CN111138590A - Acrylic ester crosslinking agent for absorbent resin, method for producing same, and biodegradable high-absorbent resin containing same - Google Patents
Acrylic ester crosslinking agent for absorbent resin, method for producing same, and biodegradable high-absorbent resin containing same Download PDFInfo
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- CN111138590A CN111138590A CN201911075769.9A CN201911075769A CN111138590A CN 111138590 A CN111138590 A CN 111138590A CN 201911075769 A CN201911075769 A CN 201911075769A CN 111138590 A CN111138590 A CN 111138590A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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Abstract
The present invention relates to a method for preparing an acrylic ester-based crosslinking agent for absorbent resins, an acrylic ester-based crosslinking agent for absorbent resins prepared thereby, and a biodegradable super absorbent resin comprising the same, which are prepared by subjecting a compound represented by the following chemical formula 1 to an acrylation reaction: chemical formula 1:
Description
Technical Field
The present invention relates to a method for producing an acrylic ester-based crosslinking agent for an absorbent resin, an acrylic ester-based crosslinking agent for an absorbent resin produced by the method, and a biodegradable super absorbent resin containing the same, and more particularly, to a method for producing an acrylic ester-based crosslinking agent for an absorbent resin, an acrylic ester-based crosslinking agent for an absorbent resin produced by the method, and a biodegradable super absorbent resin containing the same, as follows: after the biomass-based acrylate cross-linking agent is synthesized, the acrylate cross-linking agent is used as a cross-linking agent of biodegradable high-absorptivity resin with a main chain of polyitaconic acid, so that the biodegradability and water replenishing capability are improved, the environmental pollution is reduced, the consumption of petrochemical products is reduced, the energy can be saved, the discharge of pollutants is reduced, and the environment is protected.
Background
A Super Absorbent Polymer (SAP) is a resin that absorbs water several hundred to several thousand times its weight to swell and gel. The highly absorbent resin is used in various fields such as sanitary materials for paper diapers and sanitary products, medical fields for body fluid absorbing materials, civil engineering and construction fields for sealing materials (water-stopping materials) and moisture condensation preventing materials, food fields for freshness retaining materials, industrial fields for dehydrating agents for removing water from solvents, and agricultural and horticultural fields for greening. Various absorbent resins have been proposed according to their use.
Recently, sanitary materials such as disposable diapers and sanitary products have been made more functional and thinner to improve physical properties such as durability of a glue, diffusibility of an aqueous liquid, and fluidity. The crosslinking agent used in the production of the absorbent resin has an important influence on the physical properties of the absorbent resin.
Conventionally, a crosslinking agent used in the production of an absorbent resin can be easily introduced into water industrially. Conventional absorbent resins are inexpensive, have excellent affinity and polymerizability with hydrophilic unsaturated monomers, and have high stability. For example, the conventional absorbent resin may be a polyol unsaturated carboxylic acid ester. Conventionally, the content of a crosslinking agent based on such a petrochemical product has been increased in order to improve the physical properties of an absorbent resin. However, there is a problem that many properties of the absorbent resin are degraded.
In addition, most of the polyacrylate compounds conventionally used as absorbent resins are not biodegradable, and when they are disposed of as waste, they cause environmental problems. For example, in the case of landfill treatment, the waste water is not decomposed by bacteria, microorganisms, and the like in the ground, and therefore, environmental pollution and the like may be caused.
In order to solve the above problems, various studies have been made at home and abroad in korea to develop a resin having excellent biodegradability using materials derived from biomass. However, the biodegradable resin as described above has disadvantages of reduced absorbability and high production cost.
Therefore, it is necessary to study a technique for synthesizing a crosslinking agent that exhibits physical properties equivalent to or higher than those of an absorbent resin crosslinked by using a conventional petroleum-based raw material as a crosslinking agent, improves biodegradability, and reduces environmental characteristics such as discharge of pollutants.
The background art related to the present invention has korean patent laid-open publication No. 10-1779091 (granted 09/11/2017), which discloses a method for preparing an acrylate-based crosslinking agent having a biodegradable main chain.
Disclosure of Invention
The invention aims to provide a preparation method of an acrylate crosslinking agent for biomass-based absorbent resin, which comprises the following steps: has excellent biodegradability, improved water replenishing performance when preparing high-absorptivity resin, reduced consumption related to petrochemical products, reduced environmental pollution and environmental protection.
Still another object of the present invention is to provide an acrylic crosslinking agent for absorbent resin prepared by the above method for preparing an acrylic crosslinking agent for absorbent resin.
Another object of the present invention is to provide a biodegradable super absorbent resin containing the acrylic ester-based crosslinking agent for absorbent resins.
The method for producing an acrylic ester-based crosslinking agent for absorbent resins of the present invention for achieving the above object is characterized by subjecting a compound represented by the following chemical formula 1 to an acrylation reaction.
Chemical formula 1:
the present invention is characterized in that the compound represented by the above chemical formula 1 is prepared by acrylation reaction using methacrylate ester containing isocyanate group (NCO)
The present invention is characterized in that the isocyanate group-containing methacrylate contains 2-isocyanatoethyl methacrylate, and 0.8 to 1.2 moles of the isocyanate group-containing methacrylate is added to 1 mole of the compound represented by the chemical formula 1 to perform an acrylation reaction.
The present invention is characterized by being prepared by subjecting a compound represented by the above chemical formula 1 to an acrylation reaction using an epoxy oligomer epoxidized with an epichlorohydrin compound.
The epoxidation reaction is characterized in that the epoxidation reaction further includes a phase change catalyst, 5 to 10mol of the epichlorohydrin compound is added to 1mol of the compound represented by chemical formula 1 to perform a reaction, and the phase change catalyst is included in an amount of 0.2 to 0.5 wt% based on the total weight of the compound represented by chemical formula 1 and the epichlorohydrin compound.
The present invention is characterized in that, in the acrylation reaction, 0.8 to 1.2 moles of an acrylate compound containing acrylic acid (acrylic acid), methacrylic acid (methacrylic acid) and a mixture thereof is added to 1 mole of the epoxy oligomer to perform the reaction.
The method for producing an acrylic ester crosslinking agent for absorbent resin of the present invention is characterized by comprising: a step (a1) of synthesizing an urethane acrylate crosslinking agent by subjecting a compound represented by the following chemical formula 1 to an acrylation reaction using a methacrylate ester having an isocyanate group; or a step (a2) of preparing an epoxy oligomer by reacting a compound represented by the following chemical formula 1 with a mixture containing an epichlorohydrin compound; and a step (b2) of reacting the epoxy oligomer prepared in the step (a2) with an acrylate compound to synthesize an epoxy acrylate crosslinking agent.
Chemical formula 1:
the present invention is characterized in that the method for producing the acrylic ester-based crosslinking agent for absorbent resin further comprises: a step of measuring Fourier transform infrared spectroscopy (FT-IR) for the product of the step (a1) and terminating the reaction at a time point when the peak of the isocyanate group is completely disappeared; or a step of measuring an acid value (acid value) for the product of the above step (b2) and ending the reaction at a time point when the acid value is 3 or less.
The acrylic crosslinking agent for absorbent resins of the present invention for achieving the above further object is characterized by being prepared by the above method for preparing an acrylic crosslinking agent for absorbent resins, and comprising a compound represented by the following chemical formula 1.
Chemical formula 1:
the present invention is characterized in that the acrylic ester-based crosslinking agent for absorbent resin is selected from a compound represented by the following chemical formula 2, a compound represented by the chemical formula 3, or a mixture thereof.
Chemical formula 2:
chemical formula 3:
the present invention is characterized in that the acrylic ester-based crosslinking agent for absorbent resin satisfies the following formulas 1 to 4.
Formula 1: Mw-U is more than or equal to 400 and less than or equal to 500
Formula 2: PDI-U is more than or equal to 1.0 and less than or equal to 1.5
Formula 3: Mw-E is more than or equal to 450 and less than or equal to 550
Formula 4: PDI-E is more than or equal to 1.2 and less than or equal to 1.6
In the above formulas 1 and 3, Mw-U and Mw-E respectively mean the weight average molecular weight (g/mol) of the urethane acrylate crosslinking agent and the epoxy acrylate crosslinking agent of the present invention, and in the above formulas 2 and 4, PDI-U and PDI-E mean the PolyDispersity Index (polydispersindex) which is the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn).
The biodegradable super absorbent resin of the present invention for achieving the above another object is characterized by being prepared from a monomer containing (C4-C6) aliphatic dicarboxylic acid and an acrylic ester crosslinking agent for fir absorbent resin.
The present invention is characterized in that the (C4-C6) aliphatic dicarboxylic acid-containing monomer contains itaconic acid or maleic acid, and the acrylic crosslinking agent for an absorbent resin is contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the (C4-C6) aliphatic dicarboxylic acid-containing monomer.
The present invention is characterized in that the acrylic ester-based crosslinking agent for absorbent resin is selected from a compound represented by the following chemical formula 2, a compound represented by the chemical formula 3, or a mixture thereof.
Chemical formula 2:
chemical formula 3:
according to the present invention, an acrylic ester-based crosslinking agent for absorbent resins is prepared by acrylating isosorbide (isosorbide), which is 100% of a natural biomass using corn as a raw material. Thus, the crosslinking agent itself is excellent in biodegradability and biodegradability in the production of a high-absorbency resin, and a high-absorbency resin having improved water-replenishing performance can be produced.
Also, the high absorbent resin of the present invention has advantages in that the consumption of petrochemical products is reduced, and at the same time, environmental pollution occurring during the production of petrochemical products can be reduced. And, the generation of Volatile Organic Compounds (VOCs) is prevented without using an organic solvent, which is environmentally friendly and can reduce toxicity.
Further, the present invention has an effect of environmental protection because harmful substances such as dioxin are not generated when the absorbent resin prepared by including the acrylic ester-based crosslinking agent for absorbent resin is buried or incinerated.
Drawings
Fig. 1 is a flowchart showing a method for producing an acrylic ester-based crosslinking agent for absorbent resins of the present invention.
Fig. 2 shows a reaction mechanism of a step of synthesizing the urethane acrylate-based cross-linking agent according to an embodiment of the present invention.
FIG. 3 shows the reaction mechanism of the epoxy acrylate crosslinker synthesis step according to an embodiment of the present invention.
FIG. 4 is a Fourier transform infrared spectrometry chart of the urethane acrylate crosslinking agent according to an embodiment of the present invention.
FIG. 5 is a chart showing the measurement of the molecular weight of the urethane acrylate-based cross-linking agent according to an embodiment of the present invention.
FIG. 6 is a Fourier transform infrared spectrometry chart of an epoxy acrylate based cross-linking agent according to an embodiment of the present invention.
FIG. 7 is a chart of molecular weight measurements of epoxy acrylate crosslinkers in accordance with one embodiment of the present invention.
Detailed Description
Advantages and/or features of the present invention and methods of accomplishing the same may be understood more clearly by reference to the drawings and the detailed description of embodiments. However, the present invention is not limited to the embodiments disclosed below, and can be realized in various forms different from each other, and the embodiments only make the disclosure of the present invention more complete, so that those skilled in the art to which the present invention pertains can more completely understand the scope of the present invention, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.
Hereinafter, a method for producing an acrylic ester-based crosslinking agent for an absorbent resin, an acrylic ester-based crosslinking agent for an absorbent resin produced by the method, and a biodegradable super absorbent resin containing the same according to preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Isosorbide is a 100% biomass material obtained by using corn as a raw material, and is produced by a process of extracting starch from corn, and then using glucose, sorbitol, or the like. Isosorbide is used as a material for bioplastics. Unlike conventional plastics using petrochemicals as raw materials, plastics prepared using isosorbide are nontoxic, decompose well, and have excellent transparency, surface hardness, and the like.
The present invention is characterized by providing an acrylic ester-based crosslinking agent for an absorbent resin prepared by subjecting isosorbide as a biomass substance to acrylation reaction, and a biodegradable absorbent resin containing the same.
The acrylic ester cross-linking agent for the absorbent resin and the biodegradable super-absorbent resin containing the same have excellent biodegradation property and water replenishing property, and the biodegradable super-absorbent resin has the characteristics of saving energy and reducing pollutant discharge and is environment-friendly. The biodegradable high-absorbable resin is used not only for sanitary products but also for soil water-replenishing agents for horticulture, water-stopping materials for civil engineering or construction, mats for raising seedlings, freshness-keeping agents, hot packs, and the like.
Fig. 1 is a flowchart showing a method for producing an acrylic ester-based crosslinking agent for absorbent resins of the present invention.
Referring to fig. 1, the method for preparing the acrylic ester-based crosslinking agent for absorbent resin according to the present invention may include: (a1) synthesizing a urethane acrylate crosslinking agent; or (a2) an epoxy oligomer preparation step; and (b2) a step of synthesizing an epoxy acrylate crosslinking agent.
Chemical formula 1:
the following will describe (a1) the procedure for synthesizing the urethane acrylate-based crosslinking agent in detail.
(a1) Synthesis step of urethane acrylate crosslinking agent
In the urethane acrylate crosslinking agent synthesis step, a compound represented by the following chemical formula 1 is subjected to an acrylation reaction using an isocyanate group-containing methacrylate to obtain the urethane acrylate crosslinking agent.
Chemical formula 1:
isosorbide represented by the above chemical formula 1 is a bicyclic compound of a diol containing two fused furan rings and an oxygen-containing heterocyclic compound. To obtain 100% natural biomass using corn as a raw material, D-sorbitol is obtained by contact hydrogenation of D-glucose, which is sequentially produced by hydrolysis of starch, after extraction of starch from corn. Such isosorbide is useful as a material for biodegradable derivatives that can achieve various functions.
The reaction can be carried out by charging an organic solvent into a reactor containing such isosorbide, raising the temperature to the first reaction temperature, then charging a catalyst, and stirring.
The first reaction temperature may be 70 to 90 ℃, preferably 70 to 80 ℃ in order to effectively control the reaction heat and uniformly synthesize.
The catalyst is not limited to the catalyst added for increasing the reaction rate, and may include an amine-based catalyst, a tin-based catalyst, a bismuth-based catalyst, and a mixture of one or more of them. For example, one or more selected from triethylenediamine (DABCO; 1, 4-diazabicyclo [2.2.2] octane), dibutyl Tin dilaurate (DBTDL, dibutyl Tin dilaurate), Tin 2-ethylhexanoate (stannou octate, Tin 2-ethylhexoate), and bismuth 2-ethylhexanoate (Bismuthoate). Wherein, the dibutyl tin dilaurate is a light yellow liquid, the catalyst activity is high, and the reaction speed is easy to adjust.
The catalyst may be contained in an amount of 0.8 to 1 part by weight, based on 100 parts by weight of the isosorbide. In the case where the content of the catalyst is less than 0.8 part by weight, the reaction rate is slow. In contrast, in the case of more than 1 part by weight, by-products may be generated due to rapid heat generation.
The organic solvent is added to uniformly disperse isosorbide, and is selected from one or more of benzene, chloroform, diethyl ether, ethyl acetate and their mixture. More preferably, the dispersion is performed to ethyl acetate to improve the dispersion effect, thereby efficiently preparing a uniform urethane acrylate-based crosslinking agent.
Subsequently, an isocyanate group-containing methacrylate ester may be charged into the reactor to carry out the reaction. More specifically, 2-isocyanatoethyl methacrylate (2-isocyanato ethyl (meth) acrylate) may be included.
The following chemical formula 4 is a chemical formula showing ethyl 2-isocyanatoacrylate (2-isocyanato ethyl acrylate).
Referring to chemical formula 4, the structural formula of ethyl 2-isocyanatoacrylate contains CH2 ═ C —. And contains an isocyanate group (-NCO) which can easily react with-OH, -COOH, -NH2, etc. at a low temperature of 60 ℃ or lower.
Chemical formula 4:
the isocyanate group-containing methacrylate may be contained in an amount of 0.8 to 1.2mol, more preferably 0.9 to 1.1mol, relative to 1mol of the isosorbide.
When the content is in the above range, the formation of by-products such as diacrylate can be suppressed. Further, the crosslinking density of the crosslinking agent can be effectively controlled without biodegradability, and thus the water replenishing ability can be improved.
When the content of the isocyanate group-containing methacrylate ester is less than 0.8mol, there is a problem that the water-replenishing ability is lowered. On the contrary, in the case of more than 1.2mol, the amount of unreacted acrylic monomer becomes large, and there is a problem that acrylic polymerization may occur.
Preferably, the isocyanate group-containing methacrylate is dropped by a dropping funnel (dropping funnel) for 0.5 to 2 hours. More preferably, the dripping is for 0.5 to 1 hour. In the dropping process, the-OH (hydroxyl) functional group of isosorbide reacts with the-isocyanate functional group of ethyl 2-isocyanatomethacrylate to synthesize a biodegradable acrylate crosslinking agent having an amide structure (amide group (-NHCO-)).
The fourier transform infrared spectrum may be measured during the reaction to terminate the reaction at a point of time when the isocyanate peak of the above acrylic monomer completely disappears.
Specifically, it was confirmed that the peak value of the functional group was determined by measuring Fourier transform Infrared spectroscopy (FT-IR) at predetermined time intervals during the reaction. FIG. 4 is a graph showing Fourier transform infrared spectroscopy measurement of a urethane acrylate-based crosslinking agent according to an embodiment of the present invention. In this graph, it may be 3300cm-1The peak value of the urethane (CONH) was confirmed to be 1600cm-1The peak was confirmed for C ═ C double bond acrylate.
FIG. 5 is a graph showing the measurement of the molecular weight of the urethane acrylate-based crosslinking agent according to the embodiment of the present invention. The urethane acrylate crosslinking agent prepared by the above preparation method can satisfy the following formulas 1 and 2.
Formula 1: Mw-U is more than or equal to 400 and less than or equal to 500
Formula 2: PDI-U is more than or equal to 1.0 and less than or equal to 1.5
In the above formula 1, Mw-U means the weight average molecular weight (g/mol) of the urethane acrylate-based crosslinking agent of the present invention, and in the above formula 2, PDI-U means the polydispersity index, which is the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn).
When the formula 1 and the formula 2 are satisfied, the biodegradability of the urethane acrylate crosslinking agent can be improved, and the water replenishing ability can be effectively improved when the biodegradable super absorbent resin is prepared.
The following will describe in detail the (a2) epoxy oligomer production step and (b2) epoxy acrylate crosslinking agent synthesis step.
(a2) Epoxy oligomer preparation step
The above epoxy oligomer preparation step reacts a mixture containing isosorbide and an epichlorohydrin compound. More specifically, a mixture containing isosorbide and an epichlorohydrin compound is charged with a phase transition catalyst to perform a reaction, and an aqueous sodium hydroxide solution is added to perform ripening and purification.
The epichlorohydrin compound is added to introduce an epoxy group, and includes one or more of epichlorohydrin (epichlorohydrin), epibromohydrin (epibromohydrin), and epifluoropropane (epifluorohydrin). Further, epichlorohydrin is effective for improving the reactivity of epoxy ring formation and reducing the cost.
Preferably, 5 to 10mol of the above-mentioned epichlorohydrin compound is charged with respect to 1mol of isosorbide. More preferably, the epichlorohydrin compound is charged in an amount of 8 to 10mol, and a suitable epoxy oligomer can be produced by using the crosslinking agent for an absorbent resin, and therefore, it is effective. In the case where the content of the epichlorohydrin compound is less than 5mol or more than 10mol, it is difficult to adjust the molecular weight of the crosslinking agent, and therefore, it is not suitable for use as a crosslinking agent for an absorbent resin.
The phase change catalyst is charged for the epoxidation reaction. For example, as long as the phase transition catalyst is known, one or more kinds of tetramethylammonium chloride, tetrabutylammonium bromide, tetraethylammonium iodide, tetrabutylammonium iodide, trimethylhexadecylammonium chloride, dioctadecyldimethylammonium chloride, trimethylbenzylammonium chloride, and trioctylmethylammonium chloride may be used. More preferably, Tetrabutylammonium bromide (Tetrabutylammonium bromide) may be selected.
The phase transition catalyst may be contained in an amount of 0.2 to 0.5 weight percent relative to the total weight of the isosorbide and epichlorohydrin compound. More preferably, it may comprise 0.3 to 0.4 weight percent.
When the content of the phase change catalyst is within the range as described above, the epoxidation reaction is efficiently performed, and therefore, it is preferable. When the amount is less than 0.2% by weight or more than 0.5% by weight, it is difficult to control the reaction rate, and there is a concern that a problem of not uniformly synthesizing the epoxy oligomer occurs.
According to an embodiment of the present invention, the isosorbide, the epichlorohydrin compound, the phase transition catalyst, and an organic solvent can be added to the reactor independently of the order. Also, the epoxidation reaction may be carried out under an inert atmosphere such as nitrogen.
For example, isosorbide, an epichlorohydrin compound, and a phase transition catalyst are charged into a reactor, and the mixture is stirred at room temperature for 5 to 20 minutes, and then the temperature is raised to 90 to 110 ℃ which is the second reaction temperature to perform the reaction. The above reaction time may be carried out for 10 to 60 minutes. More preferably, it may be performed for 20 to 40 minutes.
The epoxy oligomer synthesized by the method as described above may also be subjected to aging and purification processes.
The reactant subjected to the above-mentioned epoxy oligomer production step of (a1) is cooled to 40 ℃ to 60 ℃, and an aqueous sodium hydroxide solution may be charged. In the charging method, in order to uniformly purify the synthesized epoxy oligomer, it is effective to perform a dropping charge for 2 to 4 hours using a dropping funnel.
The concentration of the above-mentioned aqueous sodium hydroxide solution may be 30 to 60 weight percent. Preferably, 10 to 30 weight percent of aqueous sodium hydroxide solution is added with respect to the total weight of the isosorbide and epichlorohydrin compound.
After completion of dropping of the above-mentioned aqueous sodium hydroxide solution, the mixture may be aged at a temperature of 40 ℃ to 60 ℃ for 1 hour to 5 hours. After removing the salt thus produced by washing with water and filtration, the epichlorohydrin compound contained in excess is recovered under a temperature condition of 100 to 150 ℃ to obtain an epoxy oligomer.
(b2) Synthesis step of epoxy acrylate crosslinking agent
The above epoxy acrylate-based cross-linking agent synthesizing step reacts the epoxy oligomer prepared in the above step (a2) with an acrylate compound.
The above-mentioned acrylate compound is not limited to a compound having one or more unsaturated carboxyl groups, and for example, may be selected from acrylic acid, methacrylic acid and a mixture thereof.
The step of synthesizing the epoxy acrylate crosslinking agent (b2) may further include a catalyst to increase the reaction rate. The above catalyst is used to smoothly react the epoxy ring of the epoxy oligomer prepared in the step (a) with the-COOH group of the acrylate compound. For example, the catalyst may be selected from one or more of Boron trifluoride (borontrifluoride), titanium acylate (titanylacetates), tetrabutyl titanate (tetrabutyl titanate), aluminum isopropoxide (aluminum isopropoxide), tin octoate (tinoctoate), tin acetate (tinacetate), butylstannoic acid (Butyl stannoic acid), Hydrated butyltin Oxide (Hydrated monobutyltin Oxide), monobutyltin chloride (monobutyltin dihydroxide), Stannous Oxalate (Stannous Oxide), Dibutyltin Diacetate (dibutyl Diacetate), di-n-butyltin Oxide (dibutyl Oxide), Dibutyltin dilaurate, Dibutyltin dimethoxide (dibutyl Oxide), Dibutyltin Dibutoxide (dibutyl Oxide), and triphenylPhosphine (triphenylPhosphine). More preferably, triphenylphosphine is used to effectively suppress side reactions and improve reaction efficiency.
The catalyst may be included in an amount of 0.3 to 0.7 wt% based on the total weight of the epoxy oligomer and the acrylate compound. In the case where the content of the catalyst is less than 0.3% by weight, the reaction speed is slow. In contrast, in the case of more than 0.7 weight percent, there is a risk of generating by-products by the polymerization reaction of the acrylic ester due to the sharp heat generation.
According to an embodiment of the present invention, the acrylic ester compound and the polymerization inhibitor are charged into the reactor, and the temperature is raised to 60 to 80 ℃ to charge the epoxy oligomer prepared in the epoxy oligomer preparation step (a 2). Preferably, the epoxy oligomer is divided and fed at least three times to control a rapid exothermic reaction, and is dropped and fed by a dropping funnel.
When the acrylate compound and the epoxy oligomer are uniformly mixed, an antioxidant and a catalyst are charged, and an acrylation reaction (acylation) is performed at 80 to 100 ℃ as a third reaction temperature.
When the reaction temperature of the acrylation reaction is less than 80 ℃, there is a risk that sufficient acrylation reaction cannot be performed. In contrast, in the case of more than 100 ℃, there is a risk that diacrylate or the like is generated as a by-product.
In the above acrylation reaction, the above acrylate compound may be contained in an amount of 0.8mol to 1.2mol with respect to 1mol of the above epoxy oligomer. When the amount is in the above range, the crosslinking agent can be produced suitably for the absorbent resin while suppressing the formation of by-products such as diacrylate.
In the above-mentioned acrylation reaction, an additive such as a heat stabilizer may be further included to prevent discoloration. The above-mentioned additive may be included in an amount of 0.2 to 0.5 weight percent, relative to the total weight of the epoxy oligomer and the acrylate compound, but is not limited thereto. Further, as additives such as a polymerization inhibitor and a heat stabilizer, compounds known in the art can be used.
In the above-mentioned acrylation reaction, the acid value is measured, and the reaction is terminated at a time point when the acid value is 3 or less. Also, Fourier transform infrared spectroscopy can be used to queen disappearance of the epoxy ring and generation of the acrylate double bond peak.
FIG. 6 is a graph showing Fourier transform infrared spectroscopy measurements of an epoxy acrylate based cross-linking agent in accordance with an embodiment of the present invention. In this graph, it may be at 1600cm-1The peak was confirmed for C ═ C double bond acrylate.
FIG. 7 is a graph showing the measurement of the molecular weight of an epoxy acrylate crosslinking agent according to an embodiment of the present invention. The epoxy acrylate crosslinking agent prepared by the above preparation method can satisfy the following formulas 3 and 4.
Formula 3: Mw-E is more than or equal to 450 and less than or equal to 550
Formula 4: PDI-E is more than or equal to 1.2 and less than or equal to 1.6
In the above formula 3, Mw-E means the weight average molecular weight (g/mol) of the epoxy acrylate-based crosslinking agent of the present invention. In the above formula 4, PDI-E means a polydispersity index, which is a ratio of a weight average molecular weight to a number average molecular weight (Mw/Mn).
When the above formulas 3 and 4 are satisfied, the biodegradability of the epoxy acrylate crosslinking agent can be improved, and the water replenishing ability can be effectively improved when the biodegradable super absorbent resin is prepared.
According to another embodiment of the present invention, there is provided a biodegradable super absorbent resin comprising the acrylic ester-based crosslinking agent for absorbent resins as described above.
The biodegradable super absorbent resin is prepared by using a monomer containing (C4-C6) aliphatic dicarboxylic acid and the acrylic ester cross-linking agent for the absorbent resin.
The (C4-C6) aliphatic dicarboxylic acid-containing monomer may comprise itaconic acid or maleic acid. More preferably, itaconic acid is effective to increase biodegradability.
Preferably, the acrylic crosslinking agent for absorbent resin may be contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the (C4-C6) aliphatic dicarboxylic acid-containing monomer. More preferably, 0.05 to 0.2 parts by weight may be included. When the content of the acrylic crosslinking agent for absorbent resin is less than 0.01 part by weight, there is a risk that the water-replenishing ability is lowered. On the contrary, in the case of more than 1 part by weight, it is too cured to have a risk of lowering the moisturizing ability and the biodegradation property.
More specifically, the monomer containing the (C4-C6) aliphatic dicarboxylic acid and the aqueous solution of sodium hydroxide may be charged into the reactor and stirred. It is to be noted that the heat of polymerization occurring at this time does not exceed 40 ℃. Thereafter, the temperature is raised to the reaction temperature of the high absorbent resin and an inert gas is injected. Then, the initiator and the crosslinking agent are added and stirred to perform the reaction of the high-absorbency resin for 1 to 3 hours.
For example, the initiator may be selected from bis (2, 4-6-trimethylbenzoyl) -phenylphosphine oxide, diphenyl (2, 4, 6-trimethylbenzoyl) -phosphine oxide, 2-hydroxymethylpropionitrile, 2'- (azobis (2-methyl-N- (1, 1' -bis (hydroxymethyl) -2-hydroxyethyl) acrylamide), Sodium persulfate (Na persulfate, Na)2S2O8) Persulfuric acidPotassium (potassium sulfate, K)2S2O8) One or more than two of them. More preferably, it may be potassium persulfate.
The reaction temperature of the superabsorbent resin is not limited, and is preferably 50 ℃ to 70 ℃. More preferably, the temperature of 55 ℃ to 65 ℃ is effective for controlling the reaction heat and uniformly reacting.
The biodegradable super absorbent resin generated after the reaction can be obtained by drying in an oven at 60-70 ℃ for 6-24 hours. The dried biodegradable super absorbent resin is pulverized by a pulverizer to distribute the particle size in a size of 300 to 600 μm.
Next, in order to remove impurities and improve water replenishing capacity, unreacted materials are removed by using (C1-C4) low alcohol under the temperature condition of 70-90 ℃. Then, the resulting biodegradable super absorbent resin can be obtained by drying in an oven at 60 to 70 ℃ for 6 to 24 hours.
The biodegradable super absorbent resin of the present invention has excellent biodegradability, and the water replenishing capacity measured according to a water replenishing capacity (CRC) measuring method may be 18g/g to 30 g/g.
As described above, according to the method for preparing the acrylic ester-based crosslinking agent for absorbent resin of the present invention, isosorbide, which is 100% of natural biomass that is corn as a raw material, is subjected to acrylation reaction to prepare the acrylic ester-based crosslinking agent for absorbent resin. Thus, the crosslinking agent itself is excellent in biodegradability and biodegradability in the production of a high-absorbency resin, and a high-absorbency resin having improved water-replenishing performance can be produced.
Also, the super absorbent resin of the present invention can reduce consumption related to petrochemical products, and at the same time, can reduce environmental pollution occurring during the production of petrochemical products. And, the generation of volatile organic compounds is prevented without using an organic solvent, and thus, environmental protection and toxicity reduction can be achieved.
Further, when the absorbent resin prepared by using the acrylic ester-based crosslinking agent for absorbent resins of the present invention is disposed in landfills or incinerated, harmful substances such as dioxin are not generated, and thus the environment is protected.
Specific examples of the method for producing the acrylic ester-based crosslinking agent for absorbent resin, the acrylic ester-based crosslinking agent for absorbent resin produced thereby, and the biodegradable super absorbent resin containing the same as described above are as follows.
Evaluation of physical Properties
1) Determination of acid value
1g of a sample was weighed into a 200ml Erlenmeyer flask, and the following 2: 1 toluene and butanol were mixed with 50ml of a neutral mixed solvent to dissolve. Thereafter, phenolphthalein was used as an indicator to perform titration with a 0.1N-potassium hydroxide Methanol (KOH Methanol) solution. The acid value was derived from the point of 15 seconds at which scarlet disappeared by the following calculation formula.
F: factor (Factor) of 0.1N-Potassium hydroxide methanol solution
V: 0.1 titration amount (ml) of N-Potassium hydroxide methanol solution
W: weight (g) of sample
2) Measurement of Water supplement ability
200ml of distilled water was added to the beaker, and the solution was dissolved after a quantitative charge so as to be a 0.9 weight percent aqueous NaCl solution. To a clean and dried tea bag, 0.2g of a particulate super absorbent resin was accurately quantified, and the resin was added to a beaker containing an aqueous NaCl solution and allowed to swell for 30 minutes. Thereafter, centrifugal separation was performed for 3 minutes by a centrifugal separator of 300 gravity (gravity), and the weight of the super absorbent resin including the tea bag was accurately measured and calculated according to the following calculation formula.
Water replenishing ability (Se) (W)1-W0)/W0
Calculation formula
W1Weight of swollen superabsorbent resin
W0Weight of superabsorbent resin initially charged
3) Determination of biodegradability
Determined according to the KS M ISO 14851 specification.
Preparation example 1
Preparation of urethane acrylate crosslinking agent
82g (1mol) of isosorbide was charged into a four-necked reactor, the temperature was raised to 80 ℃ and then 0.7g (0.875 part by weight) of dibutyltin dilaurate catalyst and 41g of ethyl acetate were charged and stirred. 141.12g (1.01mol) of ethyl 2-isocyanatoacrylate monomer are dropped for 20 minutes by means of a dropping funnel and stirred. After the dropping was completed, fourier transform infrared spectroscopy was measured according to the time period. The reaction is finished at the time point when the peak value of the isocyanate group of the acrylic monomer disappears to synthesize the urethane acrylate crosslinking agent. The molecular weight of the prepared cross-linking agent is Mn 425 and Mw 458.
Preparation example 2
Preparation of epoxy acrylate crosslinking agent
50g (0.38mol) of isosorbide was charged into a four-neck reactor, 355.5g (3.8mol) of epichlorohydrin and 1.5g (0.36 wt%) of tetrabutylammonium bromide (TBAB) as a phase transition catalyst were charged, and the mixture was mixed for 10 minutes at normal temperature. Then, the temperature was raised to 105 ℃ and the mixture was stirred under nitrogen atmosphere for 30 minutes to carry out the reaction.
The mixture was cooled to 50 ℃ and 80g of a 50% by weight aqueous sodium hydroxide solution was dropped for 3 hours from the dropping funnel. After completion of the dropping, the mixture was aged at 50 ℃ for 2 hours. Thereafter, washing with water and filtration are carried out to remove the salt generated, and the remaining epichlorohydrin is recovered to obtain an epoxy oligomer.
Thereafter, 167.33g of methacrylic acid and 0.3g of p-hydroxyanisole (HQMME, hydroquinone monomer methyl ether) as a polymerization inhibitor were charged into a four-neck reactor and stirred. Then, the temperature was raised to 70 ℃. After the temperature was raised, 1/4 to 81.3g of the epoxy oligomer prepared before the charge was dropped from the dropping funnel. To this mixture, 2.46g of an antioxidant, dibutylhydroxytoluene (BHT) and 3.45g of a catalyst, Triphenylphosphine (TPP) were added and stirred, and the temperature was raised to 95 ℃. At this time, attention is paid to heat generation and cooling water flows. When heat generation was not additionally applied, 325.2g of the remaining epoxy oligomer was charged in three portions. Then, 1.23g of triphenylphosphine, which is a thermal stabilizer, was charged and reacted at a temperature of 95 ℃. The acid value was measured by the following method, and the reaction was terminated at a time point at which the acid value was 3 or less. Thereafter, the fourier transform infrared spectrum was measured to confirm the formation of the acrylate peak. The molecular weight of the prepared cross-linking agent is Mn 515, Mw 714.
Example 1
A four-necked reactor was charged with 50g of itaconic acid and 50g of a 25% strength by weight aqueous sodium hydroxide solution, with care being taken that the heat of polymerization did not exceed 40 ℃ and stirring was carried out. Thereafter, the temperature was raised to 60 ℃ to inject nitrogen gas for 1 hour. Then, 0.2g of an initiator (KPS) and 0.05g of the crosslinking agent of preparation example 1 were charged, and the reaction was terminated after the reaction was carried out at 300RPM for 2 hours.
The obtained super absorbent resin is dried in an oven at 60 ℃ for 12 hours, and the dried super absorbent resin is pulverized by a pulverizer to distribute the particle size in a size of 300 to 600 μm. The partitioned sample was then heated at 80 ℃ for 30 minutes to remove unreacted materials. Thereafter, filtration was carried out and drying was carried out at a temperature of 60 ℃ for 12 hours to obtain a final biodegradable super absorbent resin.
Example 2
Biodegradable super absorbent resins were obtained in the same manner as in example 1, except that the crosslinking agent of preparation example 2 was added as shown in table 1 below.
Example 3
Biodegradable super absorbent resins were obtained in the same manner as in example 1 except that 0.02g of the crosslinking agent of preparation example 1 and 0.03g of the crosslinking agent of preparation example 2 were charged as the crosslinking agents as shown in table 1 below.
Comparative example 1
Biodegradable super absorbent resins were obtained in the same manner as in example 1, except that 0.05g of polyethylene glycol diacrylate (Mw: 500g/mol) was added as a crosslinking agent, as shown in Table 1 below.
Comparative example 2
As shown in Table 1 below, a biodegradable super absorbent resin was obtained in the same manner as in example 1, except that an itaconic acid acrylate-based crosslinking agent disclosed in Korean patent laid-open publication No. 10-177901 was used.
TABLE 1
As shown in table 1, it is understood that when the urethane acrylate-based crosslinking agent, the epoxy acrylate-based crosslinking agent, and a mixture thereof of the present invention are used as a crosslinking agent to prepare a high-absorbency resin, the water-replenishing ability is remarkably improved.
This is because the crosslinking agent of the present invention has a heterobicyclic structure containing oxygen of isosorbide which forms a main skeleton. Such a crosslinking agent is expected to have excellent biodegradability.
Further, it is found that in the case where polyethylene glycol diacrylate is used as the crosslinking agent as in comparative example 1 having a structure different from that of the crosslinking agent of the present invention, or an itaconic acid acrylate-based crosslinking agent is used as in comparative example 2, the water replenishing ability is greatly reduced as compared to the case where the crosslinking agent of the present invention is used. Moreover, the biodegradability is also expected to decrease.
The embodiments of the present invention have been described above with reference to the drawings, and the present invention is not limited to the above embodiments and can be prepared in various forms different from each other, and a person skilled in the art to which the present invention pertains can implement the present invention in other specific forms without changing the technical idea or essential features of the present invention. Therefore, the above-described embodiments are illustrative in all respects and do not limit the present invention.
Claims (14)
1. A method for preparing an acrylic ester cross-linking agent for absorbent resin is characterized in that,
prepared by subjecting a compound represented by the following chemical formula 1 to an acrylation reaction:
chemical formula 1:
2. the method of producing an acrylate-based crosslinking agent for absorbent resins according to claim 1, wherein the compound represented by the above chemical formula 1 is produced by acrylation reaction using methacrylate ester containing an isocyanate group.
3. The method for producing an acrylic ester-based crosslinking agent for absorbent resin according to claim 2,
the isocyanate group-containing methacrylate ester includes 2-isocyanatoethyl methacrylate,
the acrylation reaction is performed by adding 0.8 to 1.2 moles of the isocyanate group-containing methacrylate to 1 mole of the compound represented by the above chemical formula 1.
4. The method for producing an acrylic crosslinking agent for absorbent resins according to claim 1, wherein the compound represented by the above chemical formula 1 is produced by subjecting an epoxy oligomer epoxidized with an epichlorohydrin compound to an acrylation reaction.
5. The method for producing an acrylic ester-based crosslinking agent for absorbent resin according to claim 4,
the epoxidation further comprises a phase transition catalyst, and 5 to 10mol of the epichlorohydrin compound is added to 1mol of the compound represented by the chemical formula 1 to perform a reaction,
the above phase change catalyst is contained in an amount of 0.2 to 0.5 weight percent with respect to the total weight of the compound represented by the above chemical formula 1 and the epichlorohydrin compound.
6. The method of claim 4, wherein the acrylic acylation reaction is carried out by adding 0.8 to 1.2 moles of an acrylate compound comprising acrylic acid, methacrylic acid or a mixture thereof to 1 mole of the epoxy oligomer.
7. A method for preparing an acrylate crosslinking agent for absorbent resin, comprising:
a step (a1) of synthesizing an urethane acrylate crosslinking agent by subjecting a compound represented by the following chemical formula 1 to an acrylation reaction using a methacrylate ester having an isocyanate group; or
A step (a2) of preparing an epoxy oligomer by reacting a compound represented by the following chemical formula 1 with a mixture containing an epichlorohydrin compound; and
a step (b2) of reacting the epoxy oligomer prepared in the above step (a2) with an acrylate compound to synthesize an epoxy acrylate-based crosslinking agent:
chemical formula 1:
8. the method for producing an acrylic crosslinking agent for absorbent resins as claimed in claim 7, further comprising:
a step of measuring Fourier transform infrared spectrum of the product of the step (a1) and terminating the reaction at a point of time when the peak of the isocyanate group has disappeared completely; or
And (c) measuring the acid value of the product obtained in the step (b2), and terminating the reaction at a time when the acid value is 3 or less.
9. An acrylic ester crosslinking agent for absorbent resin, characterized in that,
the process for producing an acrylic crosslinking agent for absorbent resins according to claim 7,
comprising a compound represented by the following chemical formula 1:
chemical formula 1:
10. the acrylic ester-based crosslinking agent for absorbent resin according to claim 9,
the acrylic ester-based crosslinking agent for absorbent resin is selected from a compound represented by the following chemical formula 2, a compound represented by the chemical formula 3, or a mixture thereof:
chemical formula 2:
chemical formula 3:
11. the acrylic ester-based crosslinking agent for absorbent resin according to claim 9,
the acrylic ester-based crosslinking agent for absorbent resin satisfies the following formulae 1 to 4:
formula 1: Mw-U is more than or equal to 400 and less than or equal to 500
Formula 2: PDI-U is more than or equal to 1.0 and less than or equal to 1.5
Formula 3: Mw-E is more than or equal to 450 and less than or equal to 550
Formula 4: PDI-E is more than or equal to 1.2 and less than or equal to 1.6
In the above formulas 1 and 3, Mw-U and Mw-E respectively mean the weight average molecular weight (g/mol) of the urethane acrylate crosslinking agent and the epoxy acrylate crosslinking agent of the present invention, and in the above formulas 2 and 4, PDI-U and PDI-E mean the polydispersity index, which is the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn).
12. A biodegradable super absorbent resin characterized by comprising a monomer containing (C4-C6) aliphatic dicarboxylic acid and the absorbent resin according to claim 8 or 9, and an acrylic ester-based crosslinking agent.
13. The biodegradable super absorbent resin according to claim 12, characterized in that,
the (C4-C6) aliphatic dicarboxylic acid-containing monomer comprises itaconic acid or maleic acid,
the acrylic ester-based crosslinking agent for absorbent resin is contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the (C4-C6) aliphatic dicarboxylic acid-containing monomer.
14. The biodegradable super absorbent resin according to claim 12, characterized in that,
the acrylic ester-based crosslinking agent for absorbent resin is selected from a compound represented by the following chemical formula 2, a compound represented by the chemical formula 3, or a mixture thereof:
chemical formula 2:
chemical formula 3:
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| KR1020180135060A KR102169999B1 (en) | 2018-11-06 | 2018-11-06 | Manufacturing method of acrylic crosslinker for super absorbent resin and acrylic crosslinker for super absorbent resin by using the same and biodegradable super absorbent resin having therefrom |
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