1 part of anti-aging agent UV-531 and 1 part of CaCO ₃ with a particle size of 10nm are set aside.

8) Mix bisphenol A epoxy resin E51, butyl glycidyl ether, silane coupling agent KH550, anti-aging agent UV-531 and _CaCO3 with a particle size of 10nm, and then add diethylenetriamine, That is, the basic protective material is obtained;

9) When in use, lay the base protection material first, and then lay the surface protection material after the base material is solidified to obtain the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 1 .

The basic properties of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 1 are as follows:

Main performance indicators of primary protection materials of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection materials 1

Main performance indicators of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material surface protection material

Example 2

1) Weigh 50 parts of 3,3'-dimethyl 4,4'-dicyclohexylmethanediamine, 20 parts of dimethyl maleate, 20 parts of aminopropyl End-blocked polycyanopropyl methylsiloxane and 30 parts of end-epoxy polysiloxanes, standby;

2) Add 3,3'-dimethyl 4,4'-dicyclohexylmethanediamine into the reaction kettle, stir and feed nitrogen;

3) Slowly add dimethyl maleate dropwise to the reactor, and keep the temperature at 35°C; after the dropwise addition, raise the temperature to 90-100°C, and react for 8-20 hours to obtain polyaspartic acid ester;

4) Into the reaction kettle equipped with polyaspartic acid ester; continue to slowly add aminopropyl-terminated polycyanopropylmethylsiloxane and epoxy-terminated polysiloxane dropwise, and keep the temperature at 30-40 °C; after the dropwise addition, raise the temperature to 60-120 °C, and react for 8-20 hours to obtain polyaspartate-modified polysiloxane;

5) Take by weighing 45 parts of polyaspartic acid ester modified polysiloxane, 30 parts of 1,6-hexamethylene diisocyanate, 5 parts of three Fluoromethyltrimethylsilane, 5 parts of nano-scale silver particles, 1 part of dibutyltin dilaurate, 3 parts of silane coupling agent KH570, 0.5 parts of anti-aging agent Chinox1010, 0.5 parts of anti-aging agent SUV , 5 parts of SiO ₂ with a particle size of 10nm, 4 parts of titanium dioxide, 0.8 part of iron black, and 0.2 part of carbon black, set aside;

6) Add trifluoromethyltrimethylsilane, nanoscale silver particles, dibutyltin dilaurate, silane coupling agent KH570, anti-aging agent Chinox1010, anti-aging agent Chinox1010, Aging agent SUV, SiO ₂ with a particle size of 10nm, titanium dioxide, iron black and carbon black are mixed evenly; then 1,6-hexamethylene diisocyanate is added and mixed evenly to obtain the surface protective material;

7) Take by 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 ₃ with a particle size of 10nm are set aside.

8) Mix bisphenol F-type epoxy resin DER354, glycerol triglycidyl ether, silane coupling agent KH550, anti-aging agent KY-1010 and CaCO ₃ with a particle size of 10nm, and then add m-xylylenediamine , that is, the basic protective material is obtained;

9) When in use, lay the base protection material first, and then lay the surface protection material after the base material is solidified to obtain the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 2.

The basic properties of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 2 are as follows:

Main performance indicators of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 2 base protection material

Main performance indicators of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 2 surface protection material

Example 3

1) Weigh 40 parts of 3,3'-dimethyl 4,4'-dicyclohexylmethanediamine, 30 parts of dimethyl maleate, 20 parts of Cyanopropylmethyl siloxane and 20 parts of epoxy-terminated polysiloxanes, standby;

2) Add 3,3'-dimethyl 4,4'-dicyclohexylmethanediamine into the reaction kettle, stir and feed nitrogen;

3) Slowly add dimethyl maleate dropwise to the reactor, and keep the temperature at 30-40°C; after the dropwise addition, raise the temperature to 90-100°C, and react for 8-20 hours to obtain polyaspartic acid ester;

4) Into the reaction kettle equipped with polyaspartate; continue to slowly add aminopropyl-terminated polycyanopropylmethylsiloxane and epoxy-terminated polysiloxane dropwise, and keep the temperature at 35°C; After the dropwise addition, raise the temperature to 60-120°C and react for 8-20 hours to obtain polyaspartate-modified polysiloxane;

5) Take by weighing 45 parts of polyaspartic acid ester modified polysiloxane, 30 parts of 1,6-hexamethylene diisocyanate, 5 parts of three Fluoromethyltrimethylsilane, 5 parts of nano-scale silver particles, 1 part of dibutyltin dilaurate, 3 parts of silane coupling agent KH570, 0.5 parts of anti-aging agent Chinox1010, 0.5 parts of anti-aging agent SUV , 5 parts of SiO ₂ with a particle size of 10nm, 4 parts of titanium dioxide, 0.8 part of iron black, and 0.2 part of carbon black, set aside;

6) Add trifluoromethyltrimethylsilane, nano-scale silver particles, dibutyltin dilaurate, silane coupling agent KH570, and anti-aging agent Chinox1010 to polyaspartic ester modified polysiloxane Agent SUV, SiO ₂ with a particle size of 10nm, titanium dioxide, iron black and carbon black, mix evenly; then add 1,6-hexamethylene diisocyanate, mix evenly, and obtain the surface protection material;

7) Take by weighing 35 parts of bisphenol F type epoxy resin DER354, 20-40 parts of m-xylylenediamine, 30 parts of glycerol triglycidyl ether, 3 1 part of coupling agent KH550, 1 part of anti-aging agent KY-1010 and 1 part of CaCO ₃ with a particle size of 10nm, for later use.

8) Bisphenol F-type epoxy resin DER354, glycerol triglycidyl ether, coupling agent KH550, anti-aging agent KY-1010, and _CaCO active diluent, coupling agent, and anti-aging agent with a particle size of 10nm Mix evenly with the filler, then add m-xylylenediamine to obtain the base protection material;

9) When in use, lay the base protection material first, and then lay the surface protection material after the base material is cured to obtain the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 3 .

The basic properties of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 3 are as follows:

Polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 3 main performance indicators of base protection material

Main performance indicators of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 3 surface protection material

Example 4

1) Take by weighing 45 parts of 4,7-dioxadecane-1,10-diamine, 35 parts of methyl propyl maleate and 35 parts of tetramethyl di Siloxane, spare;

2) Add 4,7-dioxadecane-1,10-diamine into the reaction kettle, stir and feed nitrogen;

3) Slowly add methyl propyl maleate dropwise to the reaction kettle, and keep the temperature at 35°C; after the dropwise addition, raise the temperature to 90-100°C, and react for 8-20 hours to obtain polyaspartic acid ester;

4) Into the reaction kettle equipped with polyaspartic acid ester; continue to slowly add tetramethyldisiloxane dropwise, and keep the temperature at 30-40°C; 20h, namely obtain polyaspartate modified polysiloxane;

5) Take by weighing 60 parts of polyaspartic acid ester modified polysiloxane, 50 parts of p-chlorophenyl isocyanate, 5 parts of trifluoromethyltrimethyltrimethacrylate according to the ratio of raw materials of the surface protection material. silane, 0.5 parts of bis(2-dimethylaminoethyl) ether, 0.5 parts of phenyltrimethoxysilane, 1 part of anti-aging agent ChinoxB225, 5 parts of ZnO with a particle size of 50nm and 1 part of titanium White powder, spare;

6) adding trifluoromethyltrimethylsilane, bis(2-dimethylaminoethyl) ether, coupling agent, anti-aging agent, filler and pigment to polyaspartate modified polysiloxane, Mix evenly; then add p-chlorophenyl isocyanate, mix evenly, and obtain the surface protection material;

7) Weigh 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 The anti-aging agent GW-628 and 3 parts of CaCO ₃ with a particle size of 50nm are set aside.

8) Mix novolac epoxy resin, phenyl glycidyl ether, silane coupling agent KH171, anti-aging agent GW-628 and CaCO ₃ with a particle size of 50nm, and then add hexamethylenediamine to obtain the base layer protection material;

9) When in use, lay the base protection material first, and then lay the surface protection material after the base material is cured to obtain the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 4 .

The basic properties of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 4 are as follows:

Polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 4 main performance indicators of base protection material

Main performance indicators of polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 4 surface protection material

Example 5

1) Weigh 45 parts of 4,7-dioxadecane-1, 25 parts of diethyl maleate and 30 parts of polyaminopropylmethylsiloxane according to the above weight ratio, spare;

2) Add 4,7-dioxadecane-1 into the reaction kettle, stir and feed nitrogen;

3) Slowly add diethyl maleate dropwise to the reaction kettle, and keep the temperature at 30-40°C; after the dropwise addition, raise the temperature to 90-100°C, and react for 8-20 hours to obtain polyaspartic acid ester;

4) Into the reaction kettle equipped with polyaspartic acid ester; continue to slowly add polyaminopropylmethylsiloxane dropwise, and keep the temperature at 35°C; ~20h, to obtain polyaspartic acid ester modified polysiloxane;

5) Weigh 55 parts of polyaspartic acid ester modified polysiloxane, 20 parts of n-butyl isocyanate, 7 parts of heptadecylfluorodecyl according to the ratio of raw materials of the surface protective material. Trimethoxysilane, 1 part of triethylamine, N,N-dimethylbenzylamine, 2 parts of silane coupling agent KH171, 0.5 part of anti-aging agent UV-328, 7 parts of Al with a particle size of 20nm ₂ O ₃ and 2 parts of iron black, spare;

6) Add heptadecafluorodecyltrimethoxysilane, triethylamine, N,N-dimethylbenzylamine, silane coupling agent KH171, and anti-aging agent to polyaspartic ester modified polysiloxane UV-328, Al ₂ O ₃ and iron black with a particle size of 20nm, mixed evenly; then adding modified isocyanate, mixed evenly, and then the surface protective material was obtained;

7) Take by weighing 30 parts of amino-based epoxy resins, 20 parts of tetraethylenepentamine, 40 parts of cresyl glycidyl ether, 5 parts of phenyl triphenylamine according to the raw material weight ratio of the primary protective material. Ethoxysilane, 1 part of anti-aging agent UV327 and 2 parts of BaSO ₄ with a particle size of 20nm are set aside.

8) Mix amino-based epoxy resin, cresyl glycidyl ether, phenyltriethoxysilane, anti-aging agent UV327 and BaSO ₄ with a particle size of 20nm, and then add tetraethylenepentamine to obtain Basic protective materials;

9) When in use, lay the base protection material first, and then lay the surface protection material after the base material is solidified to obtain the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 5 .

The basic properties of polyurea-polysiloxane organic-inorganic hybrid concrete biofouling protection material 5 are as follows:

Polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 5 main performance indicators of base protection materials

Polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material 5 main performance indicators of surface layer protection material

Other parts not specified in detail are prior art. Although the foregoing embodiment has described the present invention in detail, it is only a part of the embodiments of the present invention, rather than all embodiments, and people can also obtain other embodiments according to the present embodiment without inventive step, these embodiments All belong to the protection scope of the present invention.

Claims (10)

1. A polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material, the pollution protection material comprises a surface layer protection material and a base layer protection material, it is characterized in that: the raw material of the surface layer protection material In terms of parts by weight, it includes: 45-60 parts of polyaspartate 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 raw materials of the basic protective material include: 30-40 parts of modified epoxy resin, 20-40 parts of epoxy resin curing agent, 20-50 parts of active diluent, 1-5 parts Coupling agent, 0.5-1 part of anti-aging agent and 1-5 parts of filler. 2. polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material according to claim 1, is characterized in that: the raw material of described polyaspartate modified polysiloxane is by weight parts The ratio includes: 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 low molecular weight difunctional primary amines, difunctional polyetheramines and difunctional heterocyclic diamines; The low molecular weight difunctional primary amine is any one of hexamethylenediamine, isophoronediamine, dicyclohexylmethanediamine and 3,3'-dimethyl4,4'-dicyclohexylmethanediamine, The difunctional polyether amine is polypropylene glycol diamine or polyethylene glycol diamine; Difunctional heterocyclic diamines are 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine and 4,7,10-trioxy Any one of heterotridecane-1,13-diamine; The maleate is any one of diethyl maleate, dimethyl maleate, dipropyl maleate, dibutyl maleate and methyl propyl maleate; Polysiloxane is polydimethylsiloxane, amino-terminated polydimethylsiloxane, epoxy-terminated polysiloxane, polymethylphenylsiloxane, propylamino-terminated polysiloxane, Aminopropyl polydimethyldiphenylsiloxane, aminopropyl-terminated polycyanopropylmethylsiloxane, siloxane containing Si-H bonds, carboxy-terminated polydimethylsiloxane, tetra Any one or more of methyldisiloxane and polyaminopropylmethylsiloxane. 3. The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material according to claim 2, characterized in that: the preparation method of the polyaspartic acid ester modified polysiloxane: comprising the following step: 1) Take polyamine, maleic acid ester and polysiloxane according to the above-mentioned weight and number ratio, and set aside; 2) Add the polyamine into the reaction kettle, stir and feed nitrogen; 3) Slowly add maleate ester dropwise to the reaction kettle, and keep the temperature at 30-40°C; after the dropwise addition, raise the temperature to 90-100°C, and react for 8-20 hours to obtain polyaspartic acid ester; 4) Into the reaction kettle equipped with polyaspartic acid ester; continue to slowly add polysiloxane dropwise, and keep the temperature at 30-40°C; A polyaspartate-modified polysiloxane was obtained. 4. The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material according to claim 1 or 2, characterized in that: the modified isocyanate is toluene diisocyanate and its modified adduct, di Phenylmethane diisocyanate and its modified adducts, toluene diisocyanate, n-butyl isocyanate, polyisocyanate, 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 pollution protection material according to claim 1 or 2, characterized in that: the biological growth inhibitor is fluorine-containing silane and nano-scale silver additives any one or more of them. 6. The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection 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, aromatic amines include pyridine, N,N'-lutidine, dibutyltin dilaurate, stannous octoate, Dibutyltin di(dodecylsulfide) and dibutyltin diacetate. 7. The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material according to claim 1 or 2, characterized in that: the modified epoxy resin is bisphenol A type epoxy resin, bisphenol Any of F-type epoxy resins, novolak epoxy resins, amine-based epoxy resins, and glycidyl ester-type epoxy resins. 8. The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material according to claim 1 or 2, characterized in that: the epoxy resin curing agent is ethylenediamine, diethylenetriamine , triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, m-xylylenediamine, triethanolamine, tetramethylguanidine, N,N'-dimethylpiperazine and triethylenediamine A sort of. 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 Glycidyl ether, butylphenyl glycidyl ether, and propylene oxide butyl ether. 9. The polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material according to claim 1 or 2, characterized in that: The coupling agent is a silane coupling agent, and the silane coupling agent is amino functional group silane, methacryloxy functional group silane, vinyl triethoxy silane, vinyl trimethoxy silane, diamino functional group Any one of silane, phenyltrimethoxysilane, phenyltriethoxysilane and methyltriethoxysilane; The filler is any one or more of talcum powder, TiO ₂ , SiO ₂ , BaSO ₄ , ZnO, Al ₂ O ₃ and CaCO ₃ , and the particle size of the filler is 5-50nm; 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-hydroxyl-4-N-octyloxybenzophenone, 2-(2-hydroxyl-3,5-dibutyl-tert-phenyl base)-5-chlorobenzotriazole, KY-1010, GW-628. 10. A preparation method of a polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material, characterized in that: comprising the following steps: 1) Weigh 30-50 parts of polyamine, 20-40 parts of maleic acid ester and 30-50 parts of polysiloxane according to the above weight ratio, and set aside; 2) Add the polyamine into the reaction kettle, stir and feed nitrogen; 3) Slowly add maleate ester dropwise to the reaction kettle, and keep the temperature at 30-40°C; after the dropwise addition, raise the temperature to 90-100°C, and react for 8-20 hours to obtain polyaspartic acid ester; 4) Into the reaction kettle equipped with polyaspartic acid ester; continue to slowly add polysiloxane dropwise, and keep the temperature at 30-40°C; Obtain polyaspartic acid ester modified polysiloxane; 5) Weigh 45-60 parts of polyaspartate-modified polysiloxane, 20-50 parts of modified isocyanate, and 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, set aside; 6) Add biological growth inhibitors, catalysts, coupling agents, anti-aging agents, fillers and pigments to polyaspartic acid ester modified polysiloxane, and mix uniformly; then add modified isocyanate, mix uniformly, and obtain surface protection material; 7) Weigh 30-40 parts of modified epoxy resin, 20-40 parts of epoxy resin curing agent, 20-50 parts of active diluent, 1-5 parts The coupling agent, 0.5-1 part of anti-aging agent and 1-5 parts of filler are used for later use. 8) Mix the modified epoxy resin, reactive diluent, coupling agent, anti-aging agent and filler evenly, and then add epoxy resin curing agent to obtain the base protection material; 9) When in use, lay the base protection material first, and then lay the surface protection material after the base material is solidified, so as to obtain the polyurea-polysiloxane organic-inorganic hybrid concrete biological pollution protection material.