阅读说明：本技术 一种利用亲水小分子环氧复合树脂改性硫酸铝盐水泥潮湿基面的方法 (Method for modifying wet basal plane of aluminum sulfate cement by using hydrophilic micromolecule epoxy composite resin ) 是由 江波 李铃 李庆 王淑嫱 柯凯 储劲松 于 2021-07-20 设计创作，主要内容包括：本发明提供一种利用亲水小分子环氧复合树脂改性硫酸铝盐水泥潮湿基面的方法,首先在装有搅拌器和冷凝装置的反应釜中加入环氧单体、还原剂和水,以350r/min的速度搅拌,水浴加热至60-70℃；然后将胺类改性单体与引发剂配制成混合溶液,滴加至反应釜中,滴加时间为1.5-2小时；滴加完混合溶液后恒温反应1-2小时后自然冷却至室温,加入中和剂,出料,得到水性环氧树脂；之后将所得水性环氧树脂与聚醚胺固化剂投入反应釜,搅拌均匀,静置熟化15-20分钟,得到环氧复合单体,补水至总质量为1000份,得到环氧复合单体水溶液,将环氧复合单体水溶液涂覆于潮湿基面提高混凝土与潮湿基面间的作用力。本发明的制备工艺简单,产品性能优异、稳定性好、适应性广。(The invention provides a method for modifying a wet base surface of aluminum sulfate cement by using hydrophilic micromolecule epoxy composite resin, which comprises the steps of firstly adding an epoxy monomer, a reducing agent and water into a reaction kettle provided with a stirrer and a condensing device, stirring at the speed of 350r/min, and heating in a water bath to 60-70 ℃; then preparing a mixed solution of the amine modified monomer and an initiator, and dropwise adding the mixed solution into the reaction kettle for 1.5-2 hours; after the mixed solution is dripped, reacting at constant temperature for 1-2 hours, naturally cooling to room temperature, adding a neutralizing agent, and discharging to obtain the water-based epoxy resin; and then putting the obtained waterborne epoxy resin and the polyether amine curing agent into a reaction kettle, uniformly stirring, standing and curing for 15-20 minutes to obtain an epoxy composite monomer, adding water until the total mass is 1000 parts to obtain an epoxy composite monomer aqueous solution, and coating the epoxy composite monomer aqueous solution on a wet base surface to improve the acting force between the concrete and the wet base surface. The preparation method has the advantages of simple preparation process, excellent product performance, good stability and wide adaptability.)

1. A method for modifying a wet basal plane of aluminum sulfate cement by using hydrophilic micromolecular epoxy composite resin is characterized by sequentially comprising the following operation steps of:

the method comprises the following steps: adding 96-112 parts of epoxy monomer, 0.5-3.4 parts of reducing agent and water into a reaction kettle provided with a stirrer and a condensing device by mass fraction, stirring at the speed of 350r/min, and heating to 60-70 ℃ in a water bath;

step two: preparing a mixed solution of 64-93 parts of amine modified monomer and 1.67-3.38 parts of initiator, and dropwise adding the mixed solution into a reaction kettle for 1.5-2 hours; after the mixed solution is dripped, reacting at constant temperature for 1-2 hours, naturally cooling to room temperature, adding 4-10 parts of neutralizing agent, and discharging to obtain the water-based epoxy resin;

step three: putting the obtained waterborne epoxy resin and 32-47 parts of polyether amine curing agent into a reaction kettle, uniformly stirring, standing and curing for 15-20 minutes to obtain an epoxy compound, adding water until the total mass is 1000 parts to obtain an epoxy compound aqueous solution, and coating the epoxy compound aqueous solution on a wet base surface to improve the acting force between concrete and the wet base surface.

2. The method for modifying the wet base surface of the aluminum sulfate salt cement by using the hydrophilic small molecule epoxy composite resin as claimed in claim 1, wherein the method comprises the following steps: the amine modified monomer is p-aminobenzoic acid.

3. The method for modifying the wet base surface of the aluminum sulfate salt cement by using the hydrophilic small molecule epoxy composite resin as claimed in claim 1, wherein the method comprises the following steps: the epoxy monomer is ethylene glycol diglycidyl ether.

4. The method for modifying the wet base surface of the aluminum sulfate salt cement by using the hydrophilic small molecule epoxy composite resin as claimed in claim 1, wherein the method comprises the following steps: the reducing agent is any one or more of sodium hydrosulfite, ascorbic acid, sodium formaldehyde sulfoxylate, maltodextrin, sodium hydrosulfite and sodium metabisulfite.

5. The method for modifying the wet base surface of the aluminum sulfate salt cement by using the hydrophilic small molecule epoxy composite resin as claimed in claim 1, wherein the method comprises the following steps: the initiator is any one or more of ammonium persulfate, azobisisobutyronitrile, diisopropyl peroxydicarbonate, benzoyl peroxide, di-tert-butyl peroxide and dicyclohexyl peroxydicarbonate.

6. The method for modifying the wet base surface of the aluminum sulfate salt cement by using the hydrophilic small molecule epoxy composite resin as claimed in claim 1, wherein the method comprises the following steps: the chain transfer agent is any one or more of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and mercaptopropanol.

7. The method for modifying the wet base surface of the aluminum sulfate salt cement by using the hydrophilic small molecule epoxy composite resin as claimed in claim 1, wherein the method comprises the following steps: the neutralizing agent is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethanolamine, diethanolamine, triethanolamine and triisopropanolamine.

8. The method for modifying the wet base surface of the aluminum sulfate salt cement by using the hydrophilic small molecule epoxy composite resin as claimed in claim 1, wherein the method comprises the following steps: the polyether amine curing agent is self-made polyether amine.

9. The method for modifying the aluminum sulfate salt cement moist base surface by using the hydrophilic small molecule epoxy composite resin as claimed in claim 1, wherein the preparation of the polyether amine curing agent sequentially comprises the following operation steps:

the method comprises the following steps: adding 109 parts of acrylic acid, 95 parts of 3-methyl-2-butene-1-amine and 0.6 part of a composition of p-benzoquinone and 4,4' -dialkylbiphenyl in a mass ratio of 1:2 into a reaction kettle with a stirrer; heating to 94 ℃ by adopting an oil bath, and reacting for 1h to obtain an amide monomer;

step two: adding the prepared 198 parts of amide monomer and 100 parts of allyloxypropanol into a reaction kettle provided with a stirrer, and heating to 83 ℃ in a water bath; preparing 112 parts of allyloxypropanol and water into solution A, preparing 2.79 parts of a composition of ammonium persulfate and di-tert-butyl peroxide in a mass ratio of 3:2, 8 parts of a composition of mercaptopropionic acid and mercaptopropanol in a mass ratio of 1:4 and water into solution B, and dropwise adding A, B into a reaction kettle by using a dropwise adding pump, wherein the dropwise adding of the solution A is carried out for 1.5 hours, and the dropwise adding of the solution B is carried out for 2 hours; after the A, B solution is dripped, the temperature is kept for 2 hours to prepare polyamine ether solution; and supplementing water to 1000 parts.

Technical Field

The invention belongs to the technical field of building materials, and particularly relates to a method for modifying a wet basal plane of aluminum sulfate cement by using hydrophilic micromolecule epoxy composite resin.

Background

The epoxy resin coating has good mechanical property and durability, so the epoxy resin coating plays an important role in the coating industry. However, the traditional solvent-based epoxy coating contains a large amount of organic solvent, which brings harm to ecological environment and human beings, so that the water-based epoxy coating is a necessary trend for the development of epoxy coatings.

Patent CN104478342A discloses a wet base layer treating agent, which is composed of a component a and a component B, wherein the component A, B comprises the following raw materials by weight percent: 50-80% of emulsified asphalt, 10-40% of modified emulsion and 1-5% of auxiliary agent; and B component: 50-70% of cement, 10-35% of graded sand, 10-30% of filler and 1-5% of auxiliary agent. The wet base surface treatment agent has the advantages of quick drying, low price, good waterproofness, strong sealing capability and the like, and experiments prove that the surface drying time of the wet base surface treatment agent is 13-15 minutes. The invention is mainly applied to basement of buildings, road and bridge surfaces and wet base surfaces of tunnels for base layer treatment, and can improve the construction adaptability of self-adhesive coiled materials, SBS modified asphalt coiled material agent polymer coiled materials and the wet base surfaces.

The invention relates to the technical field of epoxy compositions, in particular to an epoxy composition which can improve the strength and the waterproof performance of a concrete base and can be used on a wet surface and a preparation method thereof, and the epoxy composition comprises a main agent A component and a curing agent B component, wherein the main agent A component comprises the following raw materials in parts by weight: 80-90 parts of hydrogenated bisphenol A resin, 2-3 parts of penetrating agent, 0.5-2 parts of dispersing agent, 0.5-2 parts of flatting agent, 0.5-2 parts of coupling agent, 5-8 parts of silicon dioxide, 6-8 parts of aluminum oxide and 20-30 parts of diluting agent. The epoxy composition can improve the strength of the surface of a concrete structure, enhance the compactness and the waterproofness of the surface of the structure and prolong the service life of the concrete structure; and the water-containing humidity of the surface of the concrete structure is not required, the environment is protected, no toxic substance and odor are discharged, and no harm is caused to human bodies.

The patent CN108753105A discloses a primer suitable for a wet base surface and a preparation method thereof, and the invention relates to a primer suitable for a wet base surface and a preparation method thereof, wherein the primer comprises a base material and a curing agent; the base material comprises epoxy resin, epoxy active diluent, silicon micropowder and talcum powder; the curing agent comprises an underwater pleasant curing agent, an active diluent, nano calcium carbonate and an adhesion strength promoter; the primer has the advantages of novel formula, simple preparation process, convenient and quick construction, strong permeability, safe and nontoxic use, no heavy metal raw material harmful to human bodies, more environment-friendly coating and accordance with the requirement on environmental protection. Meanwhile, the method also has the advantages of solving the problem that the construction bonding of the concrete wet base surface is not firm due to the pouring of polyurethane elastomer or other polyurethane materials due to water vapor.

Different from the patents, the invention provides a method for modifying a wet basal plane of aluminum sulfate cement by using hydrophilic micromolecule epoxy composite resin, the invention takes epoxy resin as a raw material, but the traditional epoxy resin is oil-soluble substance and is insoluble in water, so a large amount of organic solvent is required to be prepared during use, and the organic solvent has great influence on environment and ecology, therefore, the amine monomer is used for modifying the epoxy resin to form the water-based epoxy resin, the water-based epoxy resin has good hydrophilic performance, water can be used as a solvent, the adhesion effect is strong when the epoxy resin is used between the wet basal planes, and the interface performance of the wet basal planes can be improved.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a method for modifying a wet basal plane of aluminum sulfate salt cement by using hydrophilic micromolecular epoxy composite resin. The preparation method has the advantages of simple preparation process, excellent product performance, good stability and wide adaptability.

The invention aims to provide a water-based epoxy resin for modifying a damp base surface.

The technical scheme of the invention is as follows:

a method for modifying a wet basal plane of aluminum sulfate cement by using hydrophilic micromolecular epoxy composite resin is characterized by sequentially comprising the following operation steps of:

the method comprises the following steps: adding 96-112 parts of epoxy monomer, 0.5-3.4 parts of reducing agent and water into a reaction kettle provided with a stirrer and a condensing device by mass fraction, stirring at the speed of 350r/min, and heating to 60-70 ℃ in a water bath;

step two: preparing a mixed solution of 64-93 parts of amine modified monomer and 1.67-3.38 parts of initiator, and dropwise adding the mixed solution into a reaction kettle for 1.5-2 hours; after the mixed solution is dripped, reacting at constant temperature for 1-2 hours, naturally cooling to room temperature, adding 4-10 parts of neutralizing agent, and discharging to obtain the water-based epoxy resin;

step three: putting the obtained waterborne epoxy resin and 32-47 parts of polyether amine curing agent into a reaction kettle, uniformly stirring, standing and curing for 15-20 minutes to obtain an epoxy compound, adding water until the total mass is 1000 parts to obtain an epoxy compound aqueous solution, and coating the epoxy compound aqueous solution on a wet base surface to improve the acting force between concrete and the wet base surface.

Further, the amine modified monomer is p-aminobenzoic acid.

Further, the epoxy monomer is ethylene glycol diglycidyl ether.

Further, the reducing agent is any one or more of sodium hydrosulfite, ascorbic acid, sodium formaldehyde sulfoxylate, maltodextrin, sodium bisulfite and sodium metabisulfite.

Further, the initiator is any one or more of ammonium persulfate, azobisisobutyronitrile, diisopropyl peroxydicarbonate, benzoyl peroxide, di-tert-butyl peroxide and dicyclohexyl peroxydicarbonate.

Further, the chain transfer agent is any one or more of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and mercaptopropanol.

Further, the neutralizing agent is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethanolamine, diethanolamine, triethanolamine and triisopropanolamine.

Further, the polyether amine curing agent is self-made polyether amine.

Further, the preparation of the polyether amine curing agent sequentially comprises the following operation steps:

the method comprises the following steps: adding acrylic acid, 3-methyl-2-butene-1-amine and a composition of p-benzoquinone and 4,4' -dialkylbiphenyl in a mass ratio of 1:2 into a reaction kettle with a stirrer; heating to 90-87 ℃ by adopting an oil bath, and reacting for 1-2h to obtain an amide monomer;

step two: adding the prepared amide monomer and allyloxypropanol into a reaction kettle provided with a stirrer, and heating to 83 ℃ in a water bath; preparing allyloxypropanol and water into solution A, preparing a composition of ammonium persulfate and di-tert-butyl peroxide in a mass ratio of 3:2, a composition of mercaptopropionic acid and mercaptopropanol in a mass ratio of 1:4 and water into solution B, and dropwise adding A, B into a reaction kettle by using a dropwise adding pump, wherein the dropwise adding of the solution A is performed for 1.5 hours, and the dropwise adding of the solution B is performed for 2 hours; after the A, B solution is dripped, the temperature is kept for 2 hours to prepare polyamine ether solution; and supplementing water to 1000 parts.

The epoxy composite monomer aqueous solution for modifying a wet base surface is prepared by polymerizing the following components, wherein the total mass of the raw materials is 1000 parts, and the components comprise:

96-112 parts of epoxy monomer;

64-93 parts of amine modified monomer;

0.5-3.4 parts of a reducing agent;

1.67-3.38 parts of an initiator;

4-8 parts of a chain transfer agent;

4-10 parts of a neutralizing agent;

32-47 parts of a polyether amine curing agent;

the balance of water.

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

1. according to the invention, the epoxy resin is modified by using the amine modifier, the hydrophilic group of the hydrophilic monomer reacts with part of active epoxy groups on the epoxy resin to cause ring-opening reaction, the amino hydrophilic group is introduced into the epoxy resin molecules, and the epoxy resin molecules form a partially cross-linked structure, so that the coupling effect of the epoxy resin is improved.

2. According to the invention, the epoxy resin is cured by adopting the polyether amine curing agent, so that molecules of the epoxy resin form a more stable three-dimensional cross-linked network, the cured epoxy resin has better bonding strength, the physical and mechanical properties are improved, and the epoxy resin has better chemical erosion resistance and thermal stability.

Detailed Description

The applicant will make further detailed descriptions of technical solutions and advantages of the present invention with reference to specific examples, but it should be understood that the following examples should not be construed as limiting the scope of the claims of the present application in any way.

Example 1: preparation of polyetheramine curing agent

The method comprises the following steps: a reaction vessel equipped with a stirrer was charged with 109 parts of acrylic acid, 95 parts of 3-methyl-2-buten-1-amine and 0.6 part of a composition of p-benzoquinone and 4,4' -dialkylbiphenyl in a mass ratio of 1: 2. Heating to 94 ℃ by adopting an oil bath, and reacting for 1h to obtain the amide monomer.

Step two: the obtained 198 parts of amide monomer and 100 parts of allyloxypropanol were charged into a reaction vessel equipped with a stirrer and heated to 83 ℃ in a water bath. Preparing 112 parts of allyloxypropanol and water into solution A, preparing 2.79 parts of a composition of ammonium persulfate and di-tert-butyl peroxide in a mass ratio of 3:2, 8 parts of a composition of mercaptopropionic acid and mercaptopropanol in a mass ratio of 1:4 and water into solution B, and dropwise adding A, B into a reaction kettle by using a dropwise adding pump, wherein the dropwise adding of the solution A is performed for 1.5 hours, and the dropwise adding of the solution B is performed for 2 hours. After the A, B solution is added, the solution is kept warm for 2 hours to obtain polyamine ether solution. And supplementing water to 1000 parts.

Example 2

The epoxy composite monomer aqueous solution is prepared by polymerizing the following components, wherein the total mass of the raw materials is 1000 parts, and the components comprise:

109 parts of ethylene glycol diglycidyl ether;

86 parts of p-aminobenzoic acid;

3.2 parts of a composition of sodium bisulfite and sodium metabisulfite with the mass ratio of 3: 1;

2.39 parts of a composition of ammonium persulfate and azobisisobutyronitrile in a mass ratio of 3: 1;

7 parts of a composition of mercaptopropionic acid and mercaptopropanol in a mass ratio of 1: 4;

6 parts of a composition of diethanolamine and triethanolamine in a mass ratio of 1: 2;

40 parts of a polyether amine curing agent;

the balance of water.

A method for modifying a wet basal plane of aluminum sulfate cement by using hydrophilic micromolecular epoxy composite resin sequentially comprises the following operation steps:

the method comprises the following steps: 3.2 parts of a composition of sodium bisulfite and sodium metabisulfite and water in a mass ratio of 3:1 are added into a reaction kettle provided with a stirrer and a condensing device, stirred at a speed of 350r/min and heated to 63 ℃ in a water bath.

Step two: 109 parts of allyl glycidyl ether, 86 parts of p-aminobenzoic acid, 7 parts of a composition of mercaptopropionic acid and mercaptopropanol in a mass ratio of 1:4 and 2.39 parts of a composition of ammonium persulfate and di-tert-butyl peroxide in a mass ratio of 3:2 are prepared into a mixed solution, and the mixed solution is dropwise added into a reaction kettle for 1.5 hours. And after the mixed solution is dropwise added, reacting at a constant temperature for 1.7 hours, naturally cooling to room temperature, adding 6 parts of a composition of diethanolamine and triethanolamine in a mass ratio of 2:3, and discharging to obtain the water-based epoxy resin.

Step three: and putting the obtained waterborne epoxy resin and 40 parts of polyether amine curing agent into a reaction kettle, stirring for 5 minutes until the mixture is uniformly stirred, and standing and curing for 15 minutes. And (3) obtaining an epoxy composite monomer, supplementing water until the total mass is 1000 parts, obtaining an epoxy composite monomer aqueous solution, and coating the epoxy composite monomer aqueous solution on a damp base surface to improve the acting force between the concrete and the damp base surface.

The methods of examples 3 to 7 are the same as those of example 2, and the differences in the raw material components are shown in Table 1, and the differences in the process parameters are shown in Table 2.

Table 1 is a comparative table of the differences of the components in examples 2 to 7 of the present invention

Table 2 is a comparison table of differences of process parameters in examples 2 to 7 of the present invention

And (3) detecting data:

the hydrophilic epoxy resin (epoxy composite monomer aqueous solution) prepared in the embodiment of the invention is coated on a wet basal plane to modify the wet basal plane, and the following table is obtained by detection. (the wet basal plane bond strength was measured according to GB/T16777-2008).

Table 3 is a table of the bonding strength between the high concrete and the wet base after the epoxy composite monomer aqueous solution prepared in examples 2 to 7 of the present invention is used to modify the wet base

According to the above table, the hydrophilic epoxy resin prepared by the invention has good bonding strength under the condition of high humidity of a wet base surface, the surface drying time and the actual drying time are shorter than those of the conventional epoxy resin, the construction efficiency can be greatly improved in the construction, the bonding strength of the wet base surface is higher, the falling is not easy, and the durability is good.

The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.