KR20160139478A - Manufacturing method of synthetic rubber latex synthetic rubber latex manufactured by the method and ecofriendly concrete composition using the same - Google Patents
Manufacturing method of synthetic rubber latex synthetic rubber latex manufactured by the method and ecofriendly concrete composition using the same Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
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- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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Abstract
The present invention relates to a method for producing a synthetic rubber latex, a synthetic rubber latex prepared by the method, and an environmentally friendly concrete composition using the latex. More particularly, the present invention relates to a synthetic latex prepared by using the seed latex having an ultrafine particle size and a monomeric butadiene, acrylonitrile, A synthetic rubber latex is prepared by using styrene, an unsaturated carboxylic acid and various additives, and the copolymer can be prepared by a primary crosslinking by an organic crosslinking agent and a secondary crosslinking by an inorganic crosslinking agent to prepare a copolymer having a macroreticular structure , A process for producing a synthetic rubber latex, and a synthetic rubber latex produced by the process, and also provides an environmentally friendly concrete composition using the synthetic rubber latex prepared as described above.
According to the present invention, it is possible to prevent the occurrence of cracks due to early shrinkage of concrete due to the enhancement of tear strength and tensile stress due to a macroreticular structure, and to exhibit early strength by bonding with cement rapidly, and by having ultrafine particles Cement and aggregate particles are filled with a large amount of latex particles, the internal structure of the concrete is tightened to prevent the permeation of moisture from the outside, thereby improving the freeze-thaw resistance and chemical resistance as well as reducing the amount of slump In addition, the present invention has an advantage in that it has an initial particle diameter of 150 nm or less, a volatile organic compound of 50 ppm or less, Formaldehyde not detected, heavy metals (lead, cadmium, chromium, mercury) not detected, plasticizer terephthalate The use of water as a solvent and a solvent makes it possible to avoid fire danger and to be environmentally friendly, and since it exhibits the above excellent properties without using a high-pressure reactor, it is safe because there is no risk of explosion due to use of a high-pressure reactor, It is easy to operate, the reaction time is short, the productivity is high, and the product concentration is high.
Description
The present invention relates to a process for producing a synthetic rubber latex by using a seed latex having an ultrafine particle size and a monomer such as butadiene, acrylonitrile, styrene, an unsaturated carboxylic acid and various additives, To a copolymer having a macroreticular structure through secondary crosslinking by a crosslinking agent, a synthetic rubber latex prepared by the method, and an environmentally friendly concrete composition using the latex.
Currently used concrete bridge pavement and polymer cement mortar usually contain styrene butadiene latex or carboxylate styrene butadiene latex in addition to polyacrylic emulsion or ethylene vinyl acetate or epoxy resin to improve concrete performance. Concrete and mortar produced by blending according to the purpose of construction. Especially, modified concrete mixed with styrene butadiene latex excellent in dispersibility, adhesive property, waterproof property, etc. is mainly used in bridge pavement, maintenance, reinforcement, surface protection agent and bridge waterproofing In recent years, there has been a growing interest in extending service life through effective maintenance of bridges and construction structures. In developed countries, bridges and maintenance are already a major concern.
In particular, concrete has been known as a durable structural civil engineering material. However, recently, it has been required to use waste in the iron or steel industry and it has been suffering from heavy snowfall due to global warming, excessive snow removal, , Chlorides and the like, deterioration and deterioration are progressing, and maintenance and reinforcement thereof is required. In addition, the durability is weakened, which is in particular a disadvantage of poor oil resistance, heat resistance, cold resistance, chemical resistance, abrasion resistance and ozone resistance.
On the other hand,
However, the concrete to which the styrene-butadiene synthetic latex is added as described above is a cement modifier, which causes a high generation of cracks on the surface due to film formation and surface drying on the early surface due to a high addition amount of 15% The quality control is difficult.
The present invention relates to a process for producing a synthetic rubber latex by using a seed latex having an ultrafine particle size and a monomer such as butadiene, acrylonitrile, styrene, an unsaturated carboxylic acid and various additives, A method of producing a synthetic rubber latex, and a synthetic rubber latex produced by the method, which can be produced as a copolymer having a macroreticular structure through secondary crosslinking by a crosslinking agent, It is an object of the present invention to provide an environmentally friendly concrete composition using synthetic rubber latex.
The present invention relates to a method for producing a synthetic rubber latex,
(S100) a seed latex using a monomer, an anionic emulsifier, a reaction initiator, a reducing agent and distilled water;
It is preferable to use the prepared seed latex, monomer, unsaturated carboxylic acid, anionic emulsifier, amphoteric stabilizer, reaction initiator, reducing agent, electrolyte, molecular weight regulator, organic crosslinking agent, nonionic emulsifier, Preparing a base crosslinked latex (S200); And
And a step (S300) of preparing a secondary crosslinked copolymer by using the primary crosslinked base latex, inorganic crosslinking agent, crosslinking accelerator, crosslinking reinforcement, and dispersant (S300). The synthetic rubber latex prepared by this method and the environmentally friendly concrete composition using the latex are used as means for solving the problems.
Specifically, in step S100, 100 parts by weight of an anionic emulsifier (1.5 parts by weight) is added to 100 parts by weight of a monomer comprising 30 to 50% by weight of butadiene, 25 to 35% by weight of styrene, and 25 to 35% by weight of acrylonitrile. , 1.0 to 2.0 parts by weight of potassium persulfate as a reaction initiator, 0.1 to 0.3 parts by weight of sodium bisulfite as a reducing agent and 100 to 200 parts by weight of distilled water were charged into a batch reactor, Lt; 0 > C for 1 to 3 hours.
In step S200, 5 to 10 parts by weight of methyl methacrylate as an unsaturated carboxylic acid, 0.3 to 0.5 parts by weight of methacrylic acid, 100 parts by weight of acrylic acid 0.1 to 3.0 parts by weight of fumaric acid, 0.2 to 0.5 parts by weight of an anionic emulsifier, 0.1 to 0.3 parts by weight of amphoteric stabilizer, 0.5 to 1.5 parts by weight of potassium carbonate as an electrolyte, 0.1 to 0.7 parts by weight of a molecular weight modifier, 0.1 to 0.7 parts by weight of divinyl benzene as an organic crosslinking agent, 1.0 to 2 parts by weight of 2hexaethylmethylacrylate To 5.0 parts by weight of acrylamide and 1.0 to 5.0 parts by weight of acrylamide were charged into a reactor and stirred for 25 to 35 minutes to raise the internal temperature to 50 to 53 ° C.,
1 to 3 parts by weight of potassium persulfate as a reaction initiator and 0.1 to 0.3 parts by weight of sodium bisulfide as a reducing agent were added at an internal temperature of 54 to 56 ° C, 20 to 20 parts by weight of styrene and 25 to 50 parts by weight of acrylonitrile are continuously supplied for 3 to 5 hours at a constant flow rate for 1 to 3 hours, To 5 hours, 0.3 to 0.5 parts by weight of methacrylic acid, which is an unsaturated carboxylic acid, and 0.3 to 0.5 parts by weight of acrylic acid,
After the pH was adjusted to 9.5 to 11 with an aqueous solution of sodium hydroxide, 1 to 3 parts by weight of a nonylphenylether emulsifier, which is a nonionic emulsifier, and 1.0 to 2.0 parts by weight of polycarboxylic acids, And then aging and reacting in a vacuum of ~ 80 ° C for 1 to 2 hours.
In step S300, 5 to 10 parts by weight of sulfur as an inorganic crosslinking agent, 3 to 5 parts by weight of a zinc oxide dispersion, and a zinc diethyl dithocaramate dispersion as a crosslinking accelerator are added to 100 parts by weight of the base latex 1.0 to 3.0 parts by weight of a dispersion of zinc salt 2-mercaptobenzothiazole, 10 to 30 parts by weight of a carbon black dispersion as a crosslinking adjuvant, ) And 10 to 30 parts by weight of a dispersant, tamol-N (10 to 30 parts by weight), dispersed in a ball mill for 20 to 25 hours, and filtered through a filter screen of 150 to 250 mesh to prepare an aqueous dispersion and,
The dispersed aqueous solution is added to the reactor and then stirred at 60 to 80 ° C for 1 to 3 hours.
The anionic emulsifier may be selected from the group consisting of polycarboxylate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate, sodium octyl sulfate, sodium toluene sulfonate, dodecyl toluene sulfonate, potassium stearyl phosphate or potassium stearate, or a combination of two or more thereof.
The amphoteric stabilizer may be used either singly or in combination with at least one of nonylphenyl ether sulfonate or nonylphenyl ether ammonium sulfonate,
The molecular weight regulator may be selected from the group consisting of n-dodecyl mercaptan, t-dodecyl mercaptan, and n-octyl mercaptan, Is preferably used.
According to the present invention, it is possible to prevent cracking due to early shrinkage of concrete due to the enhancement of tear strength and tensile stress due to a macroreticular structure, to exhibit early strength by bonding with cement rapidly, As a large amount of latex particles are filled around the aggregate particles, the internal structure of the concrete is tightened, thereby preventing the penetration of moisture from the outside, thereby improving the freeze-thaw resistance and chemical resistance. In addition, the slump, Compression, warpage, and adhesion strength can be improved. In particular, oil resistance, heat resistance, abrasion resistance, and ozone resistance are excellent in the applicability as a package.
The present invention also relates to a process for the production of a water-insoluble, water-insoluble, water-insoluble, water-insoluble, water-insoluble, water- Pressure reactor without using a high-pressure reactor, it is safe because there is no risk of explosion due to the use of a high-pressure reactor, the production facility is simple and easy to operate, the reaction time is short and productivity is high, The effect of increasing the concentration of the catalyst is high.
FIG. 1 is a graph showing a TEM photograph (enlarged image at 20000 × magnification) of a seed latex and a result of measurement of particle size distribution of an autosizer
2 is a flowchart showing a method for producing a synthetic rubber latex according to the present invention.
Fig. 3 is a graph showing the test results of heavy metal detection test results on synthetic rubber latex according to the present invention
Fig. 4 is a graph showing the results of a TVOC emission test on a synthetic rubber latex according to the present invention
5 is a graph showing the results of T-VOC emission test on synthetic rubber latex according to the present invention
Fig. 6 is a graph showing the test results of formaldehyde detection test on synthetic rubber latex according to the present invention
The present invention relates to a method for producing a synthetic rubber latex, a synthetic rubber latex prepared by the method, and an environmentally friendly concrete composition using the same, It should be noted that the description of the other portions will be omitted so as not to disturb the gist of the present invention.
Hereinafter, a method for producing a synthetic rubber latex according to the present invention, a synthetic rubber latex prepared by the method, and an environmentally friendly concrete composition using the same will be described in detail.
FIG. 2 is a flow chart showing a method for producing a synthetic rubber latex according to the present invention. The synthetic rubber latex manufacturing method according to the present invention comprises the steps of preparing a seed latex (S100), producing a primary crosslinked base latex And a step (S300) of preparing a secondary crosslinked copolymer.
The step S100 is a step of preparing a seed latex using a monomer, an anionic emulsifier, a reaction initiator, a reducing agent, and distilled water. More specifically, the batch reactor is filled with the process water in preparation for the polymerization reaction, The process of discharging is performed three times to completely build up dissolved oxygen in the reactor. The process water is filled again and the process water is discharged with butadiene gas, and the inside of the reactor is replaced with butadiene gas. Thereafter, 1.5 to 2.5 parts by weight of an anionic emulsifier was added to 100 parts by weight of a monomer composed of 30 to 50% by weight of butadiene, 25 to 35% by weight of styrene and 25 to 35% by weight of acrylonitrile, 0.1 to 0.3 parts by weight of sodium bisulfite as a reducing agent and 100 to 200 parts by weight of distilled water, and then reacted at 90 to 110 ° C for 1 to 3 hours. As shown in Fig. 1, the physical properties of the seed latex thus prepared exhibit a total solid content of 30 to 40%, an average particle size of 300 to 500 Å, a pH of 2.0 to 4.0 and a viscosity of 20 to 50 cps.
The step S200 may be performed using the seed latex, the monomer, the unsaturated carboxylic acid, the anionic emulsifier, the amphoteric stabilizer, the reaction initiator, the reducing agent, the electrolyte, the molecular weight regulator, the organic crosslinking agent, the nonionic emulsifier, Specifically, as in step S100, dissolved oxygen in the reactor is removed, and the prepared seed latex is introduced. To 100 parts by weight of the prepared seed latex, an unsaturated
1 to 3 parts by weight of potassium persulfate as a reaction initiator and 0.1 to 0.3 parts by weight of sodium bisulfide as a reducing agent were added at an internal temperature of 54 to 56 ° C, 20 to 20 parts by weight of styrene and 25 to 50 parts by weight of acrylonitrile were continuously fed for 3 to 5 hours at a constant flow rate and reacted for 1 to 3 hours and then heated to 75 to 85 ° C., 0.3 to 0.5 parts by weight of methacrylic acid, which is an unsaturated carboxylic acid, and 0.3 to 0.5 parts by weight of acrylic acid, are added to the reactor at a time point of 90% or more, that is, 3 to 5 hours after the reaction.
When the final total solid content (TSC) was 47% or more and the conversion rate was 98% or more, the stability of the latex was improved by adjusting the PH from 2 to 4 to 9.5 to 11 with 25% sodium hydroxide aqueous solution, 1 to 3 parts by weight of a nonylphenyl ether emulsifier, which is a nonionic emulsifier, and 1.0 to 2.0 parts by weight of a high-performance delayed-type polycarboxylate are added in order to improve chemical conversion and pot life, and the mixture is aged at 75 to 80 ° C. for 1 to 2 hours And reacting to react the unreacted materials completely.
The primary crosslinked base latex exhibits a total solid content of 46 to 50%, a particle size of 1400 to 1800 Å, a gel content of 80 to 85%, a viscosity of 95 to 100 cps, a PH of 10 to 12, and a solidification amount of 0.05 to 0.07%.
Here, the anionic emulsifier used in the above process may be used alone or in combination of two or more kinds selected from polycarboxylate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium octyl sulfate, sodium toluene sulfonate, potassium stearyl phosphate or potassium stearate The amphoteric stabilizer is used either singly or in combination of two or more among ammonium nonylphenyl ether sulfonate or ammonium nonylphenyl ether sulfonate. The molecular weight adjuster is used in combination with n-dodecyl mercaptan, t-dodecyl mercaptan Mercaptane or n-octylmercaptan, alone or in combination of two or more.
On the other hand, synthetic rubber latexes such as SBR, NBR, and CR can be synthesized by emulsion polymerization of unsaturated monomers. In some cases, latex is used as a product, but in most cases, various compounding agents are added to improve physical properties . In the present invention, a high-durability cement concrete composition is prepared by preparing a copolymer latex of a copolymer having acrylonitrile, styrene and butadiene macroreticular structures which are secondarily crosslinked, and theoretically, a latex and a secondary crosslinking agent Is susceptible to electron withdrawal from methylene around the double bonds for resonance and the vulcanization of the rubber by sulfur is initiated by the removal of the methylene electrons of the rubber by the sulfur radical. Then, 'S' is added to the butadiene radical, butadiene polysulfide radical is formed, which further bonds with the butadiene radical, resulting in crosslinking of butadiene having a polysulfide bond ring.
Thus, the step S300 is a step of preparing a secondary crosslinked copolymer by using the primary crosslinked base latex, inorganic crosslinking agent, crosslinking accelerator, crosslinking adjuvant, and dispersant. Specifically, 100 parts by weight of the
On the other hand, an environmentally friendly concrete composition can be prepared by adding the synthetic rubber latex prepared as described above, and it is manufactured by mixing various well-known materials used in the concrete composition together with a synthetic rubber latex. 3], but the present invention is not limited thereto and various modifications can be made.
Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited to the examples.
1. Manufacture of seed latex
(Production Example 1)
2.0 parts by weight of an anionic emulsifier polycarboxylate, 1.5 parts by weight of a potassium persulfate as a reaction initiator, 1.5 parts by weight of a sodium bisulfite as a reducing agent, 100 parts by weight of a monomer consisting of 30% by weight of butadiene, 30% by weight of styrene and 30% by weight of acrylonitrile, And 156 parts by weight of distilled water were charged into a batch reactor and reacted at 100 DEG C for 2 hours.
(Production Example 2)
1.5 parts by weight of an anionic emulsifier polycarboxylate, 1.0 part by weight of a potassium persulfate as a reaction initiator, 1.0 part by weight of a sodium bisulfite as a reducing agent, and 0.1 part by weight of a polymerization initiator were added to 100 parts by weight of a monomer comprising 30% by weight of butadiene, 35% by weight of styrene and 35% by weight of acrylonitrile. 0.1 part by weight and 100 parts by weight of distilled water were charged into a batch reactor and reacted at 90 DEG C for 3 hours.
(Production Example 3)
2.5 parts by weight of an anionic emulsifier polycarboxylate, 2.0 parts by weight of a potassium persulfate as a reaction initiator, 2.0 parts by weight of sodium persulfate, which is a reducing agent, 100 parts by weight of a monomer comprising 50% by weight of butadiene, 25% by weight of styrene and 25% by weight of acrylonitrile, And 200 parts by weight of distilled water were charged into a batch reactor and reacted at 110 DEG C for 1 hour.
2. Manufacture of base latex
(Production Example 4)
5 parts by weight of unsaturated carboxylic acid methyl methacrylate, 0.3 part by weight of methacrylic acid, 0.3 part by weight of acrylic acid, 0.1 part by weight of itaconic acid, 0.1 part by weight of fumaric acid 0.1 part by weight, , 0.2 part by weight of an anionic emulsifier, 0.1 part by weight of nonyl phenyl ether sulfonate as a light stabilizer, 0.5 part by weight of an electrolyte potassium carbonate, 0.1 part by weight of n-dodecyl mercaptan as a molecular weight regulator, 0.1 part by weight of 2-hexylethylmethyl acrylate, and 1.0 part by weight of acrylamide were added to the reactor, and the internal temperature was raised to 53 DEG C while stirring for 30 minutes. When the internal temperature reached 55 DEG C, 1 part by weight of phosphorus persulfate and 0.1 part by weight of sodium bisulfide as a reducing agent were added to the mixture, 0 parts by weight of styrene, 10 parts by weight of styrene and 25 to 50 parts by weight of acrylonitrile were continuously introduced at a constant flow rate for 4 hours and allowed to react for 2 hours. Then, the temperature was raised to 80 캜, 0.3 to 0.5 part by weight of the acid and 0.3 to 0.5 part by weight of acrylic acid were added to the reactor. When the final TSC was 47% or more and the conversion was 98% or more, the pH was adjusted to 9.5 to 11 with an aqueous solution of sodium hydroxide, 1 part by weight of a phenyl ether emulsifier and 1.0 part by weight of a polycarboxylate as a water retarding agent were added and aged and reacted at 80 DEG C under vacuum for 1 hour.
(Production Example 5)
5 parts by weight of unsaturated carboxylic acid methyl methacrylate, 0.3 part by weight of methacrylic acid, 0.3 part by weight of acrylic acid, 0.1 part by weight of itaconic acid, 0.1 part by weight of fumaric acid 0.1 , 0.2 part by weight of an anionic emulsifier, 0.1 part by weight of nonyl phenyl ether sulfonate as a light stabilizer, 0.5 part by weight of an electrolyte potassium carbonate, 0.1 part by weight of n-dodecyl mercaptan as a molecular weight regulator, , 1.0 part by weight of 2-hexylethylmethyl acrylate and 1.0 part by weight of acrylamide were charged into the reactor, and the internal temperature was raised to 53 DEG C while stirring for 25 minutes. Then, when the internal temperature reached 54 DEG C, 1 part by weight of phosphorus persulfate and 0.1 part by weight of sodium bisulfide as a reducing agent were added to the mixture, 0 parts by weight of styrene, 10 parts by weight of styrene and 25 to 50 parts by weight of acrylonitrile were continuously introduced at a constant flow rate for 3 hours and allowed to react for 1 hour. Then, the temperature was raised to 75 占 폚 and methacrylic 0.3 to 0.5 part by weight of the acid and 0.3 to 0.5 part by weight of acrylic acid were added to the reactor. When the final TSC was 47% or more and the conversion was 98% or more, the pH was adjusted to 9.5 to 11 with an aqueous solution of sodium hydroxide, 1 part by weight of a phenyl ether emulsifier and 1.0 part by weight of a polycarboxylate as a water retarding agent were added and aged and reacted under vacuum at 75 캜 for 1 hour.
(Production Example 6)
10 parts by weight of methyl methacrylate as an unsaturated carboxylic acid, 0.5 part by weight of methacrylic acid, 0.5 part by weight of acrylic acid, 0.5 part by weight of itaconic acid, and 0.5 part by weight of fumaric acid were added to 100 parts by weight of the seed latex prepared according to Preparation Example 3, 0.5 part by weight of an anionic emulsifier, 0.3 part by weight of nonyl phenyl ether sulfonate as a photopolymer stabilizer, 1.5 parts by weight of potassium carbonate as an electrolyte, 0.7 part by weight of n-dodecyl mercaptan as a molecular weight regulator, , 5.0 parts by weight of 2-hexylethylmethyl acrylate and 5.0 parts by weight of acrylamide were charged into the reactor, and the internal temperature was raised to 50 DEG C while stirring for 35 minutes. When the internal temperature reached 56 DEG C, 3 parts by weight of phosphorus persulfate and 0.3 part by weight of sodium bisulfide as a reducing agent were added to the mixture, , 20 parts by weight of styrene and 50 parts by weight of acrylonitrile were continuously introduced at a constant flow rate for 5 hours and reacted for 3 hours and then heated to 85 캜 and reacted at 5 hours with methacrylic acid of unsaturated carboxylic acid 0.5 And 0.5 parts by weight of acrylic acid were added to the reactor. When the final TSC was 47% or more and the conversion was 98% or more, the pH was adjusted to 9.5 to 11 with an aqueous solution of sodium hydroxide and then 3 parts by weight of nonylphenyl ether emulsifier And 2.0 parts by weight of a polycarboxylate, which is a retardant for depression, were added and aged and reacted under vacuum at 80 캜 for 2 hours.
3. Manufacture of synthetic rubber latex
(Example 1)
5 parts by weight of an inorganic crosslinking agent, 3 parts by weight of a zinc oxide dispersion, 1.0 part by weight of a zinc diethyldithiocarbamate dispersion as a crosslinking accelerator, 2 parts by weight of a 2-
(Example 2)
5 parts by weight of sulfur as an inorganic crosslinking agent, 3 parts by weight of a zinc oxide dispersion, 1.0 part by weight of a zinc diethyldithiocarbamate dispersion as a crosslinking accelerator, 2 parts by weight of 2-
(Example 3)
10 parts by weight of sulfur as an inorganic crosslinking agent, 5 parts by weight of a zinc oxide dispersion, 3.0 parts by weight of a zinc diethyldithiocarbamate dispersion as a crosslinking accelerator, 2 parts by weight of a 2-mercapto 30 parts by weight of carbon black dispersion, 30 parts by weight of white carbon, and 30 parts by weight of a thallone dispersant as a dispersant were mixed and dispersed in a ball mill for 25 hours. Then, the mixture was filtered through a 250-mesh screen To prepare an aqueous dispersion solution, adding the dispersion aqueous solution into a reactor, and stirring the mixture at 60 to 80 ° C for 3 hours.
(Comparative Example 1)
SB latex (product name: JAPT-1519, Central Polytec) was used.
(Comparative Example 2)
SBR latex (product name: KSL-363, KKPC) was used.
(Comparative Example 3)
Acrylic emulsion latex (product name: sample, Nature Solution) was used.
The results of measuring the physical properties of the synthetic rubber latex according to the Examples and Comparative Examples are shown in Table 1 below.
Stability (-10 ℃ ± 1 ℃)
(weight%)
As shown in Table 1, the particle size of the seed latex according to the example of the present invention is smaller than that of the comparative example, and the final particle size decreases with an increase in the amount of the seed latex. This is because the acrylonitrile styrene monomer having high hydrophilicity and hydrophilicity at the time of synthesizing the seed latex and the emulsifier having two hydrophilic groups were prepared at a reaction temperature of 100 ° C, high-speed stirring, and high-pressure reactor. When the particle size is small, a large amount of latex particles are filled around the cement and aggregate particles, thereby improving the adhesion strength and the bending strength. As a result, it was possible to synthesize latex having high gel amount, tensile and tear strength by using first and second crosslinking polymerization method and organic and inorganic crosslinking agent for each reaction, and the elongation Butadiene content was increased. When the butadiene content was high, the glass transition temperature was lowered, the elongation was improved, and the adhesion strength was improved. In addition, the chemical resistance, oil resistance, and heat resistance are greatly increased by the increase of acrylonitrile content.
In addition, test results commissioned by the Korean Chemical Fusion Test Institute for the synthetic rubber latex in Example 1 are shown in FIGS. 3 to 6. As shown in FIGS. 3 to 6, the synthetic rubber latex according to the present invention is free from heavy metals and formaldehyde such as Pb, Cd, Hg and Cr, and TVOC 0.056 mg / m 2 · h (TVOC standard for latex , But the standard for other building materials is usually 0.1 ~ 4.0 mg / m 2 · h) and T-VOC 1.81 g / L (no T-VOC standard for latex).
4. Manufacture of concrete composition
The samples of the examples and comparative examples were tested for the mixing standard of latex mixed modifying concrete for cross-pavement, which is a standard specification of Korea Highway Corporation, and polymer cement mortar for repairing concrete structures such as KS F-4042, KS F-4919, Waterproofing agent according to [Table 2].
usage
(kg / cm 3)
Latex 3)
2) Specific gravity of 2.63, granularity of 6.87, particle size by KS F 2536
3) Example 4: Use of synthetic rubber latex according to Example 1
Example 5: Use of synthetic rubber latex according to Example 2
Example 6: Use of synthetic rubber latex according to Example 3
Example 7: Use of synthetic rubber latex according to Example 1
Comparative Example 4: Using the synthetic rubber latex according to Comparative Example 1
Comparative Example 5: Use of synthetic rubber latex according to Comparative Example 2
Comparative Example 6: Use of synthetic rubber latex according to Comparative Example 3
The slump (KS F 2402), the air content (KS F 2421), the flexural strength (KS F 2408) and the compressive strength (KS F 2405) of the modified concrete prepared by blending according to the contents of the above Table 2 were tested The results are shown in Table 3 below.
(N / mm 2 )
(N / mm 2 )
According to the contents of the above Table 3, the modified concrete according to the embodiment of the present invention is superior to the modified concrete according to the comparative example in terms of slump, flexural strength and compressive strength. Styrene-butadiene according to to 4 The use of unsaturated carboxylic acids such as methyl methacrylate, methacrylic acid and the like used in the synthesis of the latex improves physical properties such as fluidity and adhesiveness of the synthetic rubber latex, It is estimated to be good. Therefore, the present invention has the property that the properties of the modified concrete are equivalent or superior to those of the comparative example, despite the fact that the synthetic rubber latex is easily synthesized at atmospheric pressure, unlike synthesizing the synthetic rubber latex by using the high pressure reactor. Demonstrating the superiority of the invention.
The term "dispersion" used in each composition means that 1 to 80 parts by weight of each composition is dispersed in various fluids (for example, distilled water, water, various solvents, etc.) It is a well-known meaning and its degree of dispersion is already known for each composition.
As described above, the synthetic rubber latex according to the present invention, the synthetic rubber latex produced by the method, and the environmentally friendly concrete composition using the synthetic rubber latex are explained through the above-mentioned preferred embodiments and their excellence is confirmed. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the following claims.
S100: Step of producing seed latex
S200: Step of producing primary crosslinked base latex
S300: Step of producing a secondary crosslinked copolymer
Claims (7)
Preparing a seed latex using a monomer, an anionic emulsifier, a reaction initiator, a reducing agent and distilled water (S100);
The base latex prepared by using the seed latex, the monomer, the unsaturated carboxylic acid, the anionic emulsifier, the amphoteric stabilizer, the reaction initiator, the reducing agent, the electrolyte, the molecular weight regulator, the organic crosslinking agent, the nonionic emulsifier, (S200); And
A step (S300) of preparing a secondary crosslinked copolymer by using the primary crosslinked base latex, inorganic crosslinking agent, crosslinking accelerator, crosslinking reinforcement, and dispersing agent (S300).
In operation S100,
1.5 to 2.5 parts by weight of an anionic emulsifier and 1.0 to 2.0 parts by weight of a potassium persulfate as a reaction initiator are added to 100 parts by weight of a monomer composed of 30 to 50% by weight of butadiene, 25 to 35% by weight of styrene and 25 to 35% by weight of acrylonitrile 0.1 to 0.3 parts by weight of sodium bisulfite as a reducing agent and 100 to 200 parts by weight of distilled water into a batch reactor and reacting at 90 to 110 ° C for 1 to 3 hours.
In operation S200,
5 to 10 parts by weight of methyl methacrylate as an unsaturated carboxylic acid, 0.3 to 0.5 parts by weight of methacrylic acid, 0.3 to 0.5 parts by weight of acrylic acid, 0.1 to 0.5 parts by weight of itaconic acid, 0.1 to 3.0 parts by weight of fumaric acid, 0.2 to 0.5 parts by weight of an anionic emulsifier, 0.1 to 0.3 parts by weight of amphoteric stabilizer, 0.5 to 1.5 parts by weight of an electrolyte potassium carbonate, 0.1 to 0.7 parts by weight of a molecular weight modifier, 1.0 to 5.0 parts by weight of 2-hexylethylmethyl acrylate, and 1.0 to 5.0 parts by weight of acrylamide were charged into a reactor and stirred for 25 to 35 minutes while raising the internal temperature to 50 to 53 ° C.,
1 to 3 parts by weight of potassium persulfate as a reaction initiator and 0.1 to 0.3 parts by weight of sodium bisulfide as a reducing agent were added at an internal temperature of 54 to 56 ° C, 20 to 20 parts by weight of styrene and 25 to 50 parts by weight of acrylonitrile are continuously supplied for 3 to 5 hours at a constant flow rate for 1 to 3 hours, To 5 hours, 0.3 to 0.5 parts by weight of methacrylic acid, which is an unsaturated carboxylic acid, and 0.3 to 0.5 parts by weight of acrylic acid,
After the pH is adjusted to 9.5 to 11 with an aqueous solution of sodium hydroxide, 1 to 3 parts by weight of a nonyl phenyl ether emulsifier as a nonionic emulsifier and 1.0 to 2.0 parts by weight of a polycarboxylate are added. And aging and reacting the mixture for 1 to 2 hours to prepare a synthetic rubber latex.
In operation S300,
5 to 10 parts by weight of sulfur as an inorganic crosslinking agent, 3 to 5 parts by weight of a zinc oxide dispersion, 1.0 to 3.0 parts by weight of a zinc diethyldithiocarbamate dispersion as a crosslinking accelerator, 2-mercaptobenzo 10 to 30 parts by weight of a carbon black dispersion, 10 to 30 parts by weight of a white carbon, and 10 to 30 parts by weight of a dispersant, a tamolene dispersant, are mixed in a ball mill for 20 to 25 hours Dispersed and filtered through a filter net of 150 to 250 mesh to prepare an aqueous dispersion solution,
Wherein the dispersion aqueous solution is added to a reactor and stirred at 60 to 80 ° C for 1 to 3 hours.
The anionic emulsifier is used singly or in combination of two or more among polycarboxylates, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium octyl sulfate, sodium toluene sulfonate, potassium stearyl phosphate or potassium stearate,
The amphoteric stabilizer is used either singly or in combination of two or more among nonylphenyl ether sulfonate or ammonium nonylphenyl ether sulfonate,
Wherein the molecular weight regulator is used alone or in combination of two or more among n-dodecyl mercaptan, t-dodecyl mercaptan and n-octyl mercaptan.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190010406A (en) * | 2018-03-09 | 2019-01-30 | 정의우 | Reforming concrete composition for semi-rigid pavement |
| KR102094432B1 (en) * | 2019-10-25 | 2020-03-27 | 주식회사 중앙폴리텍 | Latex modified ultra rapid hardening concrete composition using the hybrid synthetic rubber latex |
| KR20200105566A (en) * | 2019-02-28 | 2020-09-08 | 주식회사 중앙폴리텍 | Latex modified ultra rapid hardening self levelling finish material composition having excellent curable property in low temperature |
| KR20200105567A (en) * | 2019-02-28 | 2020-09-08 | 주식회사 중앙폴리텍 | Latex modified ultra rapid hardening concrete composition having excellent curable property in low temperature |
| KR20200109763A (en) * | 2019-03-14 | 2020-09-23 | 금호석유화학 주식회사 | Latex composition for concrete manufacturing, process for producing the same, and concrete composition comprising the same |
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| KR102094430B1 (en) * | 2019-10-22 | 2020-03-30 | 주식회사 중앙폴리텍 | Latex modified ultra rapid hardening concrete composition having excellent curable property in low temperature using the flyash and rnace slag |
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| KR20140126811A (en) * | 2013-04-22 | 2014-11-03 | 주식회사 엘지화학 | Latex and composition for dip-forming, lightweight dip-formed article and method for preparing them |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190010406A (en) * | 2018-03-09 | 2019-01-30 | 정의우 | Reforming concrete composition for semi-rigid pavement |
| KR20200105566A (en) * | 2019-02-28 | 2020-09-08 | 주식회사 중앙폴리텍 | Latex modified ultra rapid hardening self levelling finish material composition having excellent curable property in low temperature |
| KR20200105567A (en) * | 2019-02-28 | 2020-09-08 | 주식회사 중앙폴리텍 | Latex modified ultra rapid hardening concrete composition having excellent curable property in low temperature |
| KR20200109763A (en) * | 2019-03-14 | 2020-09-23 | 금호석유화학 주식회사 | Latex composition for concrete manufacturing, process for producing the same, and concrete composition comprising the same |
| KR102094432B1 (en) * | 2019-10-25 | 2020-03-27 | 주식회사 중앙폴리텍 | Latex modified ultra rapid hardening concrete composition using the hybrid synthetic rubber latex |
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