Algae-killing and corrosion-preventing functional monomer as well as preparation method and application thereof

Abstract

The invention relates to an algae-killing and corrosion-preventing functional monomer as well as a preparation method and application thereof. The algae-killing and corrosion-preventing functional monomer is prepared from the following raw materials: 50-75 parts of a modified algae-killing and corrosion-preventing compound; 0.2 to 4 parts of a polymerization inhibitor; 0.5 to 6.2 parts of a first catalyst; according to the algae-killing and anti-corrosion functional monomer prepared by the preparation method disclosed by the invention, the solubility of the algae-killing and anti-corrosion functional monomer is remarkably improved by containing the modified algae-killing and anti-corrosion compound introduced with the hydrophilic functional group, so that the compound is more uniformly dispersed in a reaction medium through the modification, and the reaction rate of the algae-killing and anti-corrosion functional monomer and other reactants is accelerated; the reaction efficiency and the performance of a final product are improved.

Description

Technical Field

[0001] The invention relates to the technical field of concrete admixtures, in particular to an algaecide and anticorrosion functional monomer and a preparation method and application thereof. Background Art

[0002] As the third generation of water reducers, polycarboxylic acid water reducers have the advantages of low dosage, high water reduction rate, high slump retention and green environmental protection. They are a concrete admixture product with broad development prospects. In practical applications, polycarboxylic acid water reducers are often used in combination with various functional components such as retarding components, early strength components, defoaming components, and air entraining components to improve the performance of concrete. However, most of these functional components are organic ingredients, which can easily become a nutrient source for the growth of bacteria, yeasts, molds and algae. For example, sodium gluconate, which is commonly used in retarding components, is mainly produced by microbial fermentation, and Aspergillus niger may remain.

[0003] During the production, storage and transportation process, polycarboxylate-based water reducers are susceptible to the invasion of microorganisms in nature due to the substandard cleanliness of containers, pipes or storage tanks, the introduction of production water or other auxiliary materials. These microorganisms multiply rapidly under suitable environmental conditions, causing the water reducer to mildew. The mildew problem is particularly serious in the case of high temperatures in summer, sea exports and long-term shutdowns. Mildew can cause the water reducer product to deteriorate and stink, the sealed container to swell and even burst, and is accompanied by stratification, precipitation and the appearance of flocculent or sticky floating objects, which seriously affects product performance and poses a hidden danger to the quality of concrete and construction safety.

[0004] At present, in order to extend the service life of polycarboxylic acid water reducers, the method of adding bactericidal preservatives is usually adopted. However, due to the wide variety of bactericidal preservatives, the effect of a single preservative is often limited, and the complex species of bacteria, the existing methods are difficult to completely solve the problem of mildew of polycarboxylic acid water reducers. Therefore, the development of a polycarboxylic acid water reducer with efficient algaecide and antiseptic functions has become the key to solving this technical problem. Summary of the invention

[0005] Based on this, it is necessary to provide an algaecidal and antiseptic functional monomer with high algaecidal and antiseptic functions and a preparation method and application thereof.

[0006] To achieve the above object, the present invention provides a technical solution:

[0007] An algaecide and antiseptic functional monomer, wherein the raw materials for preparing the algaecide and antiseptic functional monomer include, by weight:

[0008]

[0009] Wherein, the structural formula of the modified algaecide and preservative compound is:

[0010] In some embodiments, the raw materials for preparing the modified algaecide and preservative compound include, by weight:

[0011]

[0012] Wherein, the structural formula of the algaecide and preservative compound is:

[0013] In some embodiments, the polymerization inhibitor includes at least one of hydroquinone and diphenylamine.

[0014] In some embodiments, the first catalyst includes at least one of 98 wt. % concentrated sulfuric acid, benzenesulfonic acid, and p-toluenesulfonic acid.

[0015] In some embodiments, the second catalyst comprises FeCl3 and CuCl 2 At least one of .

[0016] In some embodiments, the solvent comprises dichloromethane.

[0017] In some embodiments, the first oxidizing agent is hydrogen peroxide, and the first reducing agent includes sodium sulfite.

[0018] The present invention also provides a method for preparing an algaecide and antiseptic functional monomer, comprising the steps of:

[0019] The modified algaecide and antiseptic compound is mixed with an inhibitor, and a catalyst is added to react. After the reaction is completed, the algaecide and antiseptic functional monomer is obtained.

[0020] In some embodiments, the preparation method of the algaecide and antiseptic functional monomer comprises the steps of:

[0021] The unsaturated acid, the modified algaecide preservative compound and the inhibitor are mixed and placed in a nitrogen environment, and then a catalyst is added. The temperature is then raised to 80°C to 95°C and reacted for 2 to 4 hours. After the reaction is completed, the temperature is lowered to room temperature to obtain an algaecide preservative functional monomer.

[0022] In some embodiments, the weight percentage of the unsaturated acid is 75 parts to 105 parts.

[0023] In some embodiments, the preparation steps of the modified algaecide and preservative compound include:

[0024] S210, dissolving the algaecide and antiseptic compound in a solvent to obtain an algaecide and antiseptic compound solution;

[0025] S220, adding a catalyst and an oxidant to the algaecide and preservative compound solution, stirring and reacting for 4 to 6 hours;

[0026] S230, after the reaction is completed, a reducing agent is added to remove excess oxidant to obtain a modified algaecide and preservative compound.

[0027] In some embodiments, in step S210, the reaction temperature is 0°C to 10°C.

[0028] The invention also provides an application of an algaecide and antiseptic functional monomer in a water reducing agent.

[0029] In some embodiments, the water reducing agent comprises:

[0030]

[0031] In some of the embodiments, the polyether macromonomer includes at least one of ethylene glycol monovinyl polyethylene glycol ether and methyl allyl alcohol polyoxyethylene ether, and has a molecular weight of 2000 to 4000.

[0032] In some embodiments, the unsaturated acid monomer includes at least one of acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and fumaric acid, preferably acrylic acid.

[0033] In some embodiments, the second reducing agent is at least one of bleaching powder, VC, sodium thiosulfate, sodium hypophosphite and sodium phosphite;

[0034] In some embodiments, the second oxidizing agent includes ammonium persulfate.

[0035] In some embodiments, the chain transfer agent includes at least one of mercaptoethanol and thioglycolic acid.

[0036] In some embodiments, the preparation steps of the water reducing agent include:

[0037] The algaecide and antiseptic functional monomer, the polyether macromonomer, the second oxidant and water are uniformly stirred to obtain a base liquid;

[0038] Add liquid A and liquid B dropwise to the base liquid. After the addition is completed, keep the temperature for reaction for 1 to 3 hours to obtain the water reducing agent.

[0039] Wherein, the liquid A is prepared by dissolving an unsaturated acid monomer in water;

[0040] The B liquid is prepared by mixing a reducing agent, a chain transfer agent and water.

[0041] In some embodiments, the water reducing agent is prepared at room temperature, that is, the temperature is 20°C to 35°C.

[0042] Beneficial effects of the present invention:

[0043] The algaecidal and antiseptic functional monomer prepared by the present invention uses a modified algaecidal and antiseptic compound containing a hydrophilic functional group as a preparation raw material, and by introducing a hydrophilic functional group, the solubility of the algaecidal and antiseptic functional monomer is significantly improved, so that the compound is more evenly dispersed in the reaction medium.

[0044] The present invention prepares a water reducer with excellent algaecidal performance and significant anti-corrosion performance by copolymerizing algaecidal and anti-corrosion functional small monomers, polyether macromonomers and unsaturated acid small monomers. The product also has a good collapse-preserving effect and can maintain the performance of the water reducer stable for a long time without the need to add additional preservatives. The application of the water reducer is flexible, and it can be used alone or compounded with other water reducers to meet various engineering needs.

[0045] The algae antiseptic functional monomer prepared by the invention is applied to the water reducer, which gives the material excellent algaecidal function and effectively reduces the pollution risk of storage tanks and pipelines caused by the invasion of algae and fungi, thereby improving the stability and safety during storage and transportation. DETAILED DESCRIPTION

[0046] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0047] In the examples, the test methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0048] 1. Preparation of modified algaecidal and antiseptic compounds:

[0049] S210, dissolving 30 g of the algaecidal and preservative compound in 1000 g of dichloromethane to obtain an algaecidal and preservative compound solution.

[0050] S220, add 1.8g FeCl 3 and 12g 30wt.% hydrogen peroxide, stirred and reacted for 6 hours; the reaction temperature was controlled between 0°C and 10°C.

[0051] S230. After the reaction is completed, 2 g of sodium sulfite is added to remove excess oxidant to obtain a modified algaecide and preservative compound.

[0052] 2. Preparation of algaecide and antiseptic functional monomers:

[0053] 1. Preparation of algaecide and antiseptic functional monomer A1:

[0054] 100g of acrylic acid, 82g of modified algaecide preservative compound and 0.5g of hydroquinone were mixed and placed in a nitrogen environment. 2g of benzenesulfonic acid was added, and then the temperature was raised to 90°C and reacted for 3 hours. After the reaction was completed, the temperature was cooled to room temperature to obtain the algaecide preservative functional monomer A1.

[0055] 2. Preparation of algaecide and antiseptic functional monomer A2:

[0056] 100g of acrylic acid, 100g of modified algaecide preservative compound and 0.5g of hydroquinone were mixed and placed in a nitrogen environment. 3.5g of benzenesulfonic acid was added, and then the temperature was raised to 95°C and reacted for 2 hours. After the reaction was completed, the temperature was cooled to room temperature to obtain the algaecide preservative functional monomer A2.

[0057] 3. Preparation of water reducing agent:

[0058] Example 1

[0059] At room temperature (25° C.), 55 g of algaecide and preservative functional monomer A1, 240 g of methyl allyl alcohol polyoxyethylene ether, 1.3 g of ammonium persulfate and 110 g of water were stirred evenly to obtain a base solution;

[0060] Add liquid A and liquid B dropwise to the base liquid. After the addition is completed, keep the temperature for reaction for 1 hour to obtain the water reducing agent.

[0061] Wherein, the liquid A is prepared by dissolving 35g of acrylic acid monomer in 28g of water;

[0062] The B solution is prepared by mixing 0.4 g of sodium phosphite, 1 g of mercaptoethanol and 42 g of water.

[0063] Example 2

[0064] The other steps are the same as those in Example 1, except that:

[0065]

[0066]

[0067] Example 3

[0068] The other steps are the same as those in Example 1, except that:

[0069]

[0070] Example 4

[0071] The other steps are the same as those in Example 1, except that:

[0072]

[0073] Example 5

[0074] The other steps are the same as those in Example 1, except that:

[0075]

[0076]

[0077] Example 6

[0078] The other steps are the same as those in Example 1, except that:

[0079] Example 7

[0080] The other steps are the same as those in Example 1, except that:

[0081] Comparative Example 1

[0082] Commercially available water reducing agent Point-400S (without preservatives).

[0083] Comparative Example 2

[0084] Commercially available water reducing agent Point-400S (with added preservative).

[0085] Comparative Example 3

[0086] The other steps are the same as those in Example 1, except that:

[0087] When preparing the water reducer, no algaecide and preservative functional monomer is added, and the amount of water is adjusted so that its solid content is consistent with that of the water reducer prepared in Example 1.

[0088] Comparative Example 4

[0089] The other steps are the same as those in Example 1, except that:

[0090] When preparing the water reducing agent, the algaecide and antiseptic functional monomer is replaced with an algaecide and antiseptic compound of equal mass.

[0091] Comparative Example 5

[0092] The other steps are the same as those in Example 1, except that:

[0093] When preparing the water reducing agent, the algaecide and preservative functional monomer is replaced with an equal mass of a commercially available preservative (isothiazolinone preservative, effective content 3.0%).

[0094] Table 1 Concrete water reduction performance test results

[0095]

[0096] Table 2 Algaecide and antiseptic test results

[0097]

[0098]

[0099] Note: “-” means the liquid is clear and bacteria-free, “+” means slight corruption, and “+++++” means severe corruption. The more + the number, the more serious the corruption.

[0100] As shown in Table 2, the water reducers (Examples 1 to 7) with algaecide and antiseptic functional monomers added did not show corruption during the entire test period, showing good antiseptic effects. In contrast, the water reducers (Comparative Examples 1 and 3) without preservatives or algaecide and antiseptic functional monomers added showed corruption to varying degrees over time. This shows that the algaecide and antiseptic functional monomers have a significant antiseptic effect in the water reducer.

[0101] It should be noted that the specific parameters or some reagents in the above embodiments are specific embodiments or preferred embodiments of the present invention, rather than limiting the present invention; those skilled in the art can make adaptive adjustments within the scope of the present invention.

Claims

1. An algaecide and antiseptic functional monomer, characterized in that: The raw materials for preparing the algaecide and antiseptic functional monomer include, by weight: Wherein, the structural formula of the modified algaecide and preservative compound is:

2. The algaecide and antiseptic functional monomer according to claim 1, characterized in that: The raw materials for preparing the modified algaecide and preservative compound include, by weight: Wherein, the structural formula of the algaecide and preservative compound is:

3. The algaecide and antiseptic functional monomer according to claim 1, characterized in that: The polymerization inhibitor includes at least one of hydroquinone and diphenylamine.

4. The algaecide and antiseptic functional monomer according to claim 1, characterized in that: The first catalyst includes at least one of 98 wt. % concentrated sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid.

5. The algaecide and antiseptic functional monomer according to claim 1, characterized in that: The second catalyst includes at least one of FeCl3 and CuCl2.

6. The algaecide and antiseptic functional monomer according to claim 1, characterized in that: The solvent includes dichloromethane.

7. The algaecide and antiseptic functional monomer according to claim 1, characterized in that: The first oxidizing agent is hydrogen peroxide, and the first reducing agent includes sodium sulfite.

8. A method for preparing an algaecide and antiseptic functional monomer according to any one of claims 1 to 7, characterized in that: Includes steps: The modified algaecide and antiseptic compound is mixed with an inhibitor, and a catalyst is added to react. After the reaction is completed, the algaecide and antiseptic functional monomer is obtained.

9. Use of the algaecide and antiseptic functional monomer according to any one of claims 1 to 7 in a water reducing agent.

10. The application according to claim 9, characterized in that: In parts by weight, the water reducing agent comprises:

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