KR102167272B1 - Composition of ice­melting agent - Google Patents

Abstract

The present invention is a first agent comprising an acrylamide-based polymerizable monomer, an acrylamide-based or acrylate-based crosslinkable monomer, and water; And a method for snow removal or ice making using a second agent including a polymerization initiator and water. The composition of the present invention can generate heat by itself due to the polymerization reaction to reduce energy cost, and is economical because there is no heating energy consumption due to hot air and hot water compared to the existing snow removal method. In addition, continuous snow removal and ice making is possible by forming a gel by mixing the first agent and the second agent. The formed gel is easily detached, reducing metal corrosion.

Description

Melting agent composition {Composition of icemelting agent}

The present invention relates to a release melting agent composition, and more particularly, to a more economical and efficient melting agent by performing functions such as snow removal and ice making by self-heating and being used for a lower part of a railway vehicle.

In winter, snow and ice adhering to the lower part of the high-speed rail vehicle and the bogie part fall at high speed in the road box brown section during vehicle operation and scatter gravel. This is causing damage to railway vehicle structures and facilities, and such winter damage continues after the opening of the high-speed rail. Direct damages include damage to the high-speed rail vehicle window glass, axle protection material, traveling device components, track components, and signal security devices. Indirect damages include train delays due to other obstacles, increased maintenance cost burden, and reduced driving stability.

In addition to the damage of gravel scattering caused by snow and ice in high-speed rail vehicles, it is a major factor in train delays and deterioration of the function of parts equipment due to vehicle freezing such as freezing of entrance doors, freezing of residual moisture in the brake system, and freezing of electric devices in the vehicle exposed part. There is a need for measures to prevent and respond to snow and ice damage.

In order to solve this problem, the railway operating institution has established and responded to it by establishing countermeasures in terms of operation and maintenance, such as a gravel scattering prevention net, deceleration operation, and vehicle ice-making by manpower, but it has limitations. Currently, the ice making operation when freezing and freezing of railway vehicles relies on snow removal by personnel within the vehicle base, and a mobile hot air blower is used in the case of high-speed vehicles, but the time required for ice making is quite long, energy efficiency is low, and it is temporary only in winter. There are problems that require excessive manpower. In addition, in the Gangneung vehicle base built for the PyeongChang Olympic Games, a high-pressure hot water system was installed in 2017 to make ice, but this has a problem that the remaining moisture after the ice making operation is re-frozen, and a boiler is used to heat the water. It consumes excessive energy costs, and has a problem of causing corrosion in storage tanks and transfer pipes.

The present inventors have made intensive research efforts to develop a composition for snow removal or ice making suitable for a high-speed rail vehicle in winter. As a result, the present inventors have developed a melting agent composition using a mixture of one agent including a polymerizable monomer and a polymer crosslinking agent and a second agent including a polymerization initiator.

The composition of the present invention is a melting agent having a structure of a releasing agent, and a polymerization reaction occurs within a short time by mixing the first agent and the second agent, thereby exhibiting snow removal and ice making effects by the heat of polymerization. In addition to the heat of polymerization, there is no need for a separate material or procedure for heat generation, so energy costs are reduced.

In addition, when the polymerization reaction is completed, a high-temperature gel is formed and adheres without flowing down from the ice, showing continuous melting. As the finally formed gel can be easily removed, it has little effect on corrosion when applied to the lower surface of a railroad vehicle.

Accordingly, it is an object of the present invention to provide a method for snow removal or ice making.

It is an object of the present invention to provide a composition for snow removal or ice making.

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

(a) applying or spraying a first agent in which an acrylamide-based polymerizable monomer, an acrylamide-based or acrylate-based crosslinkable monomer, and water are mixed; And

(b) applying or spraying a second agent in which a polymerization initiator and water are mixed.

The present inventors have made intensive research efforts to develop a composition for snow removal or ice making suitable for a high-speed rail vehicle in winter. As a result, the present inventors have developed a melting agent composition using a mixture of one agent containing an acrylamide-based polymerizable monomer and a polymer crosslinking agent, and a second agent containing a polymerization initiator.

The composition of the present invention is a melting agent having a structure of a releasing agent, and a polymerization reaction occurs within a short time by mixing the first agent and the second agent, thereby exhibiting snow removal and ice making effects by the heat of polymerization. In addition to the heat of polymerization, there is no need for a separate material or procedure for heat generation, so energy costs are reduced.

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

Existing ice-making and snow removal under high-speed rail vehicles uses manual ice-making, hot-air ice-making, and high-pressure hot water ice-making using manpower, but the efficiency has been a problem continuously. The melting agent of the present invention can reduce energy cost because the first agent and the second agent are mixed and generate heat by themselves within a short time. In addition, as the reaction is gradually completed, a high-temperature gel is formed, and it is attached without flowing down from the ice, so that the melting performance is shown continuously. The finally formed gel can be easily removed, thereby reducing the corrosion influence of the lower surface of the railway vehicle.

Hereinafter, the snow removal or ice making method of the present invention will be described in detail.

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

First, a polymerizable monomer, a crosslinkable monomer, and water are mixed and applied or sprayed on an object/place to be snow-removed or ice-defrosted.

The composition used in the snow removal or ice making method of the present invention includes one agent containing 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), one agent is used, and in step (b), two 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 a molecule as an acrylamide-based or acrylate-based crosslinkable monomer. For example, the acrylamide-based crosslinkable monomer may be a 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 an embodiment of the present invention, in step (a) (i) 5-60% by weight of an acrylamide polymerizable monomer based on the total composition of the first agent, (ii) 0.1-1.0 with respect to the total composition of the first agent. It is carried out by applying or spraying a composition containing an acrylamide-based or acrylate-based crosslinkable monomer, (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 the acrylamide polymerizable monomer based on 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 applying or spraying a composition containing an acrylamide-based or acrylate-based crosslinkable monomer, (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 an amount of 10-60% by weight based on the total composition of the first agent, or 15-60% by weight, 20% by weight based on 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 an amount of 5-55% by weight, or 5-50% by weight, 5-45% by weight, or 5-40% by weight based on the total composition of the first agent.

Alternatively, the acrylamide-based polymerizable monomer may be included in an amount of 10-55% by weight based on the total composition of the first agent, 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 may be included.

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% by weight, 0.6-1.0% by weight, 0.7-1.0% by weight, 0.9-1.0% by weight, or 0.8-1.0% by weight.

Alternatively, the 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 based on the total composition of the first agent. -0.4% by weight, 0.1-0.3% by weight, or 0.1-0.2% by weight may be included.

Alternatively, the acrylamide-based or acrylate-based crosslinkable monomer may be contained in an amount of 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 an amount of 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 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 based on the total composition of the first agent.

In the composition of the first agent, water may be included in the remaining amount excluding an acrylamide-based polymerizable monomer, an acrylamide-based or acrylate-based crosslinkable monomer, and a polymerization catalyst among the entire first agent composition.

Step (b): applying or spraying a mixture of a polymerization initiator and water

Then, 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 present invention, the polymerization initiator is sodium persulfate.

According to one embodiment of the present 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 based on the total composition of the second agent.

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%.

Alternatively, 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.

Alternatively, 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 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, step (b) is carried out by applying or spraying a composition comprising (i) 2-4% by weight of a polymerization initiator, and (ii) water based on the total composition of the second agent.

According to one embodiment of the present invention, the snow removal or ice making 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 step separate from step (a) and/or step (b), or to the first agent used in step (a) and/or the second agent used in step (b). It can be mixed and used.

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

According to one 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 specific embodiment of the present invention, the polymerization catalyst is triethanol amine.

In the second agent composition, water may be included in the remaining amount excluding a polymerization initiator and a polymerization reaction catalyst in the total second agent composition.

As described above, in the snow removal or ice making method of the present invention, a first agent including 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 second agent including water, this is for convenience of description.

That is, the snow removal or ice making method of the present invention is (i) in the case of reverse the above process, i.e., applying the second agent first and then applying the first agent, and (ii) mixing the first agent and the second agent immediately and at the same time. It does not preclude application.

Another aspect of the present invention is (a) one agent comprising an acrylamide-based polymerizable monomer, an acrylamide-based or acrylate-based crosslinkable monomer, and water; And (b) a polymerization initiator and a second agent comprising water.

The snow-making or ice-making composition of the present invention is the same as the composition used in the snow-making or ice-making method of the present invention, and descriptions of the contents in common between the two are omitted in order to avoid excessive complexity of the present specification.

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

According to an embodiment of the present invention, the composition comprises (a) (i) 5-60% by weight of a polymerizable monomer based on the total composition of the first agent, (ii) 0.1-1.0% by weight based on the total composition of the first agent. Of the crosslinkable monomer, (iii) 1-10% by weight of a polymerization catalyst based on the total composition of the first agent, and (iv) water; And (b) (i) 2-10% by weight of a polymerization initiator based on the total composition of the second agent, and (ii) water may be included.

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

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

In the composition of the present invention, the contents of the polymerizable monomer and the crosslinkable monomer, which are polymers, were determined in consideration of the stability of the reaction and the gelation time to determine the lower and upper limits. The lower limit value was determined in consideration of the time until gelation and the calorific value. In addition, when the content of the polymerizable monomer and the crosslinkable monomer increases, the amount of solvent (water) required for polymerization decreases, and the reaction may occur explosively, so the upper limit value was determined in consideration of the stability of the reaction.

In the present invention, a more efficient melting agent for the lower part of a high-speed rail vehicle may be provided by using a release agent. Since the melting agent of the present invention generates heat by itself within a short time while the first agent and the second agent are mixed, energy cost can be reduced. As the reaction is gradually completed, a high-temperature gel is formed and adhered without flowing down from the ice to continuously improve the melting performance. see.

In particular, the composition of the present invention reaches a maximum temperature by increasing the temperature in a short time by the heat of polymerization (see Table 2 below). Compared with calcium chloride used as a conventional snow removal and deicing agent, the time required to increase the temperature is very small, so that the melting effect can be provided 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 is gelled within 10 seconds and can reach a maximum temperature within 20 seconds.

On the other hand, the snow removal or ice-making composition of the present invention may additionally include a metal corrosion inhibitor or an antioxidant as an additive.

The metal anticorrosive agent may be selected from the group consisting of benzotriazole, tolithriazole, cyclohexylamine, molybdate, or a combination thereof.

The antioxidant may 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 a first agent comprising an acrylamide-based polymerizable monomer, an acrylamide-based or acrylate-based crosslinkable monomer, and water; And a method for snow removal or ice making using a second agent including a polymerization initiator and water.

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

In addition, continuous snow removal and ice making is possible by forming a gel by mixing the first agent and the second agent. The formed gel is easily detached, reducing metal corrosion.

1 shows the results of checking whether the compositions of Examples 1-3 and Comparative Example 1-2 of the present invention have metal corrosion. Corrosion was indicated by O or X.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for describing the present invention in more detail, and it will be apparent to those of ordinary skill 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

Example 1-3 Composition of the composition according to the present invention and Comparative Example 1 of the composition of calcium chloride used as a melting and deicing agent for general roads among the existing melting and deicing agents and high-pressure hot water as a melting and deicing agent for railway vehicles Water used as was prepared as Comparative Example 2.

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

Test Example 1: Measurement of heating temperature

The maximum temperature to generate heat was measured by mixing the solutions at room temperature (25° C.) prepared as in Examples 1-3 and Comparative Example 1-2, respectively, and are shown in Table 2 below.

Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Maximum temperature during mixing (℃) 50.1 58.9 77.9 58.7 25 Energy cost in case of heat X X X X O Time to reach maximum temperature 19 seconds 16 seconds 13 seconds More than 3 minutes -

As shown in Table 2, in Examples 1-3 and Comparative Example 1, it was confirmed that each material was mixed to generate heat of 50°C to 80°C by itself without separate 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: Melting effect measurement

Each of the solutions at room temperature (25°C) prepared as in Example 1-3 and Comparative Example 1-2 was mixed and applied to the surface of ice of the same weight (780 g), and then the amount of ice melted after 10 minutes was measured. 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, in Example 1-3, it was confirmed that the higher the maximum temperature generated when the first agent and the second agent were mixed, the greater the amount of ice melted. Comparing Example 2 and Comparative Example 1, the maximum temperature during mixing was similar, but Example 2 formed and adhered to a high-temperature gel on ice and continuously melted, whereas Comparative Example 1 was a liquid phase with ice due to gravity. Since the contact time of is short, it was confirmed that the amount of melting was less than the similar temperature. Comparative Example 2 In addition, it was confirmed that only a very small amount of ice melted because the liquid phase had a short contact time with ice and could not generate heat without external energy.

Test Example 3: Measurement of metal corrosion

Each of the solutions at room temperature (25° C.) prepared as in Examples 1-3 and Comparative Example 1-2 were mixed, and left in a beaker containing a clip for 3 days. After that, it was checked visually for corrosion.

As shown in Fig. 1, in Example 1-3, it was confirmed that no discoloration or corrosion of the clip occurred. On the other hand, in Comparative Example 1, it was confirmed that severe discoloration and corrosion occurred on the entire clip, and in Comparative Example 2, discoloration and corrosion occurred on some surfaces.

Claims (10)

Snow removal or ice making method comprising the following steps:
(a) applying or spraying a mixture of 45-60% by weight of acrylamide, 0.5-1.0% by weight of methylenebis(meth)acrylamide, 4-10% by weight of triethanolamine, and water; And
(b) applying or spraying a second agent in which 3-10% by weight of sodium persulfate and water are mixed.
delete delete delete delete delete (a) 1 agent containing 45-60% by weight of acrylamide, 0.5-1.0% by weight of methylenebis(meth)acrylamide, 4-10% by weight of triethanolamine, and water; And (b) 3-10% by weight of sodium persulfate and a second agent containing water, a snow removal or ice-making composition.
delete delete According to claim 7, wherein the composition is to further comprise a metal corrosion inhibitor or antioxidant as an additive, the snow removal or ice-making composition.

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