CN102898813A - Hydraulic cavitation-resistant material and preparation method thereof - Google Patents

Abstract

Hydraulic anti-cavitation material, which is composed of A component and B component, the A component includes at least polyaspartic acid ester, the B component includes a curing agent, and the raw material component poly The part by weight of the aspartate is 100 parts, and the part by weight of the curing agent is 30-180 parts. The protective material of the invention has excellent mechanical properties and super strong weather resistance and aging resistance. The invention also simultaneously discloses a preparation method of the hydraulic anti-cavitation material.

Description

Hydraulic anti-cavitation material and preparation method thereof

technical field

The invention relates to a hydraulic anti-cavitation material, and also relates to a preparation method of the hydraulic anti-cavitation material.

Background technique

The scouring wear and cavitation damage of hydraulic drainage structures have always been an important issue that has been concerned about in the construction of water conservancy and hydropower for a long time and needs to be properly resolved. In order to prevent hydraulic discharge structures from affecting the service life of the dam due to cavitation damage, the project must be correctly designed to ensure excellent construction quality, and special protection for hydraulic discharge structures is required (in special parts Paste a special protective layer) and careful inspection and maintenance (repair and reinforcement in time if there is a problem on the surface). my country currently has more than 80,000 dams, the country with the most dams in the world, and large dams account for 45% of the global total. In addition, the construction of the Jinping giant hydropower station on the Yalong River approved by the State Council, the Xiluodu and Xiangjiaba projects on the Jinsha River, the Xiaowan project on the Lancang River, and the Pupugou project on the Dadu River are also under intense construction. These water conservancy and hydropower projects have already existed and will inevitably have the problem of cavitation damage of hydraulic drainage structures. As time goes by, it will inevitably affect the normal and efficient performance of the functions of water conservancy and hydropower projects. The country's flood control safety, water conservancy and shipping, and electric energy have a great impact, and it is more likely to bring immeasurable losses to the national economy. Therefore, it is urgent to solve the cavitation damage research of hydraulic drainage structures.

After a lot of investigation and analysis, since the 1970s, the design, scientific research, construction, transportation management and building materials units of domestic and foreign water conservancy and hydropower departments have begun to study the use of special materials and techniques to improve the anti-scouring and abrasion resistance of hydraulic drainage structures. Cavitation ability to avoid or reduce its harmfulness. Due to the superior performance of polymer materials, easy construction, and convenient secondary repair, it is the first choice as the anti-cavitation damage protection material for hydraulic drainage structures. Since hydraulic drainage structures are continuously damaged by cavitation for a long time, the protective materials should have excellent mechanical properties and super weather resistance and aging resistance, so the research and development of materials is relatively difficult.

Contents of the invention

The first object of the present invention is to provide a hydraulic anti-cavitation material with excellent mechanical properties and super weather resistance and aging resistance, so as to protect hydraulic drainage structures from cavitation damage for a long time.

The second object of the present invention is to provide a preparation method of this hydraulic anti-cavitation material.

In order to achieve the above object, the present invention adopts the following technical scheme, hydraulic anti-cavitation material, which is composed of A component and B component, characterized in that the A component includes at least polyaspartic acid ester, the Component B includes a curing agent, the raw material component polyaspartic acid ester contains 100 parts by weight, and the curing agent contains 30-180 parts by weight.

In the above technical solution, the A component also includes inorganic nanomaterials, organic silicon coupling agents, and reactive diluents; the content of the inorganic nanomaterials is 1 to 80 parts by weight, and the organic silicon coupling agent The content in parts by weight is 1-15 parts, and the content in parts by weight of the reactive diluent is 1-100 parts.

In the above-mentioned technical scheme, the synthetic method of described polyaspartic acid ester comprises the following steps: ① adding difunctional primary amine in a four-necked flask, stirring, feeding nitrogen; ② slowly adding maleic acid ester dropwise, And keep the temperature at 35°C; ③ After the dropwise addition, raise the temperature to 90-100°C, and react for 12 hours to obtain polyaspartic acid ester.

In the above technical scheme, the difunctional primary amines are one or more of the following difunctional primary amines: ① low molecular weight difunctional primary amines: hexamethylenediamine, isophoronediamine, dicyclohexyl Methanediamine or 3,3'-dimethyl 4,4'-dicyclohexylmethanediamine; ②Difunctional polyetheramine: polypropylene glycol diamine or polyethylene glycol diamine; ③Difunctional heterocyclic diamine : 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine or 4,7,10-trioxadecane-1 , 13-diamine; The maleic acid ester is diethyl maleate, dimethyl maleate, dipropyl maleate, dibutyl maleate, methyl propyl maleate .

In the above technical solution, the inorganic nanomaterials include one or more of nano-TiO ₂ , nano-SiO ₂ , nano-ZnO, nano-CaCO ₃ , and nano-Fe ₃ O ₄ .

In the above technical scheme, the curing agent is a variety of curing agents with different structures, and the curing agent is toluene diisocyanate, n-butyl isocyanate, polyisocyanate, polyisocyanate, p-chlorophenyl isocyanate, Chlorosulfonyl isocyanate, p-toluenesulfonyl isocyanate, methyl isocyanate, isopropyl isocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate or diphenylmethane diisocyanate A homogeneous mixture of two or more isocyanates at room temperature.

In the above technical scheme, the silicone coupling agent is one or more of KH550, KH570, KH151, KH171, KH792; the reactive diluent is ethanol, ethylene glycol, propylene glycol, polyethylene glycol One or more of alcohol and polypropylene glycol.

The preparation method of hydraulic anti-cavitation material is characterized in that it includes the following steps: react with different difunctional primary amines and maleic acid esters to obtain polyaspartic acid esters with different gel times, and simultaneously add inorganic nano The material is compounded with polyaspartic acid ester material, and then the corresponding silicone coupling agent and reactive diluent are added to improve its performance, as the A component of the hydraulic anti-cavitation material; by selecting a variety of curing materials with different structures agent as the B component of the hydraulic anti-cavitation material; the content of the raw material component polyaspartic acid ester is 100 parts by weight, the content of the inorganic nanomaterial is 0 to 80 parts by weight, and the organic The content of silicon coupling agent is 0-15 parts by weight, and the content of reactive diluent is 0-100 parts by weight;

The content of the curing agent is 30-180 parts by weight.

The present invention uses different difunctional primary amines to react with maleic acid esters to obtain polyaspartic acid esters with different gel times, and selects a variety of curing agents with different structures to react with polyaspartic acid esters for curing At the same time, adding inorganic nanomaterials and polyaspartic ester materials to compound, adding corresponding silicone coupling agents and reactive diluents to improve its performance and reduce costs, and finally obtain a concrete surface protection material with excellent comprehensive performance.

The beneficial effects of the present invention are: (1) The active diluent participates in the curing reaction, which increases the solid content, reduces VOC, and is more conducive to environmental protection. At the same time, the addition of the active diluent reduces the viscosity of the material and provides convenience for construction; (2) A new type of environmentally friendly inorganic-organic composite material was prepared by combining inorganic nanomaterials with organic polyaspartic acid ester materials, which is conducive to improving the impact resistance and durability of polyaspartic acid ester materials; ( 3) By adding a silicone coupling agent as a bridge between the inorganic material and the organic material, the force between the composite material and the substrate is enhanced, and the waterproof performance of the composite material is further improved.

Detailed ways

The implementation of the present invention will be described in detail below in conjunction with specific examples, but they do not constitute a limitation to the present invention, and are only examples. At the same time, the advantages of the present invention will become clearer and easier to understand.

Hydraulic anti-cavitation material, which is composed of A component and B component, characterized in that the A component includes at least polyaspartic acid ester, the B component includes a curing agent, and the raw material group The content of the polyaspartic acid ester is 100 parts by weight, and the content of the curing agent is 30-180 parts by weight.

Wherein, component A also includes inorganic nanomaterials, organosilicon coupling agents, and reactive diluents; the content of the inorganic nanomaterials is 1 to 80 parts by weight, and the content of the organosilicon coupling agents is 1 to 80 parts by weight. 15 parts, the content of the reactive diluent is 1-100 parts by weight.

Among them, the synthesis method of polyaspartic acid ester comprises the following steps: ① adding a difunctional primary amine into a four-necked flask, stirring, and feeding nitrogen; ② slowly adding maleic acid ester dropwise, and keeping the temperature at 35°C; ③ After the dropwise addition is completed, the temperature is raised to 90-100°C, and the reaction is carried out for 12 hours to obtain polyaspartic acid ester.

Among them, the types of difunctional primary amines for preparing polyaspartate are as follows: ① low molecular weight difunctional primary amines, such as: hexamethylenediamine, isophoronediamine, dicyclohexylmethanediamine (HMDA), 3 , 3'-dimethyl 4, 4'-dicyclohexylmethanediamine, etc.; ② Difunctional polyetheramines include polypropylene glycol diamine or polyethylene glycol diamine, such as: Jeffamine D-230, Jeffamine D-400 , Jeffamine D-2000, Jeffamine D-4000, Jeffamine EDR-148, Jeffamine EDR-192, Jeffamine ED-600, Jeffamine ED-900 and Jeffamine ED-2000, etc.; ③Difunctional heterocyclic diamines, such as: 4,7- Dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine wait.

Among them, the maleic acid esters for preparing polyaspartic acid esters include: diethyl maleate, dimethyl maleate, dipropyl maleate, dibutyl maleate, methylpropyl maleate base esters etc.

Wherein, the inorganic nanomaterials include one or more of nano-TiO ₂ , nano-SiO ₂ , nano-ZnO, nano-CaCO ₃ , and nano-Fe ₃ O ₄ .

Wherein, the curing agent is a variety of curing agents with different structures, and the curing agent is toluene diisocyanate, n-butyl isocyanate, polyisocyanate, polyisocyanate, p-chlorophenyl isocyanate, chlorosulfonyl isocyanate, p-toluene Two or two of sulfonyl isocyanate, methyl isocyanate, isopropyl isocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate or diphenylmethane diisocyanate A homogeneous mixture of the above species at room temperature.

Wherein, the organosilicon coupling agent is one or more of KH550, KH570, KH151, KH171, KH792 (all commercially available); the reactive diluent is ethanol, ethylene glycol, propylene glycol, polyethylene glycol , one or more of polypropylene glycol.

The preparation method of hydraulic anti-cavitation material is characterized in that it includes the following steps: react with different difunctional primary amines and maleic acid esters to obtain polyaspartic acid esters with different gel times, and simultaneously add inorganic nano The material is compounded with polyaspartic acid ester material, and then the corresponding silicone coupling agent and reactive diluent are added to improve its performance, as the A component of the hydraulic anti-cavitation material; by selecting a variety of curing materials with different structures agent as the B component of the hydraulic anti-cavitation material; the content of the raw material component polyaspartic acid ester is 100 parts by weight, the content of the inorganic nanomaterial is 0 to 80 parts by weight, and the organic The content of silicon coupling agent is 0-15 parts by weight, and the content of reactive diluent is 0-100 parts by weight;

The content of the curing agent is 30-180 parts by weight.

When in use, just mix component A and component B. The surface-drying time of the material of the present invention ranges from a few minutes to several hours, and the time for complete curing and reaching the best performance is about 7 days.

Example 1:

Preparation of hydraulic anti-cavitation material CW830-A.

Add 3,3'-dimethyl 4,4'-dicyclohexylmethanediamine into a four-necked flask, stir, and blow in nitrogen. Slowly add diethyl maleate dropwise, and keep the temperature at about 35°C. After the dropwise addition, raise the temperature to 90-100°C, and react for about 12 hours to obtain polyaspartic acid ester.

Select the curing agent 2,4-, 2,6-toluene diisocyanate mixture (TDI) and diphenylmethane diisocyanate (MDI) in any proportion and mix well with a mixer at room temperature.

Select reactive diluents ethylene glycol and propylene glycol and mix thoroughly with a mixer at room temperature in a certain proportion.

Add nano-SiO ₂ , organic silicon coupling agent KH550 and reactive diluent into polyaspartic acid ester, and stir well. Then add the curing system to carry out the curing reaction.

Among them: 100 grams of polyaspartic acid ester, 30 grams of curing agent, 50 grams of nanomaterials, 15 grams of silicone coupling agent, and 100 grams of reactive diluent.

The basic properties of concrete surface protection material CW830-A are as follows:

Example 2:

Preparation of concrete surface protection material CW830-B.

Add dicyclohexylmethanediamine into a four-necked flask, stir, and blow in nitrogen. Slowly add dimethyl maleate dropwise, and keep the temperature at about 35°C. After the dropwise addition, raise the temperature to 90-100°C, and react for about 12 hours to obtain polyaspartic acid ester.

Select the curing agent isophorone-diisocyanate (IPDI) and 1,6-hexamethylene diisocyanate (HDI) according to a certain ratio and mix well with a mixer at room temperature.

Select the active diluent ethylene glycol and polyethylene glycol and mix thoroughly with a mixer at room temperature according to a certain ratio.

Add nano-TiO ₂ , organic silicon coupling agent KH570 and active diluent into polyaspartic acid ester, and stir well. Then add the curing system to carry out the curing reaction.

Among them: 100 grams of polyaspartic acid ester, 100 grams of curing agent, 80 grams of nanomaterials, 10 grams of silicone coupling agent, and 50 grams of reactive diluent.

The basic properties of concrete surface protection material CW830-B are as follows:

Example 3:

Preparation of concrete surface protection material CW830-C.

Add polypropylene oxide diamine Jeffamine D-230 into a four-neck flask, stir, and blow nitrogen. Slowly add dipropyl maleate, and keep the temperature at about 35°C. After the dropwise addition, raise the temperature to 90-100°C, and react for about 12 hours to obtain polyaspartic acid ester.

Select the curing agent p-phenylene diisocyanate (PPDI) and xylylene diisocyanate (XDI) in a certain proportion and mix well with a mixer at room temperature.

Select the reactive diluent propylene glycol and polypropylene glycol to mix thoroughly and evenly with a mixer at room temperature according to a certain ratio.

Add nano-SiO ₂ , organic silicon coupling agent KH550 and reactive diluent into polyaspartic acid ester, and stir well. Then add the curing system to carry out the curing reaction.

Among them: 100 grams of polyaspartic acid ester, 180 grams of curing agent, 10 grams of nanomaterials, 5 grams of silicone coupling agent, and 10 grams of reactive diluent.

The basic properties of concrete surface protection material CW830-C are as follows:

Example 4

100 grams of polyaspartic acid ester, 180 grams of curing agent, 1 gram of nanomaterials, 1 gram of silicone coupling agent, and 1 gram of reactive diluent. Wherein, the maleic acid ester for preparing polyaspartic acid ester is dipropyl maleate.

Select the curing agent n-butyl isocyanate and diphenylmethane diisocyanate in any proportion and mix well with a mixer at room temperature.

Select the reactive diluent ethanol and polypropylene glycol and mix thoroughly with a mixer at room temperature in any proportion.

Add nano-ZnO, nano-CaCO ₃ , organic silicon coupling agents KH550, KH171, KH792 and active diluent into polyaspartic acid ester, and stir well. Then add the curing system to carry out the curing reaction.

Others are the same as embodiment 3

Example 5

100 grams of polyaspartic acid ester, 30 grams of curing agent, 5 grams of nanomaterials, 3 grams of silicone coupling agent, and 20 grams of reactive diluent. Wherein, the maleic acid ester for preparing polyaspartic acid ester is dibutyl maleate.

Select the curing agent polyisocyanate, chlorosulfonyl isocyanate and isopropyl isocyanate in any proportion and mix well with a mixer at room temperature.

Select the reactive diluent ethanol and polypropylene glycol and mix thoroughly with a mixer at room temperature in any proportion.

Add nano-SiO ₂ , nano-Fe ₃ O ₄ , organosilicon coupling agents KH550, KH151, KH570 and active diluent into polyaspartic ester, and stir well. Then add the curing system to carry out the curing reaction.

Others are the same as embodiment 3

Example 6

100 grams of polyaspartic acid ester, 90 grams of curing agent, 40 grams of nanomaterials, 7 grams of silicone coupling agent, and 60 grams of reactive diluent. Wherein, the maleic acid ester for preparing polyaspartic acid ester is methyl propyl maleate.

Select the curing agent polyisocyanate, p-chlorophenyl isocyanate, p-toluenesulfonyl isocyanate and methyl isocyanate in any proportion and mix well with a mixer at room temperature.

Select the reactive diluent ethanol and polypropylene glycol and mix thoroughly with a mixer at room temperature in any proportion.

Add nano-SiO ₂ , nano-TiO ₂ , nano-CaCO ₃ , organic silicon coupling agents KH550, KH792, KH171 and active diluent into the polyaspartic ester, and stir well. Then add the curing system to carry out the curing reaction.

Others are the same as embodiment 3

Example 7

100 grams of polyaspartic acid ester (component A), 30 grams of curing agent (component B), and zero other ingredients.

Add 4,7-dioxadecane-1,10-diamine into a four-necked flask, stir, and blow in nitrogen. Slowly add dimethyl maleate dropwise, and keep the temperature at about 35°C. After the dropwise addition, the temperature was raised to 90°C, and the reaction was carried out for about 12 hours to obtain polyaspartic acid ester.

Example 8

100 grams of polyaspartic acid ester (component A), 80 grams of curing agent (component B), and zero other ingredients.

Add 4,9-dioxadodecane-1,12-diamine and 4,7,10-trioxatridecane-1,13-diamine into a four-necked flask, stir, and blow in nitrogen . Slowly add dimethyl maleate dropwise, and keep the temperature at about 35°C. After the dropwise addition, the temperature was raised to 100°C, and the reaction was carried out for about 12 hours to obtain polyaspartic acid ester.

Claims (8)

1. the anti-cavitation erosion material of water conservancy project, it is comprised of A component and B component, it is characterized in that described A component comprises polyaspartate at least, and described B component comprises solidifying agent, the weight part content of described feed composition polyaspartate is 100 parts, and the weight part content of solidifying agent is 30-180 part.

2. the anti-cavitation erosion material of water conservancy project according to claim 1 is characterized in that described A component also comprises inorganic nano material, organo-silicon coupling agent, reactive thinner; The weight part content of described inorganic nano material is 1～80 part, and the weight part content of described organo-silicon coupling agent is 1～15 part, and the weight part content of described reactive thinner is 1～100 part.

3. the anti-cavitation erosion material of water conservancy project according to claim 1 and 2 is characterized in that the synthetic method of described polyaspartate comprises the steps: 1. two functional group's primary amine to be joined in the four-hole boiling flask, stirs, and passes into nitrogen; 2. slowly drip maleic acid ester, and maintain the temperature at 35 ℃; 3. dropwise, be warming up to 90～100 ℃, reaction 12h obtains polyaspartate.

4. the anti-cavitation erosion material of water conservancy project according to claim 3, it is characterized in that described two functional group's primary amine are one or more in following two functional group's primary amine: 1. low-molecular-weight two functional group's primary amine: hexanediamine, isophorone diamine, dicyclohexyl methyl hydride diamines or 3,3 '-dimethyl 4,4 '-dicyclohexyl methyl hydride diamines; 2. two functional group's polyetheramines: polypropylene glycol diamine or polyethylene glycol diamines; 3. two functional group's heterocyclic diamines: 4,7-dioxadecane-1,10-diamines, 4,9-dioxa dodecane-1,12-diamines or 4,7,10-trioxa, three decane-1,13-diamines; Described maleic acid ester is ethyl maleate, dimethyl maleate, dipropyl maleate, dibutyl maleinate, toxilic acid methyl-propyl ester.

5. the anti-cavitation erosion material of water conservancy project according to claim 2 is characterized in that described inorganic nano material comprises nano-TiO ₂, nanometer SiO ₂, nano-ZnO, nanometer CaCO ₃, nanometer Fe ₃O ₄In one or more.

6. the anti-cavitation erosion material of water conservancy project according to claim 1, it is characterized in that described solidifying agent is multiple solidifying agent with different structure, described solidifying agent is tolylene diisocyanate, n-butyl isocyanate, polymeric polyisocyanate, polyisocyanates, parachlorobenzyl isocyanic ester, Sulfuryl chloride isocyanate, the tolysulfonyl isocyanic ester, methyl isocyanate, isopropyl isocyanate, diphenylmethanediisocyanate, 1,6-hexamethylene diisocyanate, in isophorone diisocyanate or the diphenylmethanediisocyanate two or more uniform mixture at room temperature.

7. the anti-cavitation erosion material of water conservancy project according to claim 2 is characterized in that described organo-silicon coupling agent is one or more among KH550, KH570, KH151, KH171, the KH792; Described reactive thinner is one or more in ethanol, ethylene glycol, propylene glycol, polyoxyethylene glycol, the polypropylene glycol.

8. the anti-cavitation erosion material preparation of water conservancy project method, it is characterized in that it comprises the steps: to react with different two functional group's primary amine and maleic acid ester, acquisition has the polyaspartate of different gel times, add simultaneously inorganic nano material and polyaspartate Material cladding, add again corresponding organo-silicon coupling agent and reactive thinner and improve its performance, as the A component of the anti-cavitation erosion material of water conservancy project; Multiplely has the solidifying agent of different structure as the B component of the anti-cavitation erosion material of water conservancy project by choosing; The weight part content of described material component polyaspartate is 100 parts, and the weight part content of described inorganic nano material is 0～80 part, and the weight part content of described organo-silicon coupling agent is 0～15 part, and the weight part content of described reactive thinner is 0～100 part;

The weight part content of described solidifying agent is 30-180 part.