KR20100086204A - High water absorbent polyethylenoxide resin and method thereof - Google Patents

Abstract

PURPOSE: A high water-absorbent polyethylene oxide resin is provided to ensure 200% or more water absorption level without toxicity to the human body. CONSTITUTION: A method for manufacturing a high water-absorbent polyethylene oxide resin comprises: a step of irradiating UV ray to a polyethylene oxide film at 10-600 J/cm^2 for crosslinking; a step of treating 0.1-10.0% of photoinitiator to the surface of polyethylene oxide film and irradiating UV ray; or a step of dipping polyethylene oxide film in crosslinking agent solution and irradiating UV ray. The crosslinking agent is selected from ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacraylate, and polyethylene glycol dimethacrylate.

Description

Super Absorbent Polyethylene Oxide Resin and Manufacturing Method Thereof {High Water Absorbent Polyethylenoxide Resin and Method}

The present invention relates to a superabsorbent polyethylene oxide resin and a method for preparing the same, which are crosslinked by UV irradiation and have a water absorption of 200 to 3100%, and more particularly, gelation and absorption while maintaining morphological stability. It relates to a super absorbent polymer and a method for producing the same that can improve the degree.

A study on absorbent resins was developed around 1965 by polymers crosslinked with polyvinyl alcohol (PVA), polymetacryl acid hydroxyethyl (PMAHE), polyethylene glycol (PEG), and so on. It started with the use of artificial lens. Research on super absorbent polymers has been carried out since 1974, when resins that absorbed water of about 1,000 times were developed, crosslinking water-soluble materials having functional groups such as -OH, -NH3, and -COOH to form a three-dimensional network structure. Research into producing an absorbent resin has been conducted. A superabsorbent polymer is a material having a high absorption capacity of several hundreds to thousands of times its own weight, and after absorbing water, water should not be easily released at any pressure, and it should have a fast absorption rate depending on the use. Therefore, the condition that the superabsorbent polymer should be basically required physical properties such as high absorption amount, fast absorption rate, gel strength to have a stable water retention.

The main materials forming superabsorbent polymers are partially crosslinked polyacrylates, hydrolyzed starch-acrylonitrile copolymers, polyacrylamide polymers, and the like, and have been continuously developed since the discovery of these superabsorbent resins. In addition, researches on applied materials have been actively conducted, and they are also used in various fields such as hygiene products, civil horticulture, pharmaceuticals, flocculation of sediment, dehydration from oil, and prevention of dew condensation of building materials. Polymerization methods for producing a highly moist water-based resin using partially crosslinked acrylic acid and acrylate salts include bulk polymerization, suspension polymerization, emulsion polymerization, and reverse phase suspension polymerization. However, polymerization methods other than reverse phase emulsion polymerization and reverse phase suspension polymerization are difficult to remove the heat of polymerization during the process, and the gel-effect makes it difficult to obtain the product in the form of particles.

In general, three characteristics of the superabsorbent polymer, such as absorption, absorption rate, and gel strength, are affected by particle size and shape, type of crosslinking agent, crosslinking density, type of dividing agent, and polymerization temperature.

In recent years, super absorbent polymers have been developed that can be used directly as sanitary materials, and the absorption can be maximized by the crosslinking effect of chemical crosslinking inside the particles and physical entanglement of the polymer backbone, and the absorption rate is improved by crosslinking the surface of the particles. Has been reported.

The principle of absorption is that crosslinking the water-soluble polymer increases the crosslinking density of the resin and changes to a hydrophilic resin such as an ion exchange resin.

However, if crosslinked, the superabsorbent polymer, which is a polymer electrolyte, is crosslinked between polymer ions, so that infinite expansion is impossible.

Accordingly, the inventors of the present invention have been found to improve the absorbency while maintaining the properties and shape stability of the PEO film, and have confirmed that the absorbency is improved by crosslinking using ultraviolet irradiation to complete the present invention.

It is an object of the present invention to provide a superabsorbent polyethylene oxide resin, which is crosslinked by ultraviolet irradiation and has a water absorption of 200 to 3100%.

It is another object of the present invention to provide a method for preparing the super absorbent polymer.

In order to achieve the above object, the present invention provides a superabsorbent polyethylene oxide resin, which is crosslinked by ultraviolet irradiation, the water absorption of 200 ~ 3100%.

In addition, the present invention provides a method for producing a superabsorbent polyethylene oxide resin having a water absorption of 1000 to 3000% by crosslinking by irradiating the ultraviolet light of 10 to 600 J / cm 2 to the polyethylene oxide film.

In addition, the present invention is to prepare a super absorbent polyethylene oxide resin having a water absorption of 1000 to 3000%, characterized in that the crosslinking agent solution is immersed in the polyethylene oxide film and absorbing the crosslinking agent, and then crosslinked by ultraviolet irradiation. Provide a method.

Hereinafter, the present invention will be described in detail.

In one aspect, the present invention relates to a superabsorbent polyethylene oxide resin, which is crosslinked by ultraviolet irradiation and has a water absorption of 200 to 3100%. The ultraviolet irradiation energy is preferably 10 to 600 J / cm ² , wherein the absorbance is defined as the weight ratio measured by vacuum drying at 50 ℃ after leaving for 48 hours in a constant temperature water bath of 30 ℃.

In addition, the UV irradiation in the embodiment of the present invention was used a continuous UV-curing machine (Lichtzen) having an output of 80W / cm and the UV irradiation energy is 10 when manufacturing a super absorbent resin only by UV irradiation 600 J / cm <^2> is preferable, More preferably, it is 100-400 J / cm <^2> . In the case of preparing a super absorbent polymer using adsorption of the crosslinking agent and ultraviolet irradiation, the ultraviolet irradiation energy is preferably 10 to 100 J / cm ² , more preferably 20 to 60 J / cm ² .

In another aspect, the present invention provides a method for producing a superabsorbent polyethylene oxide resin having a water absorption of 1000 to 3000% by crosslinking the polyethylene oxide film by irradiating 10 to 600 J / cm 2 of ultraviolet light.

In addition, the present invention, when the photoinitiator is added to the surface of the polyethylene oxide film 0.1 to 10.0% of the weight of the polyethylene oxide by treating the surface of the polyethylene oxide film, characterized in that the cross-linking by irradiating ultraviolet rays 200 to 500% It provides a method for producing a phosphorus superabsorbent polyethylene oxide resin. At this time, the ultraviolet irradiation energy is preferably 10 to 100 J / cm ² , the photoinitiator benzyl dimethyl ketal, benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether , Benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, 2,4-diethyl thioxanthone, 1-hydroxycyclohexylphenyl ketone, benzyl diphenyl sulfide, tetramethyl thiuram monosulfide and 2 It can be used selected from, 2-dimethoxy-2-phenylacetophenone, the concentration of the photoinitiator is preferably 0.1 to 1.0% by weight of the water-soluble polymer. The said composition ratio is a suitable composition ratio for obtaining a photoinitiation effect.

In still another aspect, the present invention provides a superabsorbent polyethylene oxide resin having a water absorption of 1000 to 3000% by immersing the polyethylene oxide film in the crosslinking agent solution, absorbing the crosslinking agent, and then crosslinking by UV irradiation. It provides a method of manufacturing. Examples of the crosslinking agent that can be crosslinked by ultraviolet irradiation include ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TEGDMA), and polyethylene glycol dimethacrylate ( PEGDMA) and to a method for preparing super absorbency according to the increase in molecular weight. Conventionally well-known crosslinking agents crosslink polymers in the form of films or fibers using high temperature thermal energy to produce superabsorbent polymers, and thus have problems in manufacturing cost and environmental pollution. Thus, in the present invention, the above-mentioned dimethacrylate, which can be crosslinked using ultraviolet irradiation, can be used as a low cost and environmentally friendly process due to more complete and less energy use.

Although the immersion time in the said crosslinking agent aqueous solution is not specifically limited, Usually, 1 second-20 minutes, Preferably they are 5 second-15 minutes.

In addition, the PEO film of the superabsorbent polymer can be obtained by UV irradiation alone without adsorption of the crosslinking agent, but after absorbing under the crosslinking agent solution, the absorbency was lower than that obtained by UV irradiation. In the case of PEO film which is a super absorbent polymer by crosslinking agent adsorption and ultraviolet irradiation, the kind of the PEO film is not particularly limited in the present invention, but in consideration of solubility in water, only a viscosity average molecular weight of 500 to 60 is preferred, and more preferred. It is 1,000 to 300,000. The thickness of a film is 50-200 micrometers, Preferably it is 100-200 micrometers.

As described in detail above, according to the present invention, the water absorption can satisfy 200% or more, and can provide a super absorbent polymer that is harmless to the human body while maintaining the properties and shape stability of the PEO resin.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to the Examples.

Experimental Example 1

Absorption of uncolored PEO film crosslinked by irradiating irradiation energy at 13.2 to 528J / cm ² by adjusting the UV irradiation time using a continuous UV-curing machine (Lichtzen) with an output of 80W / cm The crosslinking average molecular weight and the crosslinking density were also measured.

In addition, the concentration of benzophenone as a photoinitiator was 0.07 to 2.0% of the weight of the PEO when the crosslinked by irradiation with UV irradiation energy of 44 J / cm ² was measured for absorbance, high average molecular weight and crosslink density.

<Production of Example>

Example 1

Irradiation energy of 13.2J / cm ² using a continuous UV-curing machine (Lichtzen) with an output of 80W / cm for a polyethylene oxide film (Aldrich) having an average molecular weight of 300,000 and a thickness of about 200 μm. Irradiation with and crosslinking were carried out. Absorbance, crosslinking average molecular weight and crosslinking density of the obtained film were measured, and the results are shown in Table 1 below.

Examples 2-5

It was prepared in the same manner as in Example 1, except that the superabsorbent polymer was prepared by varying ultraviolet irradiation energy as shown in Table 1 below. Absorbance, crosslinking average molecular weight and crosslinking density of the obtained film were measured, and the results are shown in Table 1 below.

Examples 6-9

Prepared in the same manner as in Example 2 except using a hydrogen-substituted benzophenone (Benzophenone) as a photoinitiator to crosslink by varying the photoinitiator concentration to 0.07 to 2.0% by weight of PEO to prepare a super absorbent polymer. Absorbance, crosslinking average molecular weight and crosslinking density of the obtained film were measured, and the results are shown in Table 1 below.

Irradiation energy
(J / cm ² ) Photoinitiator
(wt%) Bridge
Number average molecular weight
(g / mol) Crosslinking density
(mol / cm ³ ) Gelation rate (%) Absorbance (%) Example 1 13.2 - 3563.8 3.2 10.2 1338.0 Example 2 44.0 - 7427.8 1.5 18.3 1458.0 Example 3 105.6 - 9404.4 1.2 19.9 1589.0 Example 4 264.0 - 30968.0 0.4 37.4 2451.0 Example 5 316.8 - 39940.5 0.3 38.8 2785.0 Example 6 44.0 0.21 810.1 13.9 60.7 292.0 Example 7 44.0 0.49 2393.3 4.7 78.4 442.0 Example 8 44.0 0.91 903.0 12.5 81.6 268.0 Example 9 44.0 2.0 960.5 11.8 89.8 264.0

Experimental Example 2

Example 10

Prepared in the same manner as in Example 2, but using a ethylene glycol dimethacrylate (Ethyleneglycol dimethacrylate) as a crosslinking agent and using a concentration of the crosslinking agent in 0.00045 to 0.0081 mol% to prepare a super absorbent polymer. Absorbance, crosslinking average molecular weight and crosslinking density of the obtained film were measured, and the results are shown in Table 2 below.

Example 11

Prepared in the same manner as in Example 10 except using diethylene glycol dimethacrylate (Dienthyleneglycol dimethacrylate) as a crosslinking agent. Each crosslinking agent aqueous solution concentration is shown in Table 2.

Example 12

Prepared in the same manner as in Example 10 except using triethylene glycol dimethacrylate (Trienthyleneglycol dimethacrylate) as a crosslinking agent. Each crosslinking agent aqueous solution concentration is shown in Table 2.

Example 13

Prepared in the same manner as in Example 10 except using polyethylene glycol dimethacrylate (Polyenthyleneglycol dimethacrylate) as a crosslinking agent. Each crosslinking agent aqueous solution concentration is shown in Table 2.

From Tables 1 and 2 above, by crosslinking the PEO film, the gelation rate is 10% or more, and the absorption rate for the PEO film left for 48 hours in a gelled PEO film at 30 ℃ water can be confirmed that more than 200% It is shown that this improves the gelation rate and the absorbency while maintaining the morphological stability.

As described above, according to the present invention, it is possible to prepare a super absorbent polymer having a water absorption degree of 200% or more, and to be harmless to a human body.

Claims (10)

A superabsorbent polyethylene oxide resin, which is crosslinked by ultraviolet irradiation and has a water absorption of 200 to 3100%. (However, absorbance: Weight ratio measured by vacuum drying at 50 ℃ after leaving for 48 hours in a constant temperature water bath of 30 ℃.) The super absorbent polyethylene oxide resin of claim 1, wherein the ultraviolet radiation energy is 10 to 600 J / cm ² . Method of producing a super absorbent polyethylene oxide resin having a water absorption of 1000 to 3000% by crosslinking the polyethylene oxide film by irradiating 10 to 600 J / cm ² by ultraviolet light. (However, absorbance: Weight ratio measured by vacuum drying at 50 ℃ after leaving for 48 hours in a constant temperature water bath of 30 ℃.) To prepare a super absorbent polyethylene oxide resin having a water absorption of 200 to 500%, characterized in that the surface of the polyethylene oxide film is treated with a photoinitiator of 0.1 to 10.0% by weight of the polyethylene oxide, and crosslinked by irradiating with ultraviolet rays. Way. The method of claim 4, wherein the ultraviolet irradiation energy is 10 to 100 J / cm ² . The method of claim 4, wherein the photoinitiator benzyl dimethyl ketal, benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl Selected from benzoin benzoate, 2,4-diethylthioxanthone, 1-hydroxycyclohexylphenyl ketone, benzyldiphenylsulfide, tetramethylthiuram monosulfide and 2,2-dimethoxy-2-phenylacetophenone Characterized in that the method. A method of producing a superabsorbent polyethylene oxide resin having a water absorption of 1000 to 3000%, characterized in that the crosslinking agent is immersed in a polyethylene oxide film and then crosslinked by irradiation with ultraviolet rays. The method of claim 7, wherein the crosslinking agent is ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TEGDMA) and polyethylene glycol dimethacrylate (PEGDMA) It is selected from among the method. The method of claim 8, wherein the concentration of the crosslinker is 0.00005 to 0.01 mol%. The method of claim 8, wherein the ultraviolet irradiation energy is characterized in that 10 to 100 J / cm ² .