KR20200053085A - Composition of ice­melting agent - Google Patents

Abstract

The present invention relates to a method of removing snow or making ice by using: a first agent including acrylamide-based polymerizable monomer, acrylamide-based or acrylate-based cross-linkable monomer, and water; and a second agent including a polymerization initiator and water. The composition of the present invention is capable of reducing energy costs by heating by oneself due to a polymerization reaction, and thus heating energy consumption according to hot air and hot water is not required compared to the existing method of removing snow, thereby having economic feasibility. In addition, the composition of the present invention allows continuous snow removal and ice making due to formation of gel by mixing of the first agent and the second agent. The formed gel is easily removed, and thus metal corrosion is reduced.

Description

Melting agent composition {Composition of ice­melting agent}

The present invention relates to a release agent composition, and more specifically, it is used for a lower portion of a railroad vehicle and relates to a more economical and efficient ice agent by performing heat removal and ice removal functions by itself.

In the winter, the snow and ice attached to the lower part of the high-speed rail vehicle and the truck are dropped at high speed in the box section to scatter gravel when the vehicle is in operation. As a result, damage to railroad structures and facilities has occurred, and this winter damage has continued since the opening of the high-speed rail. Direct damages include damage to high-speed rail vehicle window panes, axle protection materials, driving gear components, track components, and signal security devices. Indirect damages include problems such as train delays due to other obstacles, increased maintenance cost burden, and reduced driving stability.

In addition to the gravel scattering damage caused by snow-driving of high-speed rail vehicles, railroad vehicles have become a major factor in delaying trains and deteriorating parts and equipment functions due to freezing of vehicles, such as freezing of doorways, freezing of residual water in the vehicle, and freezing of electric devices in vehicle exposed areas. Prevention and countermeasures against snow damage are needed.

To solve these problems, the railroad operating organization has established and responded to measures from the viewpoint of operation and maintenance such as a gravel scattering prevention net, deceleration operation, and vehicle ice making by manpower, but has limitations. At the time of freezing and freezing of railroad cars, the ice-making operation relies on snow removal by manpower in the vehicle base, and in the case of high-speed vehicles, a mobile hot air fan is used, but the time required for ice-making is considerably longer, energy efficiency decreases, and it is limited only in winter As a result, there are problems that require excessive manpower. In addition, the Gangneung Vehicle Base, which was built for the PyeongChang Olympics, installed a high-pressure hot water system in 2017 to de-icing, but this has the problem that the remaining moisture re-freezes after de-icing and uses a boiler to heat the water. Energy cost is excessively consumed, and also has a problem of causing corrosion in the storage tank and the transport pipe.

The present inventors have made earnest research efforts to develop a composition for deicing or deicing suitable for a high-speed rail vehicle in winter. As a result, the present inventors developed a melting agent composition using a mixture of one agent containing a polymerizable monomer and a polymer crosslinking agent and two agents containing a polymerization initiator.

The composition of the present invention is a melting agent having a structure of a release agent, and the first agent and the second agent are mixed, and polymerization reaction occurs within a short time, and the snow removal and ice-making effects are caused by polymerization heat. In addition to the heat of polymerization, there is no need for a separate material or procedure for heat generation, thus reducing energy costs.

In addition, as the polymerization reaction is completed, a high-temperature gel is formed, which adheres without flowing off the ice and exhibits continuous melting properties. The final gel can be easily removed, so it has little corrosion effect when applied to the lower surface of a railroad car.

Accordingly, an object of the present invention is to provide a snow removal or deicing method.

An object of the present invention is to provide a composition for deicing or deicing.

One aspect of the present invention relates to a snow removal or deicing method comprising the following steps:

(a) applying or spraying a mixture of acrylamide-based polymerizable monomer, acrylamide-based or acrylate-based crosslinkable monomer and water; And

(b) The step of applying or spraying a mixture of a polymerization initiator and water.

The present inventors have made earnest research efforts to develop a composition for deicing or deicing suitable for a high-speed rail vehicle in winter. As a result, the present inventors developed a melting agent composition for mixing and using one agent containing an acrylamide-based polymerizable monomer and a polymer crosslinking agent and two agents containing a polymerization initiator.

The composition of the present invention is a melting agent having a structure of a release agent, and the first agent and the second agent are mixed, and polymerization reaction occurs within a short time, and the snow removal and ice-making effects are caused by polymerization heat. In addition to the heat of polymerization, there is no need for a separate material or procedure for heat generation, thus reducing energy costs.

The snow removal or de-icing composition of the present invention is a liquid composition used for the purpose of deicing and snow-removing the lower part of a high-speed rail vehicle for the safe operation of a high-speed rail vehicle in winter.

Conventional high-speed rail vehicle deicing and snow removal uses manual de-icing, hot-air de-icing, and high-pressure hot-water deicing using manpower, but the efficiency has continued to be a problem. The melting agent of the present invention can reduce energy costs because the first agent and the second agent are self-heating in a short time while being mixed. In addition, as the reaction gradually completes, a high-temperature gel is formed, which adheres without flowing out of ice, thereby continuously exhibiting melting performance. The finally formed gel can be easily detached to reduce the corrosion effect of the lower surface of the railway vehicle.

Hereinafter, the snow removing or deicing method of the present invention will be described in detail.

Step (a) mixing or spraying a polymerizable monomer, a crosslinkable monomer and water

First, a polymerizable monomer, a crosslinkable monomer, and water are mixed and applied or sprayed on a target / place to be snow-removed or de-iced.

The composition used in the snow removal or deicing method of the present invention includes a first agent comprising an acrylamide-based polymerizable monomer, an acrylamide-based or acrylate-based crosslinkable monomer, and water, and a polymerization initiator. (polymerization initiator) and two agents containing water.

In step (a), 1 agent is used, and in step (b), 2 agents are used.

In the present invention, the acrylamide-based polymerizable monomer is acrylamide; (Meth) acrylamide; And N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone It may be selected from the group containing N- substituted (meth) acrylamide such as acrylamide.

According to one embodiment of the present invention, the acrylamide-based polymerizable monomer is acrylamide.

In the present invention, it is preferable to use a monomer having two or more double bonds in the molecule of the acrylamide-based or acrylate-based crosslinkable monomer. For example, the acrylamide-based crosslinkable monomer may be polyfunctional (meth) acrylamide such as methylenebis (meth) acrylamide and ethylenebis (meth) acrylamide; The acrylate-based crosslinkable monomer may be a polyfunctional (meth) acrylate such as ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, glycerin di (meth) acrylate, and glycerin tri (meth) acrylate. have.

According to one embodiment of the present invention, the acrylamide-based crosslinkable monomer is N, N ''-methylenebisacrylamide.

According to one embodiment of the present invention, in step (a), (i) 5-60% by weight of the acrylamide-based polymerizable monomer relative to the total composition of the first agent, (ii) 0.1-1.0 based on the total composition of the first agent It is carried out by coating or spraying a composition comprising, by weight, acrylamide-based or acrylate-based crosslinkable monomers, (iii) 1-10% by weight of a polymerization catalyst, and (iv) water, based on the total composition of the first agent. .

According to another embodiment of the present invention, in step (a), (i) 20-50% by weight of acrylamide-based polymerizable monomer relative to the total composition of the first agent, (ii) 0.3-0.5 based on the total composition of the first agent It is carried out by coating or spraying a composition comprising, by weight, acrylamide-based or acrylate-based crosslinkable monomers, (iii) 1-10% by weight of a polymerization catalyst, and (iv) water, based on the total composition of the first agent. .

According to another embodiment of the present invention, the acrylamide-based polymerizable monomer may be included in 10-60% by weight relative to the total composition of the first agent, or 15-60% by weight, 20 relative to the total composition of the first agent -60% by weight, 25-60% by weight, 30-60% by weight, 35-60% by weight, 40-60% by weight, or 45-60% by weight may be included.

Alternatively, the acrylamide-based polymerizable monomer may be included in 5-55% by weight, or 5-50% by weight, 5-45% by weight, or 5-40% by weight relative to the total composition of the first agent.

Or the acrylamide-based polymerizable monomer may be included in 10-55% by weight relative to the total composition of the agent 1, or 15-50% by weight, 20-50% by weight, 25-50% by weight, 30-50% by weight , 35-50% by weight, 40-50% by weight, or 45-50% by weight.

According to another embodiment of the present invention, the acrylamide-based or acrylate-based crosslinkable monomer in the first agent composition of the present invention is 0.2-1.0% by weight, 0.3-1.0% by weight, 0.4-1.0% by weight based on the total composition of the first agent. %, 0.5-1.0 wt%, 0.6-1.0 wt%, 0.7-1.0 wt%, 0.9-1.0 wt%, or 0.8-1.0 wt%.

Or acrylamide-based or acrylate-based crosslinkable monomer is 0.1-0.9% by weight, 0.1-0.8% by weight, 0.1-0.7% by weight, 0.1-0.6% by weight, 0.1-0.5% by weight, 0.1 -0.4% by weight, 0.1-0.3% by weight, or 0.1-0.2% by weight.

Alternatively, the acrylamide-based or acrylate-based crosslinkable monomer may be included in 0.2-0.8% by weight, 0.3-0.7% by weight, or 0.4-0.6% by weight based on the total composition of the first agent.

Alternatively, the acrylamide-based or acrylate-based crosslinkable monomer may be included in 0.2-0.6% by weight, 0.3-0.5% by weight, or 0.4-0.5% by weight based on the total composition of the first agent.

According to another embodiment of the present invention, the polymerization reaction catalyst in the first agent composition of the present invention may be included in 2-10% by weight, 3-10% by weight, or 4-10% by weight relative to the total composition of the first agent.

Water in the composition of the first agent may be included in the total amount of the first agent composition except for the acrylamide-based polymerizable monomer, acrylamide-based or acrylate-based crosslinkable monomer, and polymerization catalyst.

Step (b): a step of mixing or spraying a polymerization initiator and water

Subsequently, a polymerization initiator and water are mixed and applied or sprayed.

In the present invention, the polymerization initiator is a water-soluble radical polymerization initiator, and potassium persulfate, sodium persulfate, or ammonium persulfate may be used. According to one embodiment of the invention, the polymerization initiator is sodium persulfate.

According to one embodiment of the invention, step (b) is carried out by applying or spraying a composition comprising (i) 1-10% by weight of a polymerization initiator, and (ii) water, relative to the total composition of the two agents.

According to another embodiment of the present invention, the polymerization initiator in the second agent composition of the present invention is 2-10% by weight, 3-10% by weight, 4-10% by weight, 5-10% by weight, 6 -10 wt%, 7-10 wt%, 8-10 wt%, or 9-10 wt%.

Or the polymerization initiator is 1-9% by weight, 1-8% by weight, 1-7% by weight, 1-6% by weight, 1-5% by weight, 1-4% by weight, 1-3% by weight based on the total composition of the second agent %, Or 1-2% by weight.

Or the polymerization initiator is 2-9% by weight, 2-8% by weight, 2-7% by weight, 2-6% by weight, 2-5% by weight, 2-4% by weight, or 3-4% by weight based on the total composition of the second agent It may be included in weight percent.

According to a specific embodiment of the present invention, in step (b), it is carried out by applying or spraying a composition comprising (i) 2-4% by weight of a polymerization initiator, and (ii) water, relative to the total composition of the two agents.

According to one embodiment of the present invention, the snow removal or deicing method of the present invention may additionally perform a step of applying or spraying a polymerization catalyst. The polymerization catalyst may be applied / sprayed as a separate step from step (a) and / or step (b), or may be applied to the first agent used in step (a) and / or the second agent used in step (b). It can be used in combination.

According to an embodiment of the present invention, the polymerization reaction catalyst may be used by being mixed with the first agent of step (a).

According to an embodiment of the present invention, the polymerization catalyst may be selected from the group consisting of triethanolamine, triethylamine, tributylamine, and N-benzyldimethylamine. According to a particular embodiment of the present invention, the polymerization reaction catalyst is triethanol amine.

Water in the composition of the second agent may be included in the total amount of the second agent except for the polymerization initiator and the polymerization catalyst.

As described above, in the snow removal or deicing method of the present invention, a first agent containing an acrylamide-based polymerizable monomer, an acrylamide-based or acrylate-based crosslinkable monomer, and water is first applied. Next, although it is expressed as applying a polymerization initiator and a two agent containing water, this is for convenience of description.

That is, the snow removal or deicing method of the present invention (i) when the above process is reversed, that is, applying the second agent first and then applying the first agent, and (ii) mixing the first agent and the second agent immediately and simultaneously It does not exclude application.

Another aspect of the present invention (a) acrylamide-based polymerizable monomers (polymerizable monomer), acrylamide-based or acrylate-based crosslinkable monomer (crosslinkable monomer) and a first agent comprising water; And (b) a polymerization initiator and two agents comprising water.

The snowmaking or deicing composition of the present invention is the same as the composition used in the snowmaking or deicing method of the present invention described above, and contents common to the two are omitted to avoid excessive complexity of the present specification.

The composition of the present invention may further include a polymerization reaction catalyst. The polymerization catalyst may be included in the first agent and / or the second agent.

According to one embodiment of the invention, the composition is (a) (i) 5-60% by weight of the polymerizable monomer relative to the total composition of the first agent, (ii) 0.1-1.0% by weight relative to the total composition of the first agent A crosslinkable monomer of, (iii) 1-10% by weight of a polymerization catalyst relative to the total composition of the agent, and (iv) water; And (b) (i) 2-10% by weight of the polymerization initiator relative to the total composition of the second agent, and (ii) water.

According to another embodiment of the invention, the composition (a) (i) 20-50% by weight of the polymerizable monomer relative to the total composition of the first agent, (ii) 0.3-0.5% by weight relative to the total composition of the first agent A crosslinkable monomer of, (iii) 1-10% by weight of a polymerization catalyst relative to the total composition of the agent, and (iv) water; And (b) (i) 2-4% by weight of the polymerization initiator relative to the total composition of the second agent, and (ii) water.

According to a specific embodiment of the present invention, the composition is 20-50% by weight of acrylamide, 0.3-0.5% by weight of N, N ''-methylenebisacrylamide, 1-10% by weight of triethanolamine, based on the total composition of the agent. , 40-78% by weight of water; It contains 2-4% by weight of sodium persulfate and 96-98% by weight of water relative to the total composition of the two agents.

In the composition of the present invention, the lower and upper values of the polymerizable monomer and the crosslinkable monomer were determined in consideration of stability of the reaction and gelation time. The lower limit was determined in consideration of the time to gelation and the calorific value. In addition, when the content of the polymerizable monomer and the crosslinkable monomer is increased, the amount of the solvent (water) required for polymerization decreases, so that the reaction may occur explosively, and thus the upper limit was determined in consideration of the stability of the reaction.

In the present invention, it is possible to provide a more efficient melting agent for a lower part of a high-speed rail vehicle by utilizing a release agent. The melting agent of the present invention can reduce energy cost because it heats itself within a short period of time when the first agent and the second agent are mixed, and gradually forms a gel of high temperature as the reaction is completed and adheres without flowing from the ice to continuously improve the melting performance. see.

In particular, the composition of the present invention rises in a short time by the heat of polymerization to reach the maximum temperature (see Table 2 below). Compared to the conventional snow removal and calcium chloride used as an ice-making agent, since the time required for temperature rise is very small, it is possible to provide an ice melting effect in a short time.

The composition of the present invention can be gelled by polymerization within 1 second to 1 minute. According to one embodiment of the present invention, the composition of the present invention gels within 10 seconds, and may reach a maximum temperature within 20 seconds.

Meanwhile, the snow removing or deicing composition of the present invention may additionally include a metal corrosion inhibitor or an antioxidant as an additive.

The anti-corrosion agent may be selected from the group consisting of benzotriazole, tolitriazole, cyclohexylamine, molybdate, or combinations thereof.

Antioxidants can be selected from the group consisting of sodium nitrate, dibutyl hydroxy toluene, butylhydroxy anisole, triphenylphosphate or combinations thereof.

The features and advantages of the present invention are summarized as follows:

The present invention is an acrylamide-based polymerizable monomer (polymerizable monomer), an acrylamide-based or acrylate-based crosslinkable monomer (crosslinkable monomer) and a first agent containing water; And it relates to a snow removal or deicing method using a polymerization initiator (polymerization initiator) and two agents containing water.

The composition of the present invention is economical because there is no heating energy consumption due to hot air and hot water compared to the conventional snow removal method, since it is possible to reduce the energy cost by heating itself due to the polymerization reaction.

In addition, continuous snow removal and de-icing is possible by forming a gel by mixing the first and second agents. The formed gel is easily removed and metal corrosion is reduced.

Figure 1 shows the results of confirming whether the metal corrosion of the compositions of Examples 1-3 and Comparative Examples 1-2 of the present invention. Corrosion is indicated by O or X.

Hereinafter, the present invention will be described in more detail through examples. These examples are only intended to illustrate the present invention more specifically, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. .

Example

Composition of manufacturing example

The composition of Examples 1-3 according to the present invention and the comparative example 1 of the composition of calcium chloride used as a melting agent / deicing agent for general roads among the existing melting / deicing agents and high pressure hot water as a rail car melting agent / snow removing agent Water used as Comparative Example 2 was prepared.

Unit (g) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 1 agent (polymerized monomer) Acrylamide 10 20 25 - - 1 agent (raw materials) Calcium chloride - - - 50 - 1 agent (polymer crosslinking agent) N, N ''-methylenebisacrylamide 0.15 0.2 0.25 - - 1st
(catalyst) Triethanolamine 2 5 5 - - 1 agent (solvent) water 37.85 24.8 19.75 50 100 2 drugs (polymerization initiator) Sodium persulfate 1.5 1.5 1.5 - - 2 drugs (solvent) water 48.5 48.5 48.5 - - - Sum 100 100 100 100 100

Test Example 1: Measurement of the heating temperature

It was shown in Table 2 below by measuring the maximum temperature of heating by mixing the solutions of room temperature (25 ℃) prepared as in Examples 1-3 and Comparative Examples 1-2, respectively.

Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Maximum temperature when mixing (℃) 50.1 58.9 77.9 58.7 25 Energy costs for heat X X X X O Time to reach maximum temperature 19 seconds 16 seconds 13 seconds  3 minutes or more -

As shown in Table 2, it was confirmed that in Examples 1-3 and Comparative Example 1, materials were mixed to generate heat of 50 ° C. to 80 ° C. by themselves without additional energy cost. In the case of Comparative Example 2, it was confirmed that an energy cost of 3.5 kcal was required to have heat of 60 ° C.

Test Example 2: Measurement of the melting effect

After mixing the solutions of room temperature (25 ° C) prepared as in Example 1-3 and Comparative Example 1-2, respectively, and applying them to the ice surface having the same weight (780 g), measuring the amount of ice melting after 10 minutes elapsed. It is shown in Table 3 below.

Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Melting or not O O O O O Melting amount (g) 264 377 548 193 21

As shown in Table 3, it was confirmed that in Examples 1-3, the higher the maximum temperature generated when mixing the first agent and the second agent, the greater the amount of ice. Comparing Example 2 and Comparative Example 1, the maximum temperature during mixing is similar, but Example 2 forms and attaches a hot gel on ice and continuously melts, whereas Comparative Example 1 is a liquid and is gravity-treated with ice. Since the contact time of is short, it was confirmed that the amount of ice compared to the similar temperature is small. Comparative Example 2 Also, it was confirmed that only a very small amount of ice was melted because the contact time with ice was short in the liquid phase and heat was not generated without external energy.

Test Example 3: Measurement of metal corrosion

The solutions at room temperature (25 ° C.) prepared as in Examples 1-3 and Comparative Examples 1-2 were each mixed, and left in a beaker containing clips for 3 days. Thereafter, corrosion was visually checked.

As shown in Figure 1, Example 1-3 was confirmed that the discoloration or corrosion of the clip did not occur. On the other hand, in Comparative Example 1, severe discoloration and corrosion occurred in the entire clip, and Comparative Example 2 also confirmed that discoloration and corrosion occurred on some surfaces.

Claims (10)

Snow removal or deicing method including the following steps:
(a) applying or spraying a mixture of acrylamide-based polymerizable monomer, acrylamide-based or acrylate-based crosslinkable monomer and water; And
(b) the step of applying or spraying a mixture of a polymerization initiator and water.
The method of claim 1, wherein the polymerizable monomer is acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl Snow removal or de-icing method selected from the group consisting of (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and diacetone acrylamide.
The method of claim 1, wherein the crosslinkable monomer is methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, glycerin di (meth) acrylic Rate, and glycerin tri (meth) acrylate.
The method of claim 1, wherein the polymerization initiator is potassium persulfate, sodium persulfate or ammonium persulfate.
The method of claim 1, wherein the first agent or the second agent further comprises a polymerization reaction catalyst.
The method of claim 5, wherein the polymerization reaction catalyst is triethanolamine, triethylamine, tributylamine, or N-benzyldimethylamine.
(a) 1 agent comprising an acrylamide-based polymerizable monomer, an acrylamide-based or acrylate-based crosslinkable monomer and water; And (b) a polymerization initiator and two agents comprising water.
The method of claim 7, wherein the composition (a) (i) 5-60% by weight of the polymerizable monomer relative to the total composition of the first agent, (ii) 0.1-1.0% by weight of the crosslinkability of the total composition of the first agent Monomer, (iii) 1-10% by weight of a polymerization catalyst relative to the total composition of the agent, and (iv) water; And (b) (i) 2-10% by weight of a polymerization initiator relative to the total composition of the second agent, and (ii) water.
The method of claim 7, wherein the composition (a) (i) 20-50% by weight of the polymerizable monomer relative to the total composition of the first agent, (ii) 0.3-0.5% by weight relative to the total composition of the first agent crosslinkability Monomer, (iii) 1-10% by weight of a polymerization catalyst relative to the total composition of the agent, and (iv) water; And (b) (i) 2-4% by weight of a polymerization initiator relative to the total composition of the second agent, and (ii) water.
The snow removal or deicing composition of claim 7, wherein the composition further comprises a metal corrosion inhibitor or an antioxidant as an additive.

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