CN117720692A - Algae-inhibiting solid water reducer and preparation method thereof - Google Patents

Abstract

The invention relates to an algae-inhibiting solid water reducer and a preparation method thereof, and the algae-inhibiting solid water reducer comprises the following raw materials in parts by weight: 5-12 parts of small algae removal and corrosion prevention monomer; 260-320 parts of polyether macromonomer; 10-16 parts of unsaturated ester small monomer; 32-40 parts of unsaturated acid small monomers; 0.8-1.6 parts of chain transfer agent; initiator 2.4-3.0 parts; and xylene. The algae-inhibiting solid water reducer prepared by the invention has good algae inhibiting performance, certain slump retaining performance and good water reducing performance, does not need to add any preservative, can keep the polycarboxylate water reducer from deteriorating for a long time, can be used independently, and can also be used in combination with other water reducers.

Description

Algae-inhibiting solid water reducer and preparation method thereof

Technical Field

The invention relates to the technical field of concrete, in particular to an algae-inhibiting solid water reducer and a preparation method thereof.

Background

The polycarboxylic acid water reducer has the main advantages of low mixing amount, high water reducing rate, high slump retaining property, environment-friendly production and use process and the like, and is a water reducer product with wide development prospect. The polycarboxylate water reducer is often compounded with functional components such as a retarding component, an early strength component, a defoaming component, an air entraining component and the like to improve the performance of different functions of concrete, most of the components are organic components, and can provide nutrients for the breeding of bacteria, saccharomycetes, mold and algae, wherein the retarding component is produced by a microbial fermentation method by using a wide range of sodium gluconate, and the aspergillus niger possibly remains.

In addition, the production, storage and transportation container or pipeline is not clean and has bacteria, the production water or storage tank has algae bacteria, other auxiliary small materials can bring in microorganisms such as fungi and bacteria to the polycarboxylate water reducer, so that the microorganisms are rapidly propagated in the environment, and the polycarboxylate water reducer is mildewed.

The mildew problem of polycarboxylate water reducers is particularly frequent under conditions of high temperature in summer, export in sea, long-time shutdown and the like. The water reducer is bad and smelly, the sealed container is inflated and swelled or even burst, layering or precipitation is generated, flocculent or sticky skin-shaped floaters appear on the liquid surface, economic loss is caused, the product performance is reduced, and hidden danger is caused to the quality of concrete.

Disclosure of Invention

Based on the above, it is necessary to provide an algae-inhibiting solid water reducing agent with algae-killing and corrosion-preventing effects and a preparation method thereof.

In order to achieve the above object, the present invention provides a technical solution:

the preparation raw materials of the algae-inhibiting solid water reducer comprise the following components in parts by weight:

preferably, the preparation raw materials of the small algae removal and corrosion prevention monomer comprise the following components in parts by weight:

preferably, the dehalogenation agent comprises at least one of diisopropylethylamine and triethylamine.

Preferably, the polymerization inhibitor includes at least one of para-hydroxyanisole and hydroquinone.

Preferably, the polyether macromonomer comprises at least one of ethylene glycol monovinyl polyethylene glycol ether and methallyl alcohol polyoxyethylene ether with a molecular weight of 2000-4000.

Preferably, the unsaturated ester small monomer includes at least one of methyl methacrylate, ethyl methacrylate and hydroxyethyl methacrylate.

Preferably, the unsaturated acid small monomer is one or more of acrylic acid, methacrylic acid, maleic anhydride and fumaric acid.

Preferably, the chain transfer agent comprises at least one of thioglycollic acid and thioglycollic acid.

The invention also provides a preparation method of the algae-inhibiting solid water reducer, which comprises the following steps:

mixing the polyether macromonomer with dimethylbenzene to obtain a component A;

mixing the unsaturated ester small monomer, the unsaturated acid small monomer and xylene to obtain a component B;

ultrasonically dissolving the small algae removal and corrosion prevention monomer, the chain transfer agent and xylene to obtain a component C;

dropwise adding the initiator, the component B and the component C into the component A, and preserving heat for 1-3 hours after the dropwise adding is finished, so that a reaction product is obtained after the reaction is finished; specifically, the reaction temperature is 80-95 ℃.

And (3) distilling under reduced pressure to remove dimethylbenzene in a reaction product, thus obtaining the algae-inhibiting solid water reducer.

Preferably, the step of preparing the small monomer with the algae removal and corrosion prevention functions comprises the following steps:

mixing the 2-n-octyl-4-isothiazolin-3-one with toluene to obtain a first mixture;

adding the dehalogenation agent and the polymerization inhibitor into the first mixture to obtain a second mixture, stirring the second mixture and heating the second mixture to a reflux state;

and (3) dropwise adding the mixed solution of allyl chloroformate and toluene into the second mixture in a reflux state, continuing reflux reaction for 4-6 h after the dropwise adding is finished, and washing with water, drying, concentrating and crystallizing after the reaction is finished to obtain the small algae removal and corrosion prevention monomer.

The invention has the beneficial effects that:

the algae inhibiting solid water reducer prepared by the invention is in a solid state, can be stored for a long time without deterioration, and is convenient for packaging and transportation.

The preparation method is simple, is easy for industrial production, and the used organic solvent can be recycled, so that the method does not waste resources and is environment-friendly.

The algae-inhibiting solid water reducer prepared by the invention has good algae inhibiting performance, certain slump retaining performance and good water reducing performance, does not need to add any preservative, can keep the polycarboxylate water reducer from deteriorating for a long time, can be used independently, and can also be used in combination with other water reducers.

Detailed Description

For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.

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

The preparation raw materials of the algae-inhibiting solid water reducer comprise the following components in parts by weight:

specifically, the structural formula of the small algae removal and corrosion prevention monomer is as follows:

the structural formula of the algae inhibiting solid water reducing agent is as follows:

more specifically, the molecular weight of the algae inhibiting solid water reducing agent is 20000 to 60000.

In an embodiment, the preparation raw materials of the small algae removal and corrosion prevention monomer comprise the following components in parts by weight:

specifically, the algae inhibiting solid water reducing agent can gradually release BIT (2-N-octyl-4-isothiazolin-3-ketone) molecules in water, and N-S bonds in the BIT molecules can damage protein mercaptan in algae bacteria, so that the algae inhibiting solid water reducing agent has good algae inhibiting performance.

In one embodiment, the dehalogenation agent comprises at least one of diisopropylethylamine and triethylamine.

In one embodiment, the polymerization inhibitor includes at least one of para-hydroxyanisole and hydroquinone.

In one embodiment, the polyether macromonomer comprises at least one of ethylene glycol monovinyl polyethylene glycol ether and methallyl alcohol polyoxyethylene ether having a molecular weight of 2000 to 4000.

In one embodiment, the unsaturated ester small monomer includes at least one of methyl methacrylate, ethyl methacrylate, and hydroxyethyl methacrylate.

In one embodiment, the unsaturated acid-based monomer is one or more of acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid. Hydroxyethyl methacrylate and acrylic acid are preferred.

In one embodiment, the chain transfer agent comprises at least one of thioglycolic acid and thioethanol.

In one embodiment, the initiator is a catalyst comprising azobisisobutyronitrile.

The invention also provides a preparation method of the algae-inhibiting solid water reducer, which comprises the following steps:

mixing the polyether macromonomer with dimethylbenzene to obtain a component A;

mixing the unsaturated ester small monomer, the unsaturated acid small monomer and xylene to obtain a component B;

ultrasonically dissolving the small algae removal and corrosion prevention monomer, the chain transfer agent and xylene to obtain a component C;

dropwise adding the initiator, the component B and the component C into the component A, and preserving heat for 1-3 hours after the dropwise adding is finished, so that a reaction product is obtained after the reaction is finished;

and (3) distilling under reduced pressure to remove dimethylbenzene in a reaction product, thus obtaining the algae-inhibiting solid water reducer.

In one embodiment, the step of preparing the small algae removal and corrosion prevention monomer comprises the following steps:

mixing the 2-n-octyl-4-isothiazolin-3-one with toluene to obtain a first mixture;

adding the dehalogenation agent and the polymerization inhibitor into the first mixture to obtain a second mixture, stirring the second mixture and heating the second mixture to a reflux state;

and (3) dropwise adding the mixed solution of allyl chloroformate and toluene into the second mixture in a reflux state, continuing reflux reaction for 4-6 h after the dropwise adding is finished, and washing with water, drying, concentrating and crystallizing after the reaction is finished to obtain the small algae removal and corrosion prevention monomer.

Examples

1. Preparation of small monomer with algae removal and corrosion prevention functions

The preparation method comprises the following steps:

mixing the 2-n-octyl-4-isothiazolin-3-one with toluene to obtain a first mixture;

adding the dehalogenation agent and the polymerization inhibitor into the first mixture to obtain a second mixture, stirring the second mixture and heating the second mixture to a reflux state;

and (3) dropwise adding the mixed solution of allyl chloroformate and toluene into the second mixture in a reflux state, continuing reflux reaction for 4 hours after the dropwise adding is finished, closing heating after the reaction is finished, naturally cooling, washing the reaction solution with deionized water, and drying, concentrating and crystallizing to obtain the small algae removal and corrosion prevention monomer.

Examples 1 to 7 the raw materials for preparing the small monomer with algae removal and corrosion prevention functions are shown in table 1.

Table 1 raw material tables for preparing small monomers with algae removal and corrosion prevention functions in examples 1 to 7

2. Preparation of algae-inhibiting solid water reducer

The preparation method comprises the following steps:

mixing 260-320 parts of polyether macromonomer and 90-120 parts of dimethylbenzene to obtain a component A;

10-16 parts of unsaturated ester small monomers, 32-40 parts of unsaturated acid small monomers and 25-30 parts of dimethylbenzene are mixed to obtain a component B;

ultrasonically dissolving 5-12 parts of small algae removal and corrosion prevention monomer, 0.8-1.6 parts of chain transfer agent and 38-42 parts of dimethylbenzene to obtain a component C;

dropwise adding the initiator, the component B and the component C into the component A, and preserving heat for 1-3 hours after the dropwise adding is finished, so that a reaction product is obtained after the reaction is finished; the reaction temperature is 80-95 ℃.

And (3) distilling under reduced pressure to remove dimethylbenzene in a reaction product, thus obtaining the algae-inhibiting solid water reducer.

Examples 1 to 7 the raw materials and reaction conditions for preparing the alga-inhibiting type solid water reducer are shown in Table 2

TABLE 2 raw materials and reaction conditions for preparing alga-inhibiting solid water reducer

Comparative example 1

Otherwise, the method is the same as in the embodiment 1, and the small monomer with algae killing and corrosion preventing functions is not added in the preparation of the algae inhibiting solid water reducing agent.

Comparative example 2

Otherwise, the same procedure as in example 1 was followed except that 2-n-octyl-4-isothiazolin-3-one was changed to 2-methyl-4-isothiazolin-3-one in the preparation of small monomer having algae removal and corrosion prevention functions.

Performance test:

1. water reducing property

The algicidal corrosion-resistant polycarboxylate water reducer obtained in examples 1 to 7 was used in comparison with a commercial polycarboxylate water reducer Point-400 to which no preservative was added and a commercial polycarboxylate water reducer to which a pinon preservative was added, and a water reduction test was performed. The test method is implemented by referring to the standard specification of GB 8076-2008 concrete admixture. The results of the water reduction test are shown in Table 3.

TABLE 3 concrete Performance test results

From the above table 3 data can be obtained: as is clear from the comparison, in 270d, the water-reducing performance of the algae-killing corrosion-preventing polycarboxylic acid is above 25%, the water-reducing rate of the commercial polycarboxylic acid water reducer product without the preservative is reduced due to decay at 28d, the water-reducing rate is reduced to 21.7% at 270d, the water-reducing rate of the polycarboxylic acid water reducer is reduced to 180d after the water-reducing rate of the polycarboxylic acid water reducer product is delayed to be reduced to 22.5% at 270 d. Therefore, the algae-killing corrosion-preventing polycarboxylic acid can keep 270d and still has excellent water-reducing performance.

2. Algae killing and corrosion preventing properties

The test method comprises the following steps: the fungus suspension was added in equal amounts to the algicidal and antiseptic polycarboxylate superplasticizer obtained in examples 1 to 7, and to commercial polycarboxylate superplasticizers without added preservative and commercial polycarboxylate superplasticizer with added kathon preservative, and incubated at a constant temperature of 28 ℃.

The initial colony count was recorded before the samples were placed in the petri dishes, sampled at 28d, 90d, 180d and 270d, respectively, the samples were observed, and the detection results were recorded as shown in table 4.

TABLE 4 algae removal antiseptic test results

Note that: "-" is thorough and non-growing in liquid, "+" is slight putrefaction, "+++++" is the occurrence a severe spoilage phenomenon is caused by the fact that, spoilage is severe with increasing +ions.

From the above table 4 data is available: compared with the prior art, in 270d, the algae-killing corrosion-preventing polycarboxylic acid has almost no putrefaction, the commercial polycarboxylic acid water reducing agent product without the preservative has more obvious putrefaction at 28d, floccules in liquid, little mold on liquid surface, serious putrefaction at 90d, dark red liquid and mold covering on large surface area; when the kathon preservative is added into the commercial polycarboxylate superplasticizer product, the deterioration phenomenon of the polycarboxylate superplasticizer occurs only at 180d, floccule precipitates, and the deterioration phenomenon is serious at 270 d. Comparative example 1 because no small monomer with algae removal and corrosion prevention functions was introduced during the synthesis, the synthesized product had no algae removal and corrosion prevention properties, and the putrefaction occurred at 28 d. Comparative example 2 since 2-n-octyl-4-isothiazolin-3-one was changed to 2-methyl-4-isothiazolin-3-one in the synthesis, 2-methyl-4-isothiazolin-3-one was decomposed at high temperature in the reaction, the synthesized product had no algae removal and corrosion prevention properties, and also had a putrefaction at 28 d.

Therefore, the algae-killing corrosion-preventing polycarboxylic acid has excellent algae-killing corrosion-preventing performance.

It should be noted that the specific parameters or some reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limited thereto; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.

Claims (10)

1. The algae-inhibiting solid water reducer is characterized by comprising the following raw materials in parts by weight:

2. the algae inhibiting solid water reducing agent according to claim 1, wherein the preparation raw materials of the algae killing and corrosion preventing functional small monomer comprise, in parts by weight:

3. the algae inhibiting solid water reducing agent of claim 2, wherein the dehalogenation agent comprises at least one of diisopropylethylamine and triethylamine.

4. The algae inhibiting solid water reducing agent of claim 2, wherein the polymerization inhibitor comprises at least one of para-hydroxyanisole and hydroquinone.

5. The algae-inhibiting solid water reducing agent of claim 1, wherein the polyether macromonomer comprises at least one of ethylene glycol monovinyl polyethylene glycol ether and methallyl alcohol polyoxyethylene ether having a molecular weight of 2000-4000.

6. The algae-inhibiting solid water reducer of claim 1, wherein the unsaturated ester-based small monomer comprises at least one of methyl methacrylate, ethyl methacrylate, and hydroxyethyl methacrylate.

7. The algae-inhibiting solid water reducer of claim 1, wherein the unsaturated acid-based small monomer is one or more of acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid. Hydroxyethyl methacrylate and acrylic acid are preferred.

8. The algae inhibiting solid water reducing agent of claim 1, wherein the chain transfer agent comprises at least one of thioglycollic acid and thioglycollic acid.

9. A method for preparing the algae-inhibiting solid water reducing agent as set forth in any one of claims 1 to 8, comprising the steps of:

mixing the polyether macromonomer with dimethylbenzene to obtain a component A;

mixing the unsaturated ester small monomer, the unsaturated acid small monomer and xylene to obtain a component B;

ultrasonically dissolving the small algae removal and corrosion prevention monomer, the chain transfer agent and xylene to obtain a component C;

dropwise adding the initiator, the component B and the component C into the component A, and preserving heat for 1-3 hours after the dropwise adding is finished, so that a reaction product is obtained after the reaction is finished;

and (3) distilling under reduced pressure to remove dimethylbenzene in a reaction product, thus obtaining the algae-inhibiting solid water reducer.

10. The method for preparing the algae-inhibiting solid water reducing agent according to claim 9, wherein the step of preparing the small algae-killing and corrosion-preventing monomer comprises:

mixing the 2-n-octyl-4-isothiazolin-3-one with toluene to obtain a first mixture;

adding the dehalogenation agent and the polymerization inhibitor into the first mixture to obtain a second mixture, stirring the second mixture and heating the second mixture to a reflux state;

and (3) dropwise adding the mixed solution of allyl chloroformate and toluene into the second mixture in a reflux state, continuing reflux reaction for 4-6 h after the dropwise adding is finished, and washing with water, drying, concentrating and crystallizing after the reaction is finished to obtain the small algae removal and corrosion prevention monomer.