KR102117503B1 - Composition for manufacturing multiple synthetic polymers for mortar and concrete and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a composition for preparing a multiple synthetic polymer for mortar and concrete and a method for preparing the same and, more particularly, to a composition for preparing a multiple synthetic polymer for mortar and concrete and a method for preparing the same, which can induce a polymer main chain and an anionic functional group by a primary polymerization reaction during a polymerization reaction, neutralize heavy metal cationic particles of a cement surface particle and maximally increase cement miscibility in order to selectively enhance adhesive strength, water resistance and abrasion resistance while maintaining an appropriate compressive strength of concrete compared to an existing styrene-butadiene synthetic polymer, and which can also implement a polymer main chain and a cationic functional group by a secondary polymerization reaction, and bind with an anionic functional group on a surface of fine aggregates and coarse aggregates during mixing concrete, thereby achieving a more dense concrete structure with higher void filling efficiency.

Description

Composition and manufacturing multiple synthetic polymers for mortar and concrete and method for manufacturing the same}

The present invention relates to a composition for preparing a multi-synthetic polymer for mortar and concrete, and a method for manufacturing the same, more specifically, to improve adhesion strength, water resistance, and abrasion resistance while maintaining appropriate compressive strength of concrete compared to an existing styrene-butadiene synthetic polymer. During the polymerization reaction, the polymer main chain and anionic functional groups are induced by the primary polymerization to neutralize the heavy metal cation particles of the cement surface particles, and the cement miscibility can be maximized, and the polymer main chain and cations by the secondary polymerization reaction It relates to a composition for preparing a multi-synthetic polymer for concrete and a mortar, which improves pore filling efficiency with a denser concrete structure by combining with an anionic functional group on the surface of fine aggregate and coarse aggregate when adding concrete.

In general, the fast-hard or rough-hard cement-based composition is mainly used for pavement and repair of concrete-based roads, bridges, structures, buildings, ports, and the like.

At this time, in order to improve the properties of the concrete before and after curing, admixture is used as a material added in addition to cement, water and aggregate.

These admixtures are intended to improve work performance or freeze-thaw resistance, or to obtain a strong water-reducing effect and a significant increase in strength, or to improve the fluidity of concrete, or to increase salt-resistance resistance and to suppress foaming or to prevent viscosity. Various materials are used, such as improving the cohesive action to prevent material separation, and a polymer is typical.

In particular, in the case of concrete pavement and bridge pavement, styrene and butadiene are used as main monomers, and emulsion polymerization copolymer synthetic latex that crosslinks through a vacuum or sealed high-pressure reactor is mainly used. In the case of this synthetic latex, compatibility with cement is used. Because of the poor sex, a large amount of hydrophilic emulsifiers must be used to solve this.

However, due to this, the dispersion and storage stability of the latex itself is poor, resulting in a phase separation phenomenon of latex particles during long-term storage, resulting in poor processing, and the use of such defective materials results in cement miscibility, pot life, and plastic cracks. ), And there is a problem that a deviation occurs in the waterproofness, strength and durability of each installed part.

In addition, since the admixture of the cement surface particles is inferior, the admixture with the anionic functional groups on the surfaces of fine aggregates and coarse aggregates decreases when mixing concrete, resulting in poor concrete structure and low internal pore filling efficiency. Difficulties exist in securing them.

Domestic registered patent No. 10-1355400 (2014.01.20.), 'Super-hard cement concrete composition with improved durability and road pavement maintenance method using the same' U.S. Patent No. 4710526 (1987.12.01.), 'Alkaline curing emulsions for use in cement admixtures'

The present invention was created to solve the above-mentioned problems in the prior art as described above, and it is possible to selectively improve adhesion strength, water resistance, and abrasion resistance while maintaining proper compressive strength of concrete compared to existing styrene-butadiene synthetic polymers. During the polymerization reaction, the polymer main chain and the anionic functional group are induced by the primary polymerization reaction to neutralize the heavy metal cation particles of the cement surface particles, and the cement miscibility can be maximized, and the polymer main chain and the cationic functional group by the secondary polymerization reaction The main objective is to provide a composition for manufacturing a composite composition for multi-synthetic polymers for concrete and a mortar that has a more compact and more effective pore filling efficiency by combining with anionic functional groups on the surface of fine aggregate and coarse aggregate when mixing concrete. .

The present invention as a means for achieving the above object, in a composition for making multiple synthetic polymers for mortar or concrete; The composition for preparing the synthetic polymer is benzoyl peroxide 0.1-0.3% by weight, dodecyl benzene sulfate 0.1-0.5% by weight, ethyl prop-2-enoate 30 -50 wt%, methyl 2-methyl prop-2-enoate 1.0-20 wt%, ethenyl acetate 20-40 wt%, butyl prop-2- 10-30 wt% of butyl prop-2-enoate, 1.0-5.0 wt% of prop-2-enoic acid and tertiary-butyl hydroperoxide 0.1 It provides a composition for preparing multiple synthetic polymers for mortar or concrete, characterized in that it contains ~ 0.5% by weight.

In addition, the present invention in a method for producing a multi-synthetic polymer for mortar or concrete using the composition for preparing a synthetic polymer described above; Ethylene emulsifier including benzoyl peroxide, dodecyl benzene sulfate and half of the reaction initiator are added to the primary monomer including ethyl prop-2-enoate and methyl 2-methylprop-2-enoate to initiate the primary polymerization reaction. Step 1; To the primary polymerization reaction product obtained through the first step, a second monomer including ethenyl acetate, butyl prop-2-enoate, and prop-2-enoic acid, and the remaining half of the emulsifier and reaction initiator are added, and 2 A second step of conducting a secondary polymerization reaction; A third method of terminating the polymerization reaction by introducing tertiary-butyl hydroperoxide into the secondary polymerization reaction product obtained through the second step is also provided. .

The present invention induces a polymer main chain and an anionic functional group by the primary polymerization reaction during polymerization to induce cement, while maintaining the appropriate compressive strength of concrete compared to the existing styrene-butadiene synthetic polymer while selectively improving the adhesion strength, water resistance, and abrasion resistance. It is possible to neutralize the heavy metal cation particles of the surface particles, to increase the cement miscibility as much as possible, and to give the polymer main chain and cationic functional groups by the secondary polymerization reaction to combine concrete with the anionic functional groups on the fine aggregate and coarse aggregate surfaces when mixing concrete. The structure is more compact and the effect of increasing the void filling efficiency can be obtained.

Hereinafter, a preferred embodiment according to the present invention will be described in more detail.

The present invention is ethyl prop-2-enoate (ethyl prop-2-enoate), methyl 2-methylprop-2-enoate (methyl 2-methyl prop-2-enoate), ethenyl acetate for cement mortar or concrete ( Ethyl acetate), butyl prop-2-enoate, prop-2-enoic acid (prop-2-enoic acid) copolymerization of multiple monomers such as anionic functional groups on the surface of fine aggregate and coarse aggregate It provides an acrylic synthetic polymer capable of achieving a high density of concrete structure by increasing the bonding property with and increasing the void filling efficiency to realize uniform high quality concrete.

To this end, the composition for preparing multiple synthetic polymers for mortar and concrete according to the present invention comprises 0.1-0.3% by weight of benzoyl peroxide, 0.1-0.5% by weight of dodecyl benzene sulfate, and ethyl prop-2- 30-50% by weight of ethyl prop-2-enoate, 1.0-20% by weight of methyl 2-methyl prop-2-enoate, ethenyl acetate 20-40 wt%, butyl prop-2-enoate 10-30 wt%, prop-2-enoic acid 1.0-5.0 wt% and tertiary- It is composed of 0.1 to 0.5% by weight of butyl hydroperoxide.

At this time, benzoyl peroxide is added as a reaction initiator, and dodecyl benzene sulfate is added as an emulsifier.

In addition, ethyl prop-2-enoate and methyl 2-methylprop-2-enoate are primary monomers, ethenyl acetate, butyl prop-2-enoate and prop-2-. Enoic acid (prop-2-enoic acid) is added as a secondary monomer.

In addition, tertiary-butyl hydroperoxide is added as a reaction terminator.

Here, the ethyl prop-2-enoate (molecular weight 100.1, solubility 1.5g / 100ml, Tg -24 ° C, boiling point 100 ° C) is for giving and controlling softness of the inner core film of the polymerized synthetic polymer particles As for the improvement and control of the flexural strength of the polymer-modified concrete, the amount used is 30-50% by weight when considering the polymerization rate of methyl 2-methylprop-2-enoate of the polymer main chain.

At this time, if added to less than 30% by weight, the ductility of the concrete is insufficient, and if it exceeds 50% by weight, the required compressive strength of the concrete is reduced, so it should be limited to the above range.

And, the methyl 2-methylprop-2-enoate (CH ₂ C (CH ₃ ) COOCH ₃ , molecular weight 100.13, solubility 1.6g / 100ml (20 ℃), Tg 105 ℃, boiling point 100.5 ℃) is polymerized It is possible to improve and control the compressive strength of polymer-modified concrete for imparting stiffness of the inner core film of synthetic polymer particles and enhancing abrasion resistance of the film, and the amount used is the polymerization rate of the polymer main chain with ethyl prop-2-enoate. Considering, 1.0-20% by weight is preferred.

At this time, if the amount used is less than 1.0% by weight, it is excessively softened, and when it exceeds 20% by weight, the stiffness of the polymer film and concrete increases, resulting in an increase in the breaking fatigue due to flow due to wind speed and traffic load, such as a suspension bridge. Since the risk of cracking and breakage of the package increases, it should be limited to the above range.

In addition, the ethenyl acetate (molecular weight 86.09, solubility 50ml / 1g (20 ° C), Tg 28, boiling point 72.7 ° C) reinforces the rigidity of the outer film of the polymerized synthetic polymer particles, crosslinking of the main chain and film Increases the tensile strength of Therefore, it maintains tensile strength between polymer-cement and polymer-aggregate due to the traffic volume vibration of the polymer-concrete, and improves cross-sectional fracture resistance.

At this time, if the amount of use exceeds 40% by weight, it is disadvantageous by increasing the rigidity of the synthetic polymer film, so it is important to adjust the amount of use to 40% by weight or less.

In addition, the butyl prop-2-enoate (CH ₂ CHCOOC ₄ H ₉ , molecular weight 128.17, solubility 0.14g / 100ml (20 ℃), Tg -54 ℃, boiling point 145 ℃) is a double structure of synthetic polymer particles It gives the ductility of the outer film, is effective in selectively increasing the adhesion strength of the polymer-modified concrete, and improves the adhesion strength of the synthetic polymer-mixed concrete to the deterioration and deterioration of the slab for bridge repair.

Therefore, the copolymerization ratio with ethenyl acetate is preferably 10-30% by weight, and if the amount of use exceeds 30% by weight, the ductility of the polymerized synthetic polymer film increases, so that the strength of concrete decreases, so it should be added below. .

In addition, the prop-2-enoic acid (CH ₂ CHCOOH, molecular weight 72.06, solubility 100g / 100ml (25 ℃), boiling point 141 ℃, melting point 14 ℃) is an anionic functional group in the primary polymerization polymer of the polymerization polymer Imparted, thereby neutralizing the surface of the cement particles having a large amount of cationic surface functional groups to promote dispersion and cement miscibility.

In addition, it serves as a dispersing agent to alleviate cement and concrete entanglement caused by fine and fine particles on fine and coarse aggregate surfaces. Therefore, the amount of use is preferably about 1-5% by weight, and when it exceeds 5% by weight, the effect on the particle size, viscosity, and pH of the synthetic polymer becomes large, so that the desired physical properties of the synthetic polymer cannot be obtained, so 5% by weight or less Should be added as

In addition, in the present invention, an interfacial separation inhibitor may be further added to 100 parts by weight of the synthetic polymer composition to suppress interfacial separation and prevent phase separation.

In this case, the interfacial separation inhibitor is 10 parts by weight of sodium polyacrylate, 5 parts by weight of methyl salicylate, 10 parts by weight of ethyl acrylate, 15 parts by weight of 3-hydroxy toluene, 5 parts by weight of dimethylol propionic acid and boron trifluoride amine complex salt It may be 5 parts by weight.

At this time, sodium polyacrylate is added because it has excellent buffering properties and good dispersibility because of its gelling properties, and excellent viscosity.

And, methyl salicylate is a colorless liquid with a specific gravity of 1.18, a boiling point of 223 ° C, and a melting point of -9 ° C, which is added to increase emulsification and softening properties.

In addition, ethyl ester of acrylic acid is added to increase the cohesiveness while controlling the viscosity and suppress blooming.

In addition, 3-hydroxytoluene increases the surface roughness by imparting a functional group to the surface, and through this, the increased surface roughness performs a kind of anchor or wedge function, thereby providing a strong fixing force so that the layers are not easily separated.

In addition, dimethylolpropionic acid is for introducing a hydrophilic group to mix well, and a boron trifluoride amine complex salt is added to maintain stable adhesive strength and chemical resistance.

A method for preparing a multi-synthetic polymer for mortar and concrete according to the present invention using this composition will be described.

First, the first polymerization reaction is initiated by introducing half of the emulsifier and reaction initiator including benzoyl peroxide and dodecyl benzene sulfate into the primary monomer including ethyl prop-2-enoate and methyl 2-methylprop-2-enoate. The first step is performed.

Then, a second monomer including ethenyl acetate, butyl prop-2-enoate, and prop-2-enoic acid and the remaining half of the emulsifier and reaction initiator are added to the primary polymerization reaction product obtained through the first step. The second step of proceeding the secondary polymerization reaction is performed.

Then, tertiary-butyl hydroperoxide is added to the secondary polymerization reaction product obtained through the second step to terminate the polymerization reaction.

Here, the multiple synthetic polymer for mortar or concrete according to the present invention is [ethyl prop-2-enoate]-[methyl 2-methylprop-2-enoate]-[ethenyl acetate]-[butyl prop as the main monomer. Since it is an emulsion polymerization of synthetic polymers containing 5 types of monomers such as -2-enoate]-[prop-2-enoic acid], uniform and accurate reactions can be induced by preparing and injecting them in the form of each composition before polymerization. .

For example, it is important to quantify each of the emulsifier and the reaction initiator composition, the first-stage monomer composition for the first-stage polymerization, the second-stage monomer composition, and the reaction termination composition, and then sequentially pass the polymerization to the reactor.

As described above, the polymerization of the polymer main chain can be uniformly induced by dividing the monomer composition into two types of the primary and secondary compositions using five types of monomers into the reactor in advance, and reducing the quality change of the polymer that has been polymerized as much as possible. It is effective in maximizing the quality uniformity, and by inducing the polymer main chain and anionic functional group by the primary polymerization reaction during polymerization, it is possible to neutralize heavy metal cation particles of the cement surface particles and maximize cement miscibility.

In addition, the polymer main chain and the cationic functional group by the secondary polymerization reaction are given to combine with the anionic functional groups on the surface of the fine aggregate and coarse aggregate when mixing concrete, thereby obtaining a more concrete structure and filling the internal voids. It is possible to reduce the effect on the mixing water and pot life due to the aggregate quality deviation caused by the aggregate source of the fine aggregate and coarse aggregate, which is effective not only in producing concrete of uniform quality, but also in the existing styrene and butadiene synthetic polymer modified concrete It is advantageous in terms of cost reduction because it can reduce the amount of use required.

In particular, it is preferable to raise the reactor temperature to 80 ° C during the first polymerization and proceed for 4 hours, and after 4 hours of the reaction, proceed to the second polymerization reaction for 4 hours and terminate the reaction.

In addition, after the first step, before the start of the second step, the above-described interface separation inhibitor may be further added, and then the second step may be performed.

In addition, in the third step, a water-neutralization inhibitor may be further added.

That is, before terminating the polymerization, 15 parts by weight of sodium citrate, 15 parts by weight of ferrous sulfate (FeSO ₄ .7H ₂ O), 5 parts by weight of N, N-dimethylethanolamine, based on 100 parts by weight of the synthetic polymer composition, A further waterproofing-neutralization inhibitor composed of 10 parts by weight of oleic acid may be added and mixed to cause secondary polymerization to terminate polymerization.

In this case, sodium-citrate (Na-citrate: Na ₃ C ₆ H ₅ O ₇ ) is added to form a waterproof complex, and ferrous sulfate (FeSO ₄ .7H ₂ O) has a pH of nitrate or hydrochloride upon dissolution. Because it is higher than that, it is possible to prevent the neutralization of concrete without adding a pH adjuster (Na ₂ CO ₃ , K ₂ HPO ₄ , KH ₂ PO _4, etc.) separately by adjusting the pH to a weak base region (7 ~ 9). It must be accurately weighed and formulated. Only then, the iron-citrate chelate compound can be smoothly generated to have a uniform waterproof structure having a dense structure.

In addition, N, N-dimethylethanolamine (N, NDimethylethanol amine) is added to suppress layer separation at the interface while anchoring between cracks by enhancing adhesion, that is, adhesion.

In addition, oleic acid is added to contribute to stabilization of fixation and promote viscosity by promoting gelation after crack penetration to increase penetration.

Hereinafter, examples will be described.

[Example 1]

Synthetic polymers were prepared according to the production method of the present invention.

[Example 2]

In the same manner as in Example 1, an interface separation inhibitor was further added.

[Example 3]

In the same manner as in Example 2, a water-neutralization inhibitor was further added.

In addition, the physical properties of these synthetic polymers are shown in Table 1. For comparison, the styrene-butadiene polymer was used as Comparative Example 1.

Based on the results of Table 1, Examples 1 to 3 obtained by the production method of the present invention showed that the content of the residue after polymerization was lower than that of Comparative Example 1. These results are considered to be the result of a more stable reaction than dividing the polymerization into two stages and proceeding the reaction sequentially.

In addition, polymer mixed concrete was prepared using the polymer samples of Examples 1 to 3 and Comparative Example 1 of Table 1, and the mixing conditions are shown in Table 2 below.

In Table 2, when the slump of each concrete composition was adjusted to a range of 200 ± 50 mm to prepare a sample, Comparative Example 1 was found to require more compounding quantity than Examples 1 to 3.

In the case of Comparative Example 1, while dispersibility is secured by the type and amount of surfactant added after polymerization, Examples 1 to 3 show the repulsive force of the polymer self-copolymerized prop-2-enoic acid with cement particles. When applying Examples 1 to 3 as securing dispersibility by using, it was confirmed that the amount of compounding added during the production of concrete can be kept constant and stable production and quality of concrete can be obtained because the fluctuation width is less sensitive. .

At this time, the properties of the fast-hardening cement used in the formulation table of Table 2 are shown in Table 3 below.

According to Tables 2 and 3, the adhesion strength (KS F 2762) of concrete formed in Examples 1 to 3 and Comparative Example 1 is shown in Table 4 below.

As shown in Table 4, Examples 1 to 3 were found to have better adhesion strength by age compared to Comparative Example 1. The above results indicate that the copolymer strength of ethenyl acetate and butyl prop-2-enoate and prop-2-enoic acid forming the outer regions of the polymers of Examples 1 to 3 was significantly higher than that of the Examples. It was found to be excellent, and in particular, the higher the content of butyl prop-2-enoate, the better the adhesion strength.

In addition, the strength of the concrete, as shown in Table 5, Examples 1 to 3 were found to have higher overall compressive strength than Comparative Example 1. These results show that the bonding strength between Examples 1 to 3 and the cement particles is high, thereby improving the resistance to vertical fracture strength. In addition, the difference in strength according to age was found that the polymer particles of Examples 1 to 3 impart an internal void filling effect without interfering with the generation of a strength-expressing material such as ettringite in cement particles.

In addition, in the case of abrasion resistance, Table 6 shows that the abrasive properties of Examples 1 to 3 were less than those of Comparative Example 1, and in the formation of the bonding strength between polymers and cement particles of Examples 1 to 3 and strength-enhancing components according to age. It is believed that this is due to the dense filling effect of the pores in the concrete.

In addition, as shown in Table 7, Examples 1 to 3 were found to have higher freeze-thaw stability than Examples. The above results show that the polymers of Examples 1 to 3 fill the voids of the concrete internal structure, provide filling and waterproofing properties, and promote the generation and growth of etrinsite to have a more robust and dense internal bonding structure, resulting in concrete according to temperature changes. It has been shown to have more stable dimensional stability and stability of warming change when repeated shrinkage and relaxation of.

In addition, Examples 1 to 3, as shown in Table 8, was found to have excellent salt penetration stability compared to Comparative Example 1. The above results show that the polymers of Examples 1 to 3 do not interfere with the effect of filling the pores of the concrete internal structure with the polymer film and the generation and growth of strength-enhancing materials such as etringite. This is due to more precise results.

In addition, in order to confirm the properties of the synthetic polymer according to the present invention can also be applied to crude steel cement, it was formulated in the mixing conditions as shown in Table 9 below.

In Table 9, when the slump of each concrete composition was adjusted to be within the range of 200 ± 50 mm, a comparative example 1 was found to require more compounding quantity than Examples 1 to 3. These results showed the results of the tendency shown in Table 2 above, and the cement admixture and dispersibility of the acrylic double structure polymers of Examples 1 to 3 were superior to those of the comparative examples, thereby reducing the amount of compounding used in the mixing conditions having the same slump. At the same time, it was found to be more effective in improving the durability of concrete through reduced compounding.

And, the properties of crude steel cement are shown in Table 10 below.

Based on this, the adhesion strength of the concrete, the strength of the concrete, the abrasion resistance, the freeze-thaw resistance, and the salt penetration resistance of the concrete applied to the crude steel cement according to the present invention were tested in the same manner as the above-described method, and the above-described fast-cement cement was applied. Compared to the applied one, it showed superior characteristics over the previous one.

Claims (2)

In the composition for making multiple synthetic polymers for mortar or concrete;
The composition for preparing the synthetic polymer is benzoyl peroxide 0.1-0.3% by weight, dodecyl benzene sulfate 0.1-0.5% by weight, ethyl prop-2-enoate 30 -50 wt%, methyl 2-methyl prop-2-enoate 1.0-20 wt%, ethenyl acetate 20-40 wt%, butyl prop-2- 10-30 wt% of butyl prop-2-enoate, 1.0-5.0 wt% of prop-2-enoic acid and tertiary-butyl hydroperoxide 0.1 A composition for preparing multiple synthetic polymers for mortar or concrete, characterized in that it contains ~ 0.5% by weight.
In the method for producing a multi-synthetic polymer for mortar or concrete using the composition for preparing a synthetic polymer according to claim 1;
Ethylene emulsifier including benzoyl peroxide, dodecyl benzene sulfate and half of the reaction initiator are added to the primary monomer including ethyl prop-2-enoate and methyl 2-methylprop-2-enoate to initiate the primary polymerization reaction. Step 1;
To the primary polymerization reaction product obtained through the first step, a second monomer including ethenyl acetate, butyl prop-2-enoate, and prop-2-enoic acid, and the remaining half of the emulsifier and reaction initiator are added, and 2 A second step of conducting a secondary polymerization reaction;
A method for preparing a multi-synthetic polymer for mortar or concrete comprising; a third step of terminating a polymerization reaction by introducing tertiary-butyl hydroperoxide into the secondary polymerization reaction product obtained through the second step.