CN100368608C - Method for preparing copolymerized acrylonitrile high water-absorption fiber - Google Patents
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Abstract
The present invention relates to a method for preparing a copolymerized acrylonitrile high water-absorption fiber, which comprises the following steps: 1. a copolymerized acrylonitrile fiber is prepared by the charging mass ratio formula that the total weight percentage of acrylonitrile, a methyl methacrylate monomer and a potential crosslinking agent is 100%, wherein an initiating agent accounts for 0.3 to 0.8% of the total mass of the monomer and the potential crosslinking agent, the acrylonitrile accounts for 75 to 85%, and methyl methacrylate accounts for 5 to 15%; the potential crosslinking agent with the content of 5 to 15% is one or a plurality of N-hydroxymethyl acrylamide, methacrylic acid beta-hydroxyl ethyl ester, hydroxyethyl acrylate and hydroxypropyl acrylate, and the initiating agent with the content of 0.3 to 0.8% is azobisisobutyronitrile; the substances in the formula are uniformly mixed and are dissolved in dimethyl sulfoxide, a copolymerized acrylonitrile solution is obtained by adding the initiating agent for initiation, protecting by nitrogen and copolymerizing for 6 hours to 10 hours under the holding temperature of 60 DEG C to 80 DEG C, and the copolymerized acrylonitrile fiber is obtained by wet spinning tension after vacuum defoamation; 2. the obtained fiber treated by a boiling-water bath in a relaxed state is treated by hot crosslinking at the temperature of 130 DEG C to 180 DEG C for 5 min to 15 min, hydrolyzing in proper alkalescence, washing in a weak acid, dehydrating and drying, and the copolymerized acrylonitrile high water-absorption fiber is obtained.
Description
Technical Field
The invention relates to a method for preparing a functional synthetic polymer material, in particular to a method for preparing post-crosslinking-hydrolysis copolymerized acrylonitrile high-water-absorption fiber, and the international patent classification number is supposed to be int 7 .D01D 5/34。
Background
At present, the method for preparing the high water absorption fiber by utilizing the synthetic polymer material mainly comprises two methods:
one is a hydrophilic polymer spinning process: for example, arco chemical technology company in America neutralizes (neutralization degree is 55%) maleic acid-isobutylene copolymer aqueous solution by NaOH, and the nascent fiber with fineness of 2-3 deniers is obtained by dry spinning and forming, and the superabsorbent fiber is obtained after crosslinking treatment is carried out for 10min at 180 ℃. Under the trade name "Fibersorb" (Polymer component and absorbent fibers made therefrom, le-Khac, polymer compositions and absorbent fibers produced therafter, USP 5026784, 1991.6.25); as another example, the super absorbent fiber and its manufacturing method, which is applied by the research institute of textile science in china, uses acrylic acid, sodium acrylate, acrylamide, and hydroxypropyl methacrylate as copolymerization monomers, and is initiated by a polymerization initiator, and then the copolymerization is performed in an aqueous solution to obtain a copolymer aqueous solution, and a polyvinyl alcohol aqueous solution is used as a core layer or a skin layer, and the copolymer aqueous solution is extruded through a core-and-core composite spinneret, and is subjected to dry spinning and thermal crosslinking to obtain the super absorbent fiber (sun yushan, luqiang, juqingsong, etc., the super absorbent fiber and its manufacturing method, CN 1407147, 2003.4.2).
The other method is a chemical modification treatment method for the fiber: a method of producing a super absorbent fiber by chemically treating a surface of a polyacrylonitrile fiber to contain a granular super absorbent resin layer on the fiber surface, such as by Exlan of Japan (Water absorbent acrylic fiber, sawanishi, shigeru, wakitani, mitruu, water-absorbent acrylic fibers, USP4562114, 1985.12.31); deo et al in KMnO 4 -HNO 3 A method for initiating graft copolymerization of acrylonitrile and cotton fiber and obtaining high water absorption fiber after hydrolysis (acrylonitrile monomer grafts raw cotton to make it have high water absorption performance, H.T. Deo, V.D. Gotmare, acrylonitrilometrogrargraftingtongretoglycerine and high water absorption fiber, journal of applied Polymer science,1999, 72; a process for preparing high-hydroscopicity fibre (3.33dtex 65mm polyacrylonitrile fibre) includes immersing ordinary polyacrylonitrile fibre in glycol solution, oil bath heating to a certain temp, holding temp for 40min, cooling to room temp, taking out, immersing in distilled water, centrifugal drying, vacuum drying to obtain golden fibre with cross-linking degree of 2.5%, hydrolyzing in NaOH solution, neutralizing, and drying2000，12(3)：339～342)。
Although the preparation methods of the high water absorption fiber have thousands of autumn, the preparation methods have a common defect that: the obtained high water absorption fiber is changed into gel after absorbing water, the original shape of the fiber is easily lost, namely, the shape retention is poor, the physical and mechanical properties of the fiber are lost or partially lost, the high water absorption fiber is difficult to be effectively used as a fiber material, particularly as a textile material, and simultaneously, the preparation process is relatively complex and the cost is relatively high.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem of providing the preparation method of the copolymerized acrylonitrile high-water-absorptivity fiber, which has the characteristics of controllable water-absorption rate process, simple production, lower cost, convenience for industrial implementation and the like. The copolymerized acrylonitrile high-absorbent fiber prepared by the preparation method of the copolymerized acrylonitrile high-absorbent fiber has high water absorption performance after partial hydrolysis, and can keep the original shape and good physical-mechanical properties of the fiber after water absorption while keeping good water absorption performance;
the technical scheme for solving the technical problem of the preparation method of the copolymerized acrylonitrile high-water-absorption fiber comprises the following steps: a preparation method of copolymerized acrylonitrile high-water-absorption fiber is designed, and comprises the following steps:
(1) The preparation method of the copolymerized acrylonitrile fiber comprises the following steps: acrylonitrile and methyl methacrylate monomers and 100% of latent crosslinking agent; the acrylonitrile accounts for 75-85% of the total mass of the monomer and the latent crosslinking agent, and the methyl methacrylate accounts for 5-15% of the total mass of the monomer and the latent crosslinking agent; the latent crosslinking agent is one or more of N-hydroxymethyl acrylamide, beta-hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, and the content of the latent crosslinking agent is 5-15% of the total mass of the monomer and the latent crosslinking agent; the initiator is azo diisobutyronitrile, and the content of the initiator is 0.3 to 0.8 percent of the total mass of the monomer and the latent crosslinking agent; uniformly mixing monomer acrylonitrile, methyl methacrylate and a latent crosslinking agent, dissolving the mixture in dimethyl sulfoxide, adding an initiator to initiate, carrying out nitrogen protection, keeping the temperature at 60-80 ℃, and copolymerizing for 6-10 h to obtain a copolymerized acrylonitrile solution containing the latent crosslinking agent, wherein the monomer and the latent crosslinking agent account for 18-25% of the total mass of the monomer, the latent crosslinking agent and the solvent dimethyl sulfoxide; after the obtained copolymerized acrylonitrile solution is defoamed in vacuum, 40-60% dimethyl sulfoxide aqueous solution is taken as coagulating bath, and then the copolymerized acrylonitrile fiber is obtained through wet spinning and stretching;
(2) Preparing copolymerized acrylonitrile high water-absorbing fiber, then carrying out boiling water bath treatment on the obtained copolymerized acrylonitrile fiber in a relaxed state, carrying out thermal crosslinking on the treated fiber at the crosslinking temperature of 130-180 ℃ for 5-15 min at the crosslinking time of 95-100 ℃ for 5-25% of NaOH aqueous solution for 3-9 min, washing the fiber for 5-10 min by using weak acid solution with the pH value of 3-5, dehydrating the fiber for 5-10 min by using ethanol or acetone, and drying the fiber at room temperature to obtain the copolymerized acrylonitrile high water-absorbing fiber.
Compared with the prior art, the preparation method of the copolymerized acrylonitrile high-water-absorption fiber mainly comprises the processes of copolymerization, spinning, thermal crosslinking, hydrolysis, neutralization washing, dehydration drying and the like. The invention is mainly different from the prior art in that the copolymerized acrylonitrile high-water-absorption fiber is prepared by adopting the technical processes of hydrolyzing, neutralizing, washing, dehydrating, drying and the like after the copolymerized acrylonitrile fiber is crosslinked. The preparation method of the copolymerized acrylonitrile high-water-absorption fiber has the characteristics of controllable water absorption rate of product fiber, simple production process, lower cost, no special equipment, no special process requirement, convenience for industrial popularization and implementation and the like. The copolymerized acrylonitrile high-absorbent fiber prepared by the preparation method of the copolymerized acrylonitrile high-absorbent fiber has high water absorption performance after partial hydrolysis, and the part which is not hydrolyzed inside can play a role in keeping the original shape and better physical-mechanical properties of the fiber, so that the product fiber has spinning processability, namely industrial practicability.
Detailed Description
The preparation method of the copolymerized acrylonitrile high-water-absorption fiber (hereinafter referred to as the preparation method) mainly comprises the following two steps: namely, firstly preparing copolymerized acrylonitrile fiber, and then preparing copolymerized acrylonitrile high-water-absorption fiber by partially hydrolyzing the obtained copolymerized acrylonitrile fiber. The preparation method specifically comprises the following steps:
(1) The preparation method of the copolymerized acrylonitrile fiber comprises the following steps: 100% of acrylonitrile and methyl methacrylate monomer and latent crosslinking agent; the initiator accounts for 0.3 to 0.8 percent of the total mass of the monomer and the latent crosslinking agent, the acrylonitrile accounts for 75 to 85 percent of the total mass of the monomer and the latent crosslinking agent, and the methyl methacrylate accounts for 5 to 15 percent of the total mass of the monomer and the latent crosslinking agent; the latent crosslinking agent is one or more of N-hydroxymethyl acrylamide, beta-hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, and the content of the latent crosslinking agent is 5-15% of the total mass of the monomer and the latent crosslinking agent; the initiator is azobisisobutyronitrile, and the content of the initiator is 0.3 to 0.8 percent of the total mass of the monomer and the latent crosslinking agent; uniformly mixing and dissolving monomer acrylonitrile, methyl methacrylate and a latent crosslinking agent in dimethyl sulfoxide, wherein the monomer and the latent crosslinking agent account for 18-25%, preferably 20% of the total mass of the monomer, the latent crosslinking agent and a solvent, adding an initiator for initiation, protecting with nitrogen, and maintaining the copolymerization temperature at 60-80 ℃, preferably 68-70 ℃, for 6-10 h, preferably 8h to obtain a copolymerized acrylonitrile solution containing the latent crosslinking agent; after the obtained copolymerized acrylonitrile solution is defoamed in vacuum, 40-60% dimethyl sulfoxide aqueous solution is taken as coagulating bath, and then the copolymerized acrylonitrile fiber is obtained through wet spinning and stretching;
(2) Preparing copolymerized acrylonitrile high water-absorbing fiber, namely, processing the obtained copolymerized acrylonitrile fiber in a loose state through boiling water bath, hydrolyzing the processed fiber at the crosslinking temperature of 130-180 ℃ for 5-15 min at the crosslinking time of 95-100 ℃ for 3-9 min by using a NaOH aqueous solution with the concentration of 5-25%, washing the fiber for 5-10 min by using a weak acid solution with the pH value of 3-5, dehydrating the fiber for 5-10 min by using ethanol or acetone, and drying the fiber at room temperature to obtain the copolymerized acrylonitrile high water-absorbing fiber.
The wet spinning process for preparing the copolymerized acrylonitrile fiber before copolymerizing acrylonitrile to obtain the high water absorption fiber comprises the following steps: (1) controlling the coagulation bath to be 40-60%, preferably 40% of dimethyl sulfoxide aqueous solution; (2) carrying out multi-pass stretching of 4-6 times on the obtained copolymerized acrylonitrile fiber in a boiling water bath; (3) the obtained copolymerized acrylonitrile fiber passes through a water bath at 95-100 ℃ in a relaxed state to achieve the purpose of relaxed heat setting. The wet spinning process (3) plays an important role in maintaining the dimensional stability of the fibers in the thermal crosslinking process. The copolymerized acrylonitrile high-water-absorption fiber and the technology which is not described in the wet spinning process are suitable for the prior art.
The thermal crosslinking process of the preparation method of the invention refers to the thermal treatment of the relaxed copolymerized acrylonitrile high water-absorbing fiber (hereinafter referred to as fiber or high water-absorbing fiber) at 130-180 ℃, preferably 170-180 ℃, and the crosslinking time is 5-15 min, preferably 10min. The selection and the use of the latent crosslinking agent are one of the technical keys of the invention. The selection basis is as follows: (1) self-crosslinking reaction can be carried out at a certain temperature, and the super absorbent fiber is endowed with a certain three-dimensional network structure; (2) before spinning and forming, the latent crosslinking agent can not generate crosslinking action so as to ensure that the fiber-forming polymer macromolecules have good linear structure and the spinning solution has good spinnability; (3) no physical damage and no chemical damage to the finally formed fiber. Accordingly, the latent crosslinking agents of the present invention should be selected from materials that do not affect fiber formation and that self-crosslink at a certain temperature, such as N-methylolacrylamide, beta-hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and the like. They all satisfy the above selection principle of the latent crosslinking agent. The preferred latent crosslinker for embodiments of the invention is N-methylolacrylamide, preferably present at 10% by weight of the total of comonomer and latent crosslinker. This does not prevent the selection of other latent crosslinking agents that meet the above criteria for their selection. In contrast, conventional crosslinking agents generally crosslink product macromolecules (such as N-N' methylenebisacrylamide) during polymerization, and the obtained product macromolecules have no linear structure, and the solution or melt thereof has no spinnability, so that the practicability is poor.
The hydrolysis in the preparation method of the invention refers to alkaline hydrolysis of the crosslinked copolymerized acrylonitrile fiber. The process conditions are as follows: the hydrolysis temperature is 95-100 ℃, the concentration of NaOH aqueous solution is 5-25%, preferably 20%, and the hydrolysis time is 3-9 min. The hydrolysis process aims to convert hydrophobic cyano groups on copolymerized acrylonitrile macromolecules into amide groups, carboxyl groups and carboxylate groups with stronger hydrophilicity. The hydrolysis conditions determine the number of hydrophilic groups contained in the fiber. Obviously, under certain crosslinking conditions, moderate hydrolysis can make the fiber contain as many hydrophilic groups as possible so as to improve the water absorption and retention performance of the fiber. The fiber skin obtained after partial hydrolysis has high water absorption performance, and the inner unhydrolyzed part can play the role of maintaining fiber shape and physical-mechanical properties.
The neutralization washing is to wash for 5-10 min by weak acid (such as acetic acid) solution with pH value of 3-5, preferably 3, and the washing time is preferably 5min. The main purpose of this is to make the fibre neutral, it being clear that the lower the pH of the weak acid solution used, the shorter the washing time. The preferred process of the embodiment of the invention is as follows: washing with acetic acid solution of pH 3 for 5min. The dehydration drying is to dehydrate for 5-10 min by adopting ethanol or acetone and then dry at room temperature. The fiber which is not dehydrated by the method is not easy to dry, and the directly dried fiber can be hardened and hardened, so that the water absorption performance is obviously poor, and the practical value is low. In order to fully dehydrate the fibers and considering the low toxicity of ethanol, the preferred process of the embodiment of the invention is to dehydrate the fibers with ethanol for 10min.
The preparation method of the invention is applicable to the prior art.
According to the preparation method provided by the invention, functional fibers with stronger water absorption and retention properties, namely super absorbent fibers, can be directly prepared. The water absorption and retention properties of the fiber depend on the degree of crosslinking and hydrolysis conditions of the fiber, among others. Wherein the degree of crosslinking determines the perfection of the crosslinked network of fibers. If the content of the latent crosslinking agent is low, the crosslinking temperature is low or the crosslinking time is short, the crosslinked network structure of the fiber is imperfect, so that the fiber has poor hydrolysis resistance, the hydrolysis process is not easy to control, the phenomenon of dissolution while hydrolysis occurs, the hydrophilic group of the obtained high-water-absorption fiber is only limited on the surface of the fiber, and the water absorption and water retention performance of the fiber is poor; if the content of the latent cross-linking agent is too high, the cross-linking temperature is higher or the cross-linking time is too long, the cross-linked network structure of the fiber is too compact, which is not favorable for water molecules to diffuse into the fiber and is also not favorable for improving the water absorption and water retention performance of the fiber. The content of the latent crosslinking agent is 5-15%, preferably 10%, of the total mass of the monomer and the latent crosslinking agent, the crosslinking temperature is 130-180 ℃, preferably 170 ℃, and the crosslinking time is 5-15 min, preferably 10min. The high water absorption fiber prepared by the process has ideal mechanical property, water absorption rate, water retention rate and the like. The thermal crosslinking and hydrolysis process of the invention is designed to have important significance after the copolymerized acrylonitrile fiber is spun, so the fiber of the invention can also be specifically called post-crosslinking-hydrolysis type copolymerized acrylonitrile high water absorption fiber.
The fiber prepared by the preparation method disclosed by the invention has excellent water absorption and retention properties, can keep the fiber shape and certain mechanical properties after water absorption, can be processed into textiles or non-woven products, is easy to recycle and can be recycled.
Specific examples of the preparation process according to the invention are given below:
example 1
Acrylonitrile and methyl methacrylate are used as monomers, N-hydroxymethyl acrylamide is used as a latent cross-linking agent, the content of N-hydroxymethyl acrylamide is controlled to be 5%, 7%, 10% and 15% of the total mass of the monomers and the latent cross-linking agent, azodiisobutyronitrile is used as an initiator, the use amount of the azodiisobutyronitrile is 0.5% of the total mass of the monomers and the latent cross-linking agent, solution polymerization is carried out in dimethylsulpholane under nitrogen protection and heating at 68-70 ℃, the reaction time is 8h, after vacuum defoaming of the obtained copolymer solution, wet spinning is carried out by taking 40% dimethyl sulfoxide aqueous solution as a coagulating bath, 5 times of stretching is carried out in a boiling water bath and relaxation and heat setting is carried out by the boiling water bath, copolymerized acrylonitrile fiber is obtained, then heat crosslinking is carried out at 170 ℃ for 10min, hydrolysis is carried out by 20 NaOH solution for 3min, after washing is carried out for 5min by adopting acetic acid solution with pH value of 3, ethanol dehydration is carried out for 10min, and drying is carried out at room temperature, and high water absorption fiber with four proportions can be prepared.
The four fibers are respectively immersed in pure water, and the saturated water absorption rates are respectively 11.2g/g, 21.5g/g, 54.5g/g and 33.2g/g; and placing the four saturated fibers after water absorption into a centrifuge, and rotating and dehydrating at the centrifugal speed of 1000r/min for 5min to obtain the water retention rates of 58.5%, 72.0%, 83.5% and 90.5% respectively.
The calculation formula of the saturated water absorption is as follows:
in the formula: Q-Water absorption (g/g)
W 0 -mass of fibres before water absorption (g)
W 1 -mass of fibres after water absorption (g)
The water retention rate is calculated by the following formula:
in the formula: R-Water Retention ratio (wt%)
M 1 Fiber quality before centrifugal dewatering (g)
M 2 -fiber mass after centrifugal dewatering (g).
Example 2
Four kinds of super absorbent fibers can be prepared by designing the content of N-methylolacrylamide to be 10% of the total mass of the monomers and the N-methylolacrylamide, and respectively taking the contents of azodiisobutyronitrile as an initiator to be 0.3%, 0.5%, 0.7% and 0.8% of the total mass of the monomers and the N-methylolacrylamide, and the rest of the steps are the same as in example 1. The saturated water absorption of the four obtained fibers is detected to be 52.0g/g, 54.5g/g, 45.5g/g and 42.5g/g respectively; the water retention rates were 85.5%, 87.5%, 80.0%, and 78.5%, respectively.
Example 3
Four kinds of high water absorption fibers can be prepared by designing the N-methylolacrylamide content to be 10% of the total mass of the monomers and the N-methylolacrylamide, and respectively adopting the cross-linking temperatures of 130 ℃, 150 ℃, 170 ℃ and 180 ℃ as in example 1. The saturated water absorption of the four fibers is respectively 20.0g/g, 31.5g/g, 54.5g/g and 48.5 g/g; the water retention rates were 73.0%, 69.0%, 87.5% and 89.3%, respectively.
Example 4
Four types of fibers can be obtained by designing the content of N-methylolacrylamide to be 10% of the total mass of the monomers and the N-methylolacrylamide, and taking the concentrations of NaOH aqueous solution of 5%, 10%, 15% and 20% respectively in the hydrolysis process, and the rest of the procedure is the same as that of example 1. The saturated water absorption of the series of fibers is respectively 9.0g/g, 22.5g/g, 24.5 g/g and 40.5g/g.
Example 5
The content of N-hydroxymethyl acrylamide is designed to be 10% of the total mass of the monomers, the hydrolysis time is 9min, the alkali concentration in the hydrolysis process is respectively 5%, 10%, 15% and 20%, and the rest is the same as the example 1, so that the high water-absorbing fiber can be prepared. The saturated water absorption of the series of fibers is respectively 18.5g/g, 30.0 g/g, 52.5g/g and 47.5g/g.
Example 6
Four kinds of fibers can be obtained by designing the content of N-methylolacrylamide to be 10% of the total mass of the monomers and the N-methylolacrylamide, and hydrolyzing for 3min, 5min, 7min and 9min, respectively, as in example 1. The saturated water absorption of the series of fibers is respectively 40.5g/g, 45.0g/g, 48.3g/g and 46.5g/g.
Example 7
The content of N-hydroxymethyl acrylamide is 10% of the total mass of the monomers, the concentration of NaOH aqueous solution is 5%, the hydrolysis time is 3min, 5min, 7min and 9min respectively, and the rest is the same as that in example 1, so that the high water-absorbing fiber can be prepared. The saturated water absorption of the series of fibers measured by detection is respectively 9.0g/g, 12.3g/g, 15.2g/g and 18.5g/g.
Example 8
The content of N-methylolacrylamide is designed to be 10% of the total weight of the monomer and the monomer, and in the preparation process of the copolymerized acrylonitrile fiber, the fiber is respectively stretched by 4 times, 5 times and 6 times in boiling water bath, and the rest is the same as the embodiment 1, and three kinds of fibers can be prepared. The saturated water absorption of the obtained series of fibers is respectively 40.5g/g, 38.5g/g and 35.5g/g, which shows that the water absorption performance of the fibers is slightly reduced after stretching, but the mechanical properties of the fibers are increased after the stretching treatment, and the breaking strength is respectively 0.41CN/dtex, 0.63CN/dtex and 0.86CN/dtex.
Example 9
According to the method of the embodiment 1, a series of high water absorption fibers can reach or approach the saturated water absorption rate within 5min after meeting water, and have a relatively high water absorption rate.
Example 10
A series of superabsorbent fibers were prepared according to the method of example 1, having slightly improved mechanical properties after absorption compared to before absorption, and having a 4-fold elongation N-methylolacrylamide content of 0.41CN/dtex before absorption and a break strength after absorption of 0.45 CN/dtex, as exemplified by 10% of the total monomer and mass. After repeating the water absorption-dehydration for 5 times, the water absorption performance of the obtained high water absorption fiber is not changed obviously. The obtained high water absorption fiber can have the original mechanical property after absorbing water and has better reusability.
Example 11
Three kinds of superabsorbent fibers were prepared by replacing the latent crosslinking agent with beta-hydroxyethyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate, respectively, according to the method of example 3, at a thermal crosslinking temperature of 170 c under the same conditions as in example 3. The saturated water absorption of the three high water absorption fibers is respectively 40.5g/g, 38.5g/g and 45.5g/g; the water retention rates were 73.0%, 87.5%, and 69.0%, respectively.
Claims (8)
1. A preparation method of copolymerized acrylonitrile high-water-absorption fiber comprises the following steps:
(1) The preparation method of the copolymerized acrylonitrile fiber comprises the following steps: acrylonitrile and methyl methacrylate monomers and 100 percent of latent crosslinking agent; the acrylonitrile accounts for 75-85% of the total mass of the monomer and the latent crosslinking agent, and the methyl methacrylate accounts for 5-15% of the total mass of the monomer and the latent crosslinking agent; the latent crosslinking agent is one or more of N-hydroxymethyl acrylamide, beta-hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, and the content of the latent crosslinking agent is 5-15% of the total mass of the monomer and the latent crosslinking agent; the initiator is azobisisobutyronitrile, and the content of the initiator is 0.3 to 0.8 percent of the total mass of the monomer and the latent crosslinking agent; uniformly mixing monomer acrylonitrile, methyl methacrylate and a latent cross-linking agent, dissolving the mixture in dimethyl sulfoxide, adding an initiator into the mixture to initiate, and carrying out nitrogen protection and copolymerization for 6-10 h while keeping the temperature at 60-80 ℃ to obtain a polyacrylonitrile solution containing the latent cross-linking agent, wherein the monomer and the latent cross-linking agent account for 18-25% of the total mass of the monomer, the latent cross-linking agent and the solvent dimethyl sulfoxide; after the obtained copolymerized acrylonitrile solution is defoamed in vacuum, 40-60% dimethyl sulfoxide water solution is taken as coagulating bath, and copolymerized acrylonitrile fiber is obtained by wet spinning and stretching;
(2) The copolymerized acrylonitrile high water-absorbing fiber is prepared by treating the obtained copolymerized acrylonitrile fiber in a loose state by boiling water bath, hydrolyzing the treated fiber at the crosslinking temperature of 130-180 ℃ for 5-15 min at the temperature of 95-100 ℃ and the concentration of NaOH aqueous solution of 5-25% for 3-9 min, washing the fiber for 5-10 min by using weak acid solution with the pH value of 3-5, dehydrating the fiber for 5-10 min by using ethanol or acetone, and drying the fiber at room temperature to obtain the copolymerized acrylonitrile high water-absorbing fiber.
2. The method for preparing the copolymerized acrylonitrile high water absorption fiber according to claim 1, wherein the latent crosslinking agent is N-methylolacrylamide, and the content of the N-methylolacrylamide is 10% of the total mass of the comonomer and the latent crosslinking agent; the monomer and the latent crosslinking agent account for 20 percent of the total mass of the monomer, the latent crosslinking agent and the solvent dimethyl sulfoxide.
3. The method for preparing copolymerized acrylonitrile high absorbent fiber according to claim 1, characterized in that the copolymerization temperature is 68-70 ℃, and the copolymerization time is 8h.
4. The method for preparing copolymerized acrylonitrile high water-absorbing fiber according to claim 1, wherein the crosslinking temperature is 170-180 ℃ and the crosslinking time is 10min.
5. The method for preparing copolymerized acrylonitrile high water-absorbent fiber according to claim 1, wherein the concentration of the NaOH aqueous solution is 20%.
6. The method for preparing copolymerized acrylonitrile superabsorbent fiber according to claim 1, wherein the weak acid solution is acetic acid solution, pH is 3, and washing time is 5min.
7. The method for preparing copolymerized acrylonitrile high absorbent fiber according to claim 1, characterized in that the dehydration uses ethanol, and the dehydration time is 10min.
8. The method for preparing copolymerized acrylonitrile superabsorbent fiber according to any one of claims 1 to 7, characterized in that the wet spinning process comprises: (1) controlling the coagulation bath to be 40% of dimethyl sulfoxide water solution; (2) carrying out multi-pass stretching on the obtained copolymerized acrylonitrile fiber by 4-6 times in a boiling water bath; (3) the obtained copolymerized acrylonitrile fiber is subjected to relaxation heat setting in a water bath at the temperature of 95-100 ℃ in a relaxation state.
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| JPS57139510A (en) * | 1981-02-16 | 1982-08-28 | Toray Ind Inc | Special acrylic fiber |
| JPH0441709A (en) * | 1990-05-31 | 1992-02-12 | Mitsubishi Rayon Co Ltd | Production of acrylic fiber having high water retention ratio |
| JPH04119114A (en) * | 1990-09-06 | 1992-04-20 | Kanebo Ltd | Quickly skrinkable acrylic synthetic fiber and its production |
| CN1068339A (en) * | 1991-07-08 | 1993-01-27 | 中国科学院成都分院分析测试中心 | The manufacture method of High hydrophilous resin |
-
2005
- 2005-09-30 CN CNB2005100152965A patent/CN100368608C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57139510A (en) * | 1981-02-16 | 1982-08-28 | Toray Ind Inc | Special acrylic fiber |
| JPH0441709A (en) * | 1990-05-31 | 1992-02-12 | Mitsubishi Rayon Co Ltd | Production of acrylic fiber having high water retention ratio |
| JPH04119114A (en) * | 1990-09-06 | 1992-04-20 | Kanebo Ltd | Quickly skrinkable acrylic synthetic fiber and its production |
| CN1068339A (en) * | 1991-07-08 | 1993-01-27 | 中国科学院成都分院分析测试中心 | The manufacture method of High hydrophilous resin |
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|---|---|
| CN1743517A (en) | 2006-03-08 |
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