CN109294716B

CN109294716B - Preparation method and application of novel concrete release agent

Info

Publication number: CN109294716B
Application number: CN201811348836.5A
Authority: CN
Inventors: 陈杰; 颜义; 田应兵; 方世昌; 皮永奇
Original assignee: Guizhou Shiboshi Technology Co ltd
Current assignee: Guizhou Shiboshi Technology Co ltd
Priority date: 2018-11-13
Filing date: 2018-11-13
Publication date: 2021-08-20
Anticipated expiration: 2038-11-13
Also published as: CN109294716A

Abstract

The invention provides a preparation method and application of a novel concrete release agent. The method comprises the following steps: (a) adding unsaturated fatty acid into a mixture of water and an emulsifier, adding a catalyst and an active monomer A respectively, and curing after reaction; (b) adding the active monomer B, the active monomer C and the active monomer D into a mixture of water and an emulsifier, and curing after reaction; (c) and (3) adding the products of the steps (a) and (b) and optional auxiliary materials into a mixture of water and an emulsifier, and stirring and mixing to obtain the novel concrete release agent. In the invention, different oily substances are emulsified under different HLB, and then different emulsions and related auxiliary agents are compounded and fused to obtain the novel emulsion type release agent. After the release agent is sprayed for use, a film is formed compactly, a certain waterproof effect is achieved, and meanwhile, the release agent has a good inhibition effect on air bubbles on the surface of concrete. Meanwhile, the release agent has wide raw material sources and low finished product price.

Description

Preparation method and application of novel concrete release agent

Technical Field

The invention relates to the technical field of concrete, in particular to a preparation method and application of a novel concrete release agent.

Background

The concrete release agent is a common concrete additive, and is usually applied to the inner surface of a template in a surface coating or spraying mode, so that the adhesion between concrete and the template is reduced, and the concrete is prevented from adhering to the template after being cured to influence the integrity of a concrete structure and the surface finish. With the increasing annual use of concrete, research on concrete release agents that play a very important role in the development and application of concrete technology and building materials is constantly evolving.

For example, PCT/CN2016/091770 FaIR-FACED CONCRETE RELEASE AGENT AND CONCRETE METHOD thermal release agent of the prior art discloses an as-cast-finish CONCRETE release agent and a PREPARATION METHOD thereof, wherein the CONCRETE comprises the following raw materials by weight: 2-10 parts of tributyl phosphate, 80-220 parts of waste engine oil, 2-8 parts of sodium nitrite, 15-65 parts of mineral oil, 50-150 parts of vegetable oil, 5-25 parts of antirust agent and 3-18 parts of antirust agent. 10-30 parts of polyvinyl alcohol, 10-30 parts of rosin oil, 5-25 parts of methyl cellulose and 2-8 parts of active soil.

Meanwhile, PCT/CN2016/091769 (Water-SOLUBLE CONCRETE RELEASE AGENT AND CONCRETE METHOD thermal remover) in the prior art discloses a WATER-SOLUBLE CONCRETE release agent and a PREPARATION METHOD thereof, wherein the CONCRETE release agent comprises the following raw materials in parts by weight: 15-55 parts OF coconut oil diethanolamide, 25-75 parts OF triethanolamine oleate, 200-500 parts OF glycerol, 10-45 parts OF lauryl alcohol diethanolamide, 20-50 parts OF dodecyl diethanolamide, 1-10 parts OF OF colorant, 3-18 parts OF sodium benzoate, 10-30 parts OF rosin, 5-25 parts OF methyl cellulose and 2-8 parts OF sodium carbonate.

Similarly, CN201410786051.1, "a concrete release agent prepared from rapeseed oil and a preparation method thereof" in the prior art also discloses a concrete release agent prepared from rapeseed oil and a preparation method thereof, wherein the concrete release agent comprises the following raw materials in parts by weight: 30-50 parts of modified rapeseed oil, 15-20 parts of zinc stearate, 5-8 parts of chlorinated paraffin, 8-10 parts of dimethyl silicone oil, 4-5 parts of methyltrimethoxysilane, 0.5-1.0 part of sodium polyacrylate solution, 4-5 parts of tributyl citrate, 600.6-1.0 part of span, 2-4 parts of zinc oxide and 250 parts of deionized water.

Although the prior art as exemplified above has been studied and searched for concrete release agents of different compositions and different systems, these prior art release agents still have certain drawbacks in practical use, specifically:

first, a pure oil type release agent: the pure oil release agent is mainly used by mineral oil, animal oil, vegetable oil and waste oil (waste engine oil, waste diesel oil, kitchen waste grease and the like) of the mineral oil, the animal oil and the vegetable oil as the release agent, although the raw materials are wide in source, the pure oil release agent has the defects that the surface bubbles are more, the animal oil and the vegetable oil are easy to deteriorate and decay, the effect is lost and the like;

secondly, emulsion type release agent: the release agent has the characteristics of wide raw material source, contribution to industrial production, stable production, low price and the like, and can form a layer film after water is evaporated to play a role in releasing after the emulsion which achieves the Tyndall phenomenon is sprayed on a template, however, the emulsion type release agent cannot contact with rainwater, so that the actual application scene and application range of the release agent are greatly limited;

thirdly, paint releasing agent: the existing paint system is applied to a concrete template after being improved and modified, although the release agent has high film forming strength and good film ductility, the release agent also has the defects of difficult cleaning, difficult repairing, high price and the like, and the scheme is rarely adopted in the actual production.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The invention aims to provide a novel concrete release agent which has wide raw material sources, low price, good stability and water resistance and good inhibiting effect on concrete surface bubbles.

In order to achieve the above purpose of the present invention, the following technical solutions are adopted:

a preparation method of a novel concrete release agent comprises the following steps: (a) adding unsaturated fatty acid into a mixture of water and an emulsifier, uniformly dispersing, adding a catalyst and an active monomer A, reacting and curing; (b) adding the active monomer B, the active monomer C and the active monomer D into a mixture of water and an emulsifier, uniformly dispersing, and curing after reaction; (c) adding the products of the steps (a) and (b) and optional auxiliary materials into a mixture of water and an emulsifier, and stirring and mixing to obtain a novel concrete release agent; wherein the unsaturated fatty acids comprise: at least one of safflower seed oil, flaxseed oil, linolenic acid, or arachidonic acid; and/or, the reactive monomer A comprises: at least one of acrylic acid, methacrylic acid, or acrylamide; and/or, the reactive monomer B comprises: at least one of maleic anhydride, fumaric acid, or methacrylic acid; and/or, the reactive monomer C comprises: at least one of styrene, or vinyl toluene and/or the reactive monomer D comprises: at least one of isooctyl acrylate or n-butyl acrylate.

Meanwhile, the invention also provides a novel concrete release agent obtained by the method.

The invention also provides the application of the prepared novel concrete release agent in the preparation of concrete.

Furthermore, the invention also provides a concrete preparation method, and in the preparation method, the novel concrete release agent prepared by the method is applied.

Compared with the prior art, the invention has the beneficial effects that:

in the invention, different oily substances are emulsified under different HLB, and then different emulsions and related auxiliary agents are compounded and fused to obtain a novel emulsion type release agent;

after the release agent is sprayed on the surface of a mould, the formed film is compact, a certain waterproof effect is achieved, the ductility of the formed film is enhanced by adding the styrene substance in a targeted manner in combination with the characteristics of paint, and the release agent has a good inhibition effect on air bubbles on the surface of concrete;

meanwhile, the raw material for preparing the release agent has wide sources, and the finished product has the advantages of low price and the like.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.

FIG. 1 is a schematic view showing the appearance of a blank concrete in Experimental example 1 after the concrete is demolded;

FIG. 2 is a schematic view showing the appearance of a commercially available concrete sample in Experimental example 1 after demolded;

FIG. 3 is a schematic view showing the appearance of the concrete of example 1 after it was demolded in Experimental example 1;

FIG. 4 is a schematic view showing the appearance of the concrete of example 2 of Experimental example 1 after it is demolded;

FIG. 5 is a schematic view showing the appearance of the concrete of example 3 in Experimental example 1 after it was demolded.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The concrete release agent provided by the invention is a new composition and system concrete release agent which is provided for overcoming the defects of the existing release agent in the aspects of product stability, waterproofness, manufacturing cost, actual use performance and the like.

Specifically, the novel concrete release agent provided by the invention can be prepared by the following method:

(i) stirring and mixing 50 parts of water and an emulsifier in an emulsifying machine, controlling the HLB value to be 6-8 by adjusting the type and the number of the emulsifier, preferably stirring for 30min, and heating to 60-70 ℃;

in this step, the emulsifiers used were: sodium dodecylbenzene sulfonate, polyoxyethylene octyl phenol ether-10 (OP-10), polyoxyethylene sorbitan monooleate (Tween-80), or sorbitan fatty acid ester.

(ii) Adding 20-30 parts of unsaturated fatty acid into the mixture obtained in the step (i) under the condition of stirring, and stirring until oil droplets are dispersed;

in this step, the unsaturated fatty acids are: at least one of safflower seed oil, linseed oil, linolenic acid, or arachidonic acid.

(iii) After the temperature of the mixed system obtained in the step (ii) is stabilized at 70-80 ℃, adding 0.03-0.06 part of catalyst, then dropwise adding 12-18 parts of monomer A solution with activity within 30-60 min, and then curing for 1h to obtain a product, namely a substance M;

wherein the active monomer A is at least one of acrylic acid, methacrylic acid or acrylamide;

wherein the catalyst is at least one of ammonium persulfate, potassium persulfate or azobisisobutyronitrile;

(iv) stirring and mixing an emulsifier and 89.7 parts of water in a stirrer, controlling the HLB value to be 13-15 by adjusting the type and the number of the emulsifier, and then respectively adding 4-6 parts of an active monomer B, 1-4 parts of an active monomer C and 1-5 parts of an active monomer D;

then, heating to 70-80 ℃, and stirring until oil droplets are uniformly dispersed; stirring and reacting under the condition of heat preservation, curing for 60min after the reaction, and recording the obtained product as a substance N;

in this step, the emulsifiers are: at least one of sodium dodecylbenzene sulfonate, polyoxyethylene octyl phenol ether-10 (OP-10), polyoxyethylene sorbitan monooleate (Tween-80), or sorbitan fatty acid ester;

meanwhile, the catalyst is at least one of ammonium persulfate, potassium persulfate or azodiisobutyronitrile;

the active monomer B is: at least one of maleic anhydride, fumaric acid, or methacrylic acid;

the reactive monomer C is: at least one of styrene, or vinyl toluene;

the reactive monomer D is: at least one of isooctyl acrylate or n-butyl acrylate.

(v) Adding 55-65 parts of substance M, 30-40 parts of substance N, 1-3 parts of defoaming agent, 1-4 parts of preservative and stabilizing reinforcing agent into an emulsifying and stirring device; then, stirring and mixing for 30min under the condition of high-speed stirring to obtain a novel concrete release agent;

meanwhile, the defoaming agent is: at least one of polyether siloxane copolymer emulsion or dimethyl silicone oil;

the preservative is as follows: at least one of sodium benzoate, 2-methyl-4-isothiazolin-3-one, or potassium sorbate;

the stability enhancer is: at least one of triethanolamine or diethanolamine.

As can be seen from the above preparation process, the raw materials used in the steps of the invention are all the existing and easily available raw materials; meanwhile, the control of the reaction conditions of each step can be realized by conventional equipment under the condition of common heating temperature. Therefore, the concrete release agent product has lower overall cost. Meanwhile, by controlling reaction conditions (including raw material selection, reaction control of different raw materials under different HLB conditions and the like), the product prepared by the method has good practical use performance, not only has certain waterproofness, but also is easy to clean and repair, and the defects of the existing release agent are well overcome.

Furthermore, the release agent of the invention obtained by the method has good performance, so the release agent can be further used for preparing various concrete and obtaining various concrete members.

Example 1

S1: adding 50 parts of water and 0.3 part of polyoxyethylene sorbitan monooleate and 0.8 part of sorbitan fatty acid ester into the mixture, starting stirring, stirring for 30 minutes, and heating to 60-70 ℃;

s2: after S1, adding 23.8 parts of safflower seed oil, and stirring until oil droplets are uniformly dispersed;

s3: adding a catalyst when the temperature is stabilized at 70-80 ℃; then, dropwise adding 14.9 parts of acrylic acid and 9.5 parts of aqueous solution at a constant speed within 30-60 minutes, and curing for 1 hour to obtain a substance M;

s4: adding 89.7 parts of water, 0.18 part of sodium dodecyl benzene sulfonate and 0.7 part of polyoxyethylene octyl phenol ether-10 into an emulsifying machine, starting stirring, and stirring for 30 minutes;

then, 4.5 parts of maleic anhydride, 2.1 parts of styrene and 3 parts of n-butyl acrylate are added; heating to 70-80 ℃, stirring until oil droplets are uniformly dispersed, and curing for 60 minutes after the reaction is finished to obtain a substance N;

s5: and (2) adding 59 parts of the substance M, 35 parts of the substance N, 1 part of polyether siloxane copolymer emulsion, 2 parts of sodium benzoate and 3 parts of triethanolamine into an emulsifying and stirring device, and stirring at a high speed for 30 minutes to obtain the novel concrete release agent.

Example 2

S1: adding 50 parts of water, 0.5 part of sorbitan fatty acid ester and 0.35 part of sodium dodecyl benzene sulfonate into the mixture, stirring the mixture for 30 minutes, and heating the mixture to 60-70 ℃;

s2: after S1, adding 15 parts of linseed oil and 10 parts of linolenic acid, and stirring until oil droplets are uniformly dispersed;

s3: adding a catalyst when the temperature is stabilized at 70-80 ℃; then dropwise adding 16.3 parts of methacrylic acid and 9.5 parts of aqueous solution at a constant speed within 30-60 minutes, and curing for 1 hour to obtain a substance M;

s4: adding 89.7 parts of water, 0.6 part of polyoxyethylene sorbitan monooleate and 0.3 part of sodium dodecyl benzene sulfonate into an emulsifying machine, starting stirring, and stirring for 30 minutes;

then, 4.5 parts of fumaric acid, 2.1 parts of vinyl toluene, and 3 parts of isooctyl acrylate were added; heating to 70-80 ℃, stirring until oil droplets are uniformly dispersed, and curing for 60 minutes after the reaction is finished to obtain a substance N;

Example 3

S1: adding 50 parts of water, 0.6 part of sorbitan fatty acid ester and 0.2 part of polyoxyethylene octyl phenol ether-10 into the mixture, starting stirring, stirring for 30 minutes, and heating to 60-70 ℃;

s2: after S1, adding 23.8 parts of arachidonic acid, and stirring until oil droplets are uniformly dispersed;

s3: adding a catalyst when the temperature is stabilized at 70-80 ℃; then dropwise adding 5 parts of acrylic acid, 10 parts of acrylamide and 9.5 parts of aqueous solution at a constant speed within 30-60 minutes, and curing for 1 hour to obtain a substance M;

s4: adding 89.7 parts of water, 0.34 part of sodium dodecyl benzene sulfonate and 0.78 part of polyoxyethylene octyl phenol ether-10 into an emulsifying machine, starting stirring, and stirring for 30 minutes;

then, 4.5 parts of methacrylic acid, 1 part of styrene, 1.2 parts of vinyl toluene, 1 part of isooctyl acrylate and 1 part of n-butyl acrylate are added; heating to 70-80 ℃, stirring until oil droplets are uniformly dispersed, and curing for 60 minutes after the reaction is finished to obtain a substance N;

Experimental example 1

The test method comprises the following steps: respectively coating different release agents on new concrete test molds, simultaneously loading the uniformly mixed concrete into the test molds in three layers according to a quartering method, curing and demolding after the same vibration, and comparing the surface appearance of the concrete. The blank was concrete without any release aid applied.

The results are shown in FIGS. 1 to 5, in which FIG. 1 is a blank sample, FIG. 2 is a commercial sample, and FIGS. 3 to 5 are examples 1 to 3.

As can be seen from the comparison of the appearance diagrams after the different sets of coagulation figures are demolded, the samples using the products of examples 1-3 of the present invention as the demolding agent have obviously smoother surfaces, less bubbles and better application effect compared with the samples without the demolding agent or with the commercial demolding agent.

While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. A preparation method of a concrete release agent is characterized by comprising the following steps:

(a) adding unsaturated fatty acid into a mixture of water and an emulsifier, uniformly dispersing, adding a catalyst and an active monomer A, reacting and curing;

(b) adding the active monomer B, the active monomer C and the active monomer D into a mixture of water and an emulsifier, uniformly dispersing, and curing after reaction;

(c) adding the products of the steps (a) and (b) and optional auxiliary materials into a mixture of water and an emulsifier, and stirring and mixing to obtain a concrete release agent;

wherein the unsaturated fatty acids comprise: at least one of safflower seed oil, flaxseed oil, linolenic acid, or arachidonic acid;

and, the reactive monomer a comprises: at least one of acrylic acid, methacrylic acid, or acrylamide;

and, the reactive monomer B comprises: at least one of maleic anhydride, fumaric acid, or methacrylic acid;

and, the reactive monomer C comprises: at least one of styrene, or vinyl toluene;

and, the reactive monomer D comprises: at least one of isooctyl acrylate or n-butyl acrylate;

in the step (a), the HLB value is 6-8;

in step (b), the HLB value is 13-15;

in the step (b), the reaction temperature is 70-80 ℃.

2. The method for producing a concrete mold release agent according to claim 1, wherein in step (a), the emulsifier comprises: at least one of sodium dodecyl benzene sulfonate, polyoxyethylene octyl phenol ether-10, polyoxyethylene sorbitan monooleate, or sorbitan fatty acid ester;

and/or, in step (b), the emulsifier comprises: at least one of sodium dodecyl benzene sulfonate, polyoxyethylene octyl phenol ether-10, polyoxyethylene sorbitan monooleate, or sorbitan fatty acid ester;

and/or, in step (c), the emulsifier comprises: sodium dodecylbenzene sulfonate, polyoxyethylene octyl phenol ether-10, polyoxyethylene sorbitan monooleate, or sorbitan fatty acid ester.

3. The method for preparing the concrete mold release agent according to claim 1, wherein the auxiliary materials comprise: at least one of a defoamer, a preservative, and a stability enhancer.

4. The method for producing a concrete mold release agent according to claim 3, characterized in that the defoaming agent comprises: at least one of polyether siloxane copolymer emulsion or dimethyl silicone oil;

and/or, the preservative comprises: at least one of sodium benzoate, 2-methyl-4-isothiazolin-3-one, or sorbic acid or potassium sorbate;

and/or, the stability enhancing agent comprises: at least one of triethanolamine or diethanolamine.

5. The method for preparing a concrete mold release agent according to claim 1, characterized in that step (a) comprises:

stirring and mixing water and an emulsifier, heating, adding unsaturated fatty acid, and stirring until oil droplets are uniformly dispersed;

then, a catalyst is added, an active monomer A is added dropwise for reaction, and the mixture is cured after the reaction.

6. The method for preparing a concrete mold release agent according to claim 1, characterized in that step (b) comprises:

stirring and mixing water and an emulsifier, adding an active monomer B, an active monomer C and an active monomer D, heating, and stirring until oil droplets are uniformly dispersed; and then aged after the reaction.

7. The method for preparing a concrete mold release agent according to claim 1, characterized in that step (c) comprises:

adding water into an emulsifier, stirring, then adding the products of the step (a) and the step (b) and auxiliary materials comprising a defoaming agent, an antiseptic and a stabilizer, and stirring at a high speed to obtain the concrete release agent.

8. A concrete release agent obtained by the method of any one of claims 1 to 7.

9. Use of the concrete release agent of claim 8 in the preparation of concrete.

10. A method for producing concrete, characterized in that the concrete mold release agent according to claim 8 is used in the method for producing concrete.