KR20120070749A - Release-rate controlled road antifreezing agent - Google Patents
Release-rate controlled road antifreezing agent Download PDFInfo
- Publication number
- KR20120070749A KR20120070749A KR1020100132188A KR20100132188A KR20120070749A KR 20120070749 A KR20120070749 A KR 20120070749A KR 1020100132188 A KR1020100132188 A KR 1020100132188A KR 20100132188 A KR20100132188 A KR 20100132188A KR 20120070749 A KR20120070749 A KR 20120070749A
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- South Korea
- Prior art keywords
- water
- cryoprotectant
- polyhydric alcohol
- soluble polyhydric
- adsorbent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C11/00—Details of pavings
- E01C11/24—Methods or arrangements for preventing slipperiness or protecting against influences of the weather
- E01C11/245—Methods or arrangements for preventing slipperiness or protecting against influences of the weather for preventing ice formation or for loosening ice, e.g. special additives to the paving material, resilient coatings
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
Abstract
Description
The present invention relates to a road cryoprotectant which is sprayed on the road surface in winter to stably prevent snow and freezing for a long time because the release rate of the freezing point depressant is controlled by the adsorbent and the thickener.
In the winter snowing season, for smooth road traffic, frictional agents such as sand and freezing inhibitors such as calcium chloride are sprayed or removed from snow every time by snow removal vehicles. In order to remove snowfall already in a short time without being obstructed by road traffic, it is difficult to input a large amount of equipment and manpower and work quickly.
The method of preventing slippage by spraying friction material such as sand or crushed stone does not have a snow melting effect and it is difficult to expect an effect because it is buried in the snow when additional snow is deposited.
Currently used cryoprotectants include calcium chloride, sodium chloride, acetate, ethylene glycol, propylene glycol, etc. These or their aqueous solutions are easy to flow down the road due to their low viscosity. There is a hassle to do. In particular, chloride salts such as calcium chloride and sodium chloride are problematic because of the accumulation of chloride, such as environmental pollution, corrosion of vehicles and bridges.
On the other hand, sustained-release cryoprotectants using salts of stearic acid, hydrophobic coating materials and the like have been reported [Japanese Patent Laid-Open No. 1995-189226], but there is a lack of fast-acting effect, which is insufficient.
A method of reducing the freezing of the road surface by adding a slow-release cryoprotectant to road pavement materials such as ascon has been proposed [Korean Patent Publication No. 1997-0042931]. There is a difficulty in packaging and lack of fast-acting has become an obstacle to the commercialization.
An object of the present invention is to provide a road freezing inhibitor that satisfies both fastness and continuity at the same time by controlling the release rate of the freezing point depressant and is easy to apply.
In order to achieve the above object, the present invention is a C 2-6 water-soluble polyhydric alcohol 35? 75 wt%; At least one porous adsorbent selected from the group consisting of activated carbon, zeolite and activated alumina; 60 wt%; And 0.01 to one or more thickeners selected from Xanthan, acrylic polymers and mixtures thereof. It is characterized by a road cryoprotectant comprising 10% by weight.
In the present invention, the water-soluble polyhydric alcohol having excellent fast-acting effect as a freezing point depressant is adsorbed and stored in a porous adsorbent for sustained release, and the sustained release is enhanced. Has the effect of increasing.
When the cryoprotectant of the present invention is applied to the road surface in winter, the formation of ice sheets is suppressed for a long time, and snow removal is easily performed, thereby reducing the damage caused by winter ice and snow.
The cryoprotectant of the present invention has an effect of minimizing the consumption of the cryoprotectant by controlling the outflow rate of the freezing point depressant while changing to sol-gel according to the road traffic.
The cryoprotectant of the present invention has an effect of improving the antifreeze sustainability while reducing the environmental pollution than the conventional chloride freezing point depressant by containing a water-soluble polyhydric alcohol as the freezing point lowering agent.
Referring to each component of the composition contained in the road cryoprotectant of the present invention in detail.
In the present invention, the water-soluble polyhydric alcohol having 2 to 6 carbon atoms as the freezing point depressant has the advantage that the water-soluble polyhydric alcohol is excellent in quickness and environmentally friendly. Specifically, the water-soluble polyhydric alcohol may be used one or two or more selected from ethylene glycol, propylene glycol, glycerin, diethylene glycol, sorbitol, isocitol, mannitol and the like. Among the above-mentioned water-soluble polyhydric alcohols, ethylene glycol, propylene glycol, glycerin and the like having a relatively high water solubility are preferable. The water-soluble polyhydric alcohol described above in the road cryoprotectant of the present invention is preferably included in the content range of 35 to 75% by weight, preferably 45 to 65% by weight. When the content of the water-soluble polyhydric alcohol is out of the above range, it is difficult to simultaneously obtain fast-acting and sustained-release properties desirable as antifreezing agents.
In the present invention, a porous adsorbent is selected and used as a sustained release functional material, and the adsorbent uses at least one porous material selected from the group consisting of activated carbon, zeolite, and activated alumina. The porosity of the porous adsorbent has a specific surface area of 200 to 1500 m 2 / g, preferably 500 to 1200 m 2 / g, and preferably has a particle diameter of 0.001 to 3 mm. In the present invention, the fast-acting and sustained-release properties are controlled by adsorbing a water-soluble polyhydric alcohol having a fast-acting effect on the porous adsorbent and sustained release. In order to adsorb the water-soluble polyhydric alcohol to the porous adsorbent, the adsorbent and the water-soluble polyhydric alcohol are mixed and stirred under atmospheric pressure or reduced pressure to form an adsorption phase equilibrium, and the water-soluble polyhydric alcohol is adsorbed into the pores of the adsorbent and stored. The adsorbent described above in the road cryoprotectant of the present invention is preferably included in the content range of 20 to 60% by weight, preferably 30 to 50% by weight. If the content of the adsorbent is out of the above range, it is difficult to attain the desired fast and sustained release simultaneously as a cryoprotectant.
In the present invention, as a thickener, Xanthan, an acrylic polymer or a mixture thereof is selected and included. Xanthan and acrylic polymers selected by the present invention as a thickener have excellent water solubility and have good miscibility with polyhydric alcohols, so that excess polyhydric alcohols can be included and stored in the thickener gel. Do. In addition, xanthan and acrylic polymers are characterized in that the gel form is maintained under low shear force and then converted into a sol form when high shear force is applied. When the sol-gel principle of the thickener is applied to the road cryoprotectant, the cryoprotectant is coated on the road surface in gel form due to the high viscosity of the antifreeze agent in spite of the temperature change and the elapse of time when the vehicle is not in traffic. If a high shear force occurs on the road surface, such as by car traffic, the viscosity of the cryoprotectant is lowered and converted into a sol (Sol) form. In addition, the thickener is expected to control the outflow of the freezing point depressant by the sol-gel principle, as well as another effect of suppressing the loss of the water-soluble polyhydric alcohol used as the freezing point depressant. That is, although the water-soluble polyhydric alcohol is adsorbed and stored in the porous adsorbent as a freezing point depressant to control the fast-acting, the excess (excess) water-soluble polyhydric alcohol used in excess can be easily lost because it is not adsorbed to the adsorbent, but includes a thickener in the present invention By adding a viscosity to the cryoprotectant, an excessive amount of water-soluble polyhydric alcohol is preserved in a gel state, thereby obtaining an effect of not being easily spilled. Therefore, the present invention is expected to have an effect of controlling the outflow of the freezing point depressant according to the traffic volume by using the thickener, and to minimize the loss of excess freezing point depressant to increase the effectiveness of the cryoprotectant. The above-mentioned thickener in the road cryoprotectant of the present invention is preferably included in the content range of 0.01 to 10% by weight, preferably 0.01 to 1% by weight. If the content of the thickener is less than the above range, the viscosity of the cryoprotectant is small and the sustainability is reduced. If the content of the thickener exceeds the above range, the viscosity is too high, which causes difficulty in spraying on the road surface.
Water-soluble polyalcohols, porous adsorbents and thickeners as described above are mixed to produce the cryoprotectant of the present invention, where necessary water may be further added for even mixing between them. At this time, the amount of water is used within the range of 10 to 50 parts by weight based on 100 parts by weight of the total content of the cryoprotectant consisting of a water-soluble polyhydric alcohol, a porous adsorbent and a thickener, the viscosity of the cryoprotectant when the slurry is added by adding too much water May be too low to flow, and the polyhydric alcohol may flow out without being immobilized in the adsorbent, resulting in loss of the polyhydric alcohol.
The cryoprotectant of the present invention is prepared as a gel (Gel) form, and the gel form cryoprotectant is sprayed on the road surface. Gel-type cryoprotectant is sprayed on exposed road surface before snow accumulates, so that snow contacting road surface melts during snowing, and the snow is separated from road surface and becomes floating, so it is not only snow plow Traffic can also make snow removal easier and prevent slippage. And at -5 ℃, the freezing of the road surface is prevented, so it is possible to reduce the slip of the vehicle in the air and the exposed road surface such as bridges, in the sun or in the mountainous areas. The amount of application of the cryoprotectant according to the present invention is slightly different depending on the content of the freezing point depressant and the porosity of the adsorbent, but it is generally preferred to spray 10 to 300 g per square meter (m 2) of the road surface.
The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited to these examples.
Examples 1-13 and Comparative Examples 1-10. Preparation of Cryoprotectants
A cryoprotectant was prepared by mixing the 500 mL volumetric flask in the composition ratio shown in Table 1 below. First, polyhydric alcohol and an adsorbent were added and mixed at room temperature for 30 minutes to adsorb and store the polyhydric alcohol in the adsorbent. Then, a thickener and water were added and stirred for 10 minutes to prepare a cryoprotectant in a gel state.
Experimental example. Measurement of fast and sustained efficacy of cryoprotectant
In order to evaluate the fastness and sustainability of each of the cryoprotectants prepared in Examples 1 to 13 and Comparative Examples 1 to 10, melting time and freezing time were measured by the following method, and the results are shown in Table 1 below. .
[Effectiveness Evaluation Method by Measuring Melting Time]
20 ml of water was placed in a 50 ml glass sample bottle having a diameter of 40 mm, the cap was closed, and the water was frozen in a cooling bath maintained at -5 ° C. After complete freezing, 0.1 g of a cryoprotectant was taken on the ice, and then uniformly applied. The melting time of the ice surface was observed at intervals of 3 minutes over time. The short-acting efficacy of the cryoprotectant was evaluated to be excellent as the melting time was short.
[Effectiveness Evaluation Method by Measuring Freezing Time]
After the ice surface melting sample obtained by the melting time measuring method was put into a cooling bath maintained at -5 ° C for 3 hours from the melting point, the melting time was aged, and the freezing time according to the passage of time at -5 ° C was measured at intervals of 4 hours. It was. The sustained effectiveness of the cryoprotectant was evaluated to be superior as the freezing time increased.
(minute)
(time)
Ethylene glycol (C 2 H 6 O 2 ): Mw 62.07, propylene glycol (C 3 H 8 O 2 ): Mw 76.09,
Glycerin (C 3 H 6 O 3 ): Mw 92.09, Sorbitol (C 6 H 14 O 6 ): Mw 182.17, Mannitol (C 6 H 14 O 6 ): Mw 182.17
[absorbent]
Activated carbon: specific surface area 1,150 ㎡ / g, average particle diameter 1.5 mm
Zeolite: Specific surface area 920 ㎡ / g, Average particle size 1.3 mm
Activated alumina: specific surface area 350 m 2 / g, average particle diameter 1.3 mm
[Thickener]
Polysaccharide gum: Mw> 10 6 , aqueous solution highly pseudoplastic.
Acrylic polymer ((C 3 H 4 O 2 ) n ): Mw 1,250,000 (Aldrich No.306223)
As shown in Table 1, the cryoprotectant prepared in Examples 1 to 13 containing all of the water-soluble polyalcohol, the adsorbent and the thickener according to the present invention was prepared in the form of a gel, without excessive spillage of the polyalcohol. It did not freeze until much later, and it was confirmed that the sustainability was excellent. In addition, Examples 6 to 13 containing an excess of polyhydric alcohol was confirmed that the melting time is excellent within 6 minutes of fast-acting. Among polyhydric alcohols, when ethylene glycol, propylene glycol, and glycerin having a relatively low molecular weight were used, it was confirmed that the fast-acting property was more excellent.
On the contrary, the cryoprotectant of Comparative Examples 1 to 5 containing only water-soluble polyhydric alcohols were prepared in a liquid phase, and were sprayed on the road surface and immediately dissolved in ice and diluted in the form of an aqueous solution. Dilution with water shortens the freezing time, which has a disadvantage of poor sustainability, and when sprayed on the road surface, the liquid polyhydric alcohol is not coated on the road surface and flows down into rain pipes, so the freezing prevention performance rapidly decreases.
In addition, the cryoprotectant of Comparative Examples 6-10 prepared by mixing the water-soluble polyhydric alcohol and the adsorbent had a higher melting time compared to Comparative Examples 1-5, but the fast-acting effect was decreased, but it was confirmed that the freezing time was increased due to the slow release time. In comparison with Examples 1 to 13, the freezing time is small and the sustainability is remarkably decreased.
The cryoprotectant currently applied to the road is composed of only the freezing point lowering agent, as in Comparative Examples 1 to 5, in this case, as described above, there is a short-acting effect is excellent, but the slow release effect is poor. However, the cryoprotectant of the present invention was excellent in sustaining efficacy, and in particular, Examples 6 to 13 were confirmed to be excellent in fastening as well as sustaining efficacy.
Claims (4)
At least one porous adsorbent selected from the group consisting of activated carbon, zeolite and activated alumina; 60 wt%; And
Thickener selected from Xanthan, acrylic polymer or mixtures thereof 0.01? 10 wt%;
Road cryoprotectant, characterized in that it comprises a.
The water-soluble polyhydric alcohol is at least one member selected from the group consisting of ethylene glycol, propylene glycol, glycerin, diethylene glycol, sorbitol, isocitol, and mannitol.
The adsorbent has a specific surface area of 200 to 1500 m 2 / g, and the freezing agent, characterized in that the particle diameter of 0.001 to 3 mm.
Cryoprotective agent, characterized in that prepared in the form of a gel (Gel).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20100132188A KR101164034B1 (en) | 2010-12-22 | 2010-12-22 | Release-rate controlled road antifreezing agent |
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| Application Number | Priority Date | Filing Date | Title |
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| KR20100132188A KR101164034B1 (en) | 2010-12-22 | 2010-12-22 | Release-rate controlled road antifreezing agent |
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| KR20120070749A true KR20120070749A (en) | 2012-07-02 |
| KR101164034B1 KR101164034B1 (en) | 2012-07-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103518824A (en) * | 2013-10-15 | 2014-01-22 | 浙江海洋学院 | Ice-temperature fresh-keeping method for large yellow croakers |
| CN107686278A (en) * | 2017-08-17 | 2018-02-13 | 中盐金坛盐化有限责任公司 | A kind of freeze proof material based on temperature adjusting and its preparation method and application |
| CN108691248A (en) * | 2018-05-18 | 2018-10-23 | 汕头方大印刷包装科技有限公司 | The resistance to frost kink paper of one kind and its production technology |
| CN112457108A (en) * | 2020-12-10 | 2021-03-09 | 山东思科生物科技有限公司 | Medium-trace element water-soluble fertilizer and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101495902B1 (en) | 2014-07-25 | 2015-02-25 | 주식회사 한국환경사업단 | Solidification snow removal materials manufacturing method of liquid calcium chloride snow removal materials using expanded perite |
| KR20160123895A (en) | 2015-04-17 | 2016-10-26 | (주)올젠테크놀로지 | Water ionizer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10251622A (en) | 1997-03-13 | 1998-09-22 | Nof Corp | Antifreezing agent and particle thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103518824A (en) * | 2013-10-15 | 2014-01-22 | 浙江海洋学院 | Ice-temperature fresh-keeping method for large yellow croakers |
| CN107686278A (en) * | 2017-08-17 | 2018-02-13 | 中盐金坛盐化有限责任公司 | A kind of freeze proof material based on temperature adjusting and its preparation method and application |
| CN107686278B (en) * | 2017-08-17 | 2020-05-22 | 中盐金坛盐化有限责任公司 | Anti-freezing material based on temperature regulation and control, and preparation method and application thereof |
| CN108691248A (en) * | 2018-05-18 | 2018-10-23 | 汕头方大印刷包装科技有限公司 | The resistance to frost kink paper of one kind and its production technology |
| CN112457108A (en) * | 2020-12-10 | 2021-03-09 | 山东思科生物科技有限公司 | Medium-trace element water-soluble fertilizer and preparation method thereof |
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| KR101164034B1 (en) | 2012-07-17 |
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