CN109736084B - Hyperbranched structure high water absorption fiber and preparation method thereof - Google Patents
Hyperbranched structure high water absorption fiber and preparation method thereof Download PDFInfo
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- CN109736084B CN109736084B CN201811650836.0A CN201811650836A CN109736084B CN 109736084 B CN109736084 B CN 109736084B CN 201811650836 A CN201811650836 A CN 201811650836A CN 109736084 B CN109736084 B CN 109736084B
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Abstract
The invention relates to a hyperbranched structure high water-absorbent fiber and a preparation method thereof, wherein the preparation method comprises the following steps: fiber fulcrum introduction: performing esterification reaction on acrylic acid and natural fibers to prepare fiber acrylic ester; branched graft copolymerization: carrying out copolymerization reaction on the prepared fiber acrylic ester, a grafting monomer and a trifunctional branching monomer to obtain a branched modified fiber, and filtering and washing; hydrophilic treatment: carrying out metal ion exchange on the branched modified fiber, wherein the exchange degree is 60-80%; dissolving pulp and spinning: preparing filamentous long fibers; immobilization and surface heat treatment of long fibers; and (4) airflow drying and carding. The fiber has a hyperbranched structure, the water absorption rate of the fiber can reach more than 360g/g, and the fiber is applied to the fields of hygienic products, medical products, water retention materials and the like and has a wide application prospect.
Description
Technical Field
The invention belongs to the field of high polymer materials, relates to a high water-absorbing fiber and a preparation method thereof, and particularly relates to a high water-absorbing fiber with a hyperbranched structure and a preparation method thereof.
Background
The high water absorption fiber (SAF) is a high molecular functional fiber developed after high water absorption resin (SAP), and the water absorption rate of the high water absorption fiber is dozens of times or even higher than that of the common fiber. The high water absorption fiber not only has the chemical structure characteristics of water absorption, water retention, swelling and the like of the high water absorption resin, but also has the characteristics of high water absorption rate, comfortable hand feeling, good processability and the like due to the physical form and size particularity of the fiber, and the fiber is not easy to migrate or fall off. The method for preparing the high water absorption fiber in the prior art is various, the preparation process is complex, residues or degradation products with certain toxicity can exist in the prepared high water absorption fiber, and the fiber obtained by the traditional preparation method can not necessarily meet the high water absorption requirement.
The fibrous super absorbent material has large surface area, high water absorption rate, softness, comfortable contact with skin, no gel flow after water absorption, original strength and integrity of the water absorption fiber, simplified manufacturing process of sanitary articles and perfect solution of the defects of the granular super absorbent material (SAP). The SAF can be woven into cloth and can be prepared into an integrated absorption core body, the SAF can be compounded with different natural fibers to endow the integrated absorption core body with various functions, for example, chitosan or trehalose fibers can be added to prepare antibacterial and deodorant water-absorbing textiles, the SAF can be compounded with bamboo fibers to prepare a high-permeability absorption core body and the like, the SAF can be applied to multiple fields of hygienic products, moisture-preserving packaging materials, agriculture and forestry water-preserving materials and the like, and the SAF has a very considerable application prospect as a multifunctional polymer material in the future.
At present, worldwide, the countries in the uk and japan that produce SAF as a commodity have a water absorption rate of about 350 times and an annual output of less than 2000 tons in total. Some enterprises in China claim to sell SAF products at present, but through sampling tests, the water absorption multiplying power of the enterprises is about 100 times, the water absorption speed is low, the water retention effect is poor, certain difference exists between the commercial quality and the foreign technology, the difference is larger compared with the foreign technology, and China is relatively scarce in the aspects of research and development, industrial application and the like of high water absorption fibers.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a hyperbranched superabsorbent fiber and a method for preparing the same.
A preparation method of super-branched structure superabsorbent fibers comprises the following steps:
1) fiber fulcrum introduction: performing esterification reaction on acrylic acid and natural fibers to prepare fiber acrylic ester;
2) branched graft copolymerization: carrying out copolymerization reaction on the fiber acrylic ester prepared in the step 1), a grafting monomer and a trifunctional branching monomer to obtain a branched modified fiber, and filtering and washing;
3) hydrophilic treatment: carrying out metal ion exchange on the branched modified fiber, wherein the exchange degree is 60-80%;
4) dissolving pulp and spinning: preparing the fiber after hydrophilic treatment into filamentous long fiber;
5) drying and fixing the filamentous long fibers, and carrying out surface treatment and heat treatment on the filamentous long fibers;
6) carrying out airflow drying and carding on the fibers after the heat treatment;
the natural fiber in the step 1) comprises more than one of cotton fiber, bagasse fiber and wood pulp fiber;
the reaction process of the step 1) also comprises adding a neutral organic titanium esterification catalyst, wherein the organic titanium esterification catalyst comprises more than one of tetra-n-butyl titanate, titanium isooctanolate, poly-n-butyl titanate and tetra-isopropyl titanate;
the grafting monomer in the step 2) comprises more than one of acrylic acid, acrylamide, allyl polyethylene glycol, methallyl polyethylene glycol and allyloxy polyoxyethylene ether;
the trifunctional branched monomer in the step 2) comprises one of trimethylolpropane triacrylate, nonamethylol propane triacrylate and pentadecyl methylol propane triacrylate;
step 3) adding sodium hydroxide or potassium hydroxide into the branched modified fiber, and performing sodium ion or potassium ion exchange to improve the exposed degree of the branched hydrophilic group and further improve the hydrophilicity and water absorption capacity of the product;
the immobilization and surface heat treatment of step 5) comprises drying and immobilization, surface treatment and heat treatment.
The super-branched structure high water absorption fiber is prepared with natural fiber as base material and through branching modification, and has super-branched structure and water absorption rate as high as 360 g/g.
The invention has the following beneficial effects:
1. the preparation process can realize the hyperbranched grafting of the water-absorbing group of the fiber by controlling the polymerization reaction condition of the reaction monomer, and compared with the currently adopted fiber single-layer water-absorbing group modification technology, the water-absorbing and water-locking performance of the fiber is greatly improved;
2. compared with the prior art, the hyperbranched structure superabsorbent fiber adopts natural fiber as a base material, can reduce the dependence of superabsorbent material products on petrochemical raw materials, has less influence of wastes on the nature, and is safer, more comfortable and more green to use in the field of sanitary products;
3. the high water absorption fiber has a hyperbranched structure, and the water absorption capacity of the fiber is improved, so that the high water absorption fiber has high hydrophilicity and high water absorption capacity, has physical properties and mechanical properties which are not easy to deform, can be applied to the fields of sanitary products, medical products, water retention materials and the like, and has a wide application prospect.
Drawings
FIG. 1 is a schematic diagram of a chemical reaction scheme introduced at the fulcrum of a fiber;
FIG. 2 is a chemical reaction scheme for branched graft copolymerization.
Detailed Description
The present invention is described in further detail below by way of specific embodiments and accompanying illustrations, it being understood that these examples are intended only to illustrate the invention and not to limit the scope of the invention, which is defined by the claims appended hereto, and that modifications of various equivalent forms to the invention by those skilled in the art which are, after reading the present invention, within the scope of the claims appended hereto.
Example 1
A preparation method of hyperbranched structure superabsorbent fibers comprises the following steps:
1) fiber fulcrum introduction: carrying out esterification reaction on 30g of acrylic acid and 30g of cotton fiber by using 10g of tetrabutyl titanate as a catalyst to prepare fiber acrylate;
2) branched graft copolymerization: carrying out copolymerization reaction on the fiber acrylate prepared in the step 1), 10g of acrylic acid, 10g of acrylamide and 15g of trimethylolpropane triacrylate to obtain branched modified fibers, filtering and washing with water;
3) hydrophilic treatment: adding 40g of sodium hydroxide into branched modified fibers for metal ion exchange, wherein the exchange degree is 60-80%;
4) dissolving pulp and spinning: preparing the fiber after hydrophilic treatment into filamentous long fiber;
5) drying and fixing the filamentous long fibers, performing surface treatment and heat treatment: drying and fixing the filament fibers at 80 ℃, performing surface treatment and performing heat treatment at 120 ℃;
6) and (3) carrying out air flow drying and carding on the fibers after the heat treatment to finally obtain the hyperbranched structure high-water-absorption fibers.
Example 2
A preparation method of hyperbranched structure superabsorbent fibers comprises the following steps:
1) fiber fulcrum introduction: taking 10g of isooctyl alcohol titanium as a catalyst, and carrying out esterification reaction on 30g of acrylic acid and 30g of bagasse fibers to prepare fiber acrylate;
2) branched graft copolymerization: carrying out copolymerization reaction on the fiber acrylate prepared in the step 1), 10g of acrylic acid, 10g of allyl polyethylene glycol and 15g of nonahydroxymethyl propane triacrylate to obtain branched modified fibers, filtering and washing with water;
3) hydrophilic treatment: adding 40g of sodium hydroxide into branched modified fibers for metal ion exchange, wherein the exchange degree is 60-80%;
4) dissolving pulp and spinning: preparing the fiber after hydrophilic treatment into filamentous long fiber;
5) drying and fixing the filamentous long fibers, performing surface treatment and heat treatment: drying and fixing the filament fibers at 90 ℃, performing surface treatment and performing heat treatment at 125 ℃;
6) and (3) carrying out air flow drying and carding on the fibers after the heat treatment to finally obtain the hyperbranched structure high-water-absorption fibers.
Example 3
A preparation method of hyperbranched structure superabsorbent fibers comprises the following steps:
1) fiber fulcrum introduction: carrying out esterification reaction on 30g of acrylic acid and 30g of cotton fibers by using 10g of poly-n-butyl titanate as a catalyst to obtain fiber acrylate;
2) branched graft copolymerization: carrying out copolymerization reaction on the fiber acrylic ester prepared in the step 1), 10g of methyl allyl polyethylene glycol, 10g of allyloxy polyoxyethylene ether and 15g of trimethylolpropane triacrylate to obtain branched modified fiber, filtering and washing with water;
3) hydrophilic treatment: adding 40g of sodium hydroxide into branched modified fibers for metal ion exchange, wherein the exchange degree is 60-80%;
4) dissolving pulp and spinning: preparing the fiber after hydrophilic treatment into filamentous long fiber;
5) drying and fixing the filamentous long fibers, performing surface treatment and heat treatment: drying and fixing the filament fibers at 110 ℃, performing surface treatment and performing heat treatment at 130 ℃;
6) and (3) carrying out air flow drying and carding on the fibers after the heat treatment to finally obtain the hyperbranched structure high-water-absorption fibers.
Example 4
A preparation method of hyperbranched structure superabsorbent fibers comprises the following steps:
1) fiber fulcrum introduction: carrying out esterification reaction on 30g of acrylic acid and 30g of wood pulp fiber by using 10g of tetrabutyl titanate as a catalyst to prepare fiber acrylate;
2) branched graft copolymerization: carrying out copolymerization reaction on the fiber acrylate prepared in the step 1), 10g of acrylic acid, 10g of methallyl polyethylene glycol and 15g of pentadecyl hydroxymethyl propane triacrylate to obtain branched modified fibers, filtering and washing with water;
3) hydrophilic treatment: adding 40g of sodium hydroxide into branched modified fibers for metal ion exchange, wherein the exchange degree is 60-80%;
4) dissolving pulp and spinning: preparing the fiber after hydrophilic treatment into filamentous long fiber;
5) drying and fixing the filamentous long fibers, performing surface treatment and heat treatment: drying and fixing the filament fibers at 110 ℃, performing surface treatment and performing heat treatment at 135 ℃;
6) and (3) carrying out air flow drying and carding on the fibers after the heat treatment to finally obtain the hyperbranched structure high-water-absorption fibers.
Example 5
A preparation method of hyperbranched structure superabsorbent fibers comprises the following steps:
1) fiber fulcrum introduction: taking 10g of tetraisopropyl titanate as a catalyst, and carrying out esterification reaction on 30g of acrylic acid and 30g of bagasse fibers to prepare fiber acrylate;
2) branched graft copolymerization: carrying out copolymerization reaction on the fiber acrylic ester prepared in the step 1), 10g of allyl polyethylene glycol, 10g of allyloxy polyoxyethylene ether and 15g of nonahydroxymethyl propane triacrylate to obtain branched modified fibers, filtering and washing with water;
3) hydrophilic treatment: adding 40g of sodium hydroxide into branched modified fibers for metal ion exchange, wherein the exchange degree is 60-80%;
4) dissolving pulp and spinning: preparing the fiber after hydrophilic treatment into filamentous long fiber;
5) drying and fixing the filamentous long fibers, performing surface treatment and heat treatment: drying and fixing the filament fibers at 120 ℃, performing surface treatment and performing heat treatment at 140 ℃;
6) and (3) carrying out air flow drying and carding on the fibers after the heat treatment to finally obtain the hyperbranched structure high-water-absorption fibers.
The hyperbranched structure superabsorbent fiber products prepared in examples 1 to 5 were subjected to a water absorption rate test, the test results of which are shown in the following table:
TABLE 1 Water absorption and Water locking Properties of hyperbranched superabsorbent fibers
Claims (4)
1. A preparation method of super-branched structure superabsorbent fibers is characterized by comprising the following steps:
1) fiber fulcrum introduction: performing esterification reaction on acrylic acid and natural fibers, and adding a neutral organic titanium esterification catalyst to prepare fiber acrylate;
2) branched graft copolymerization: carrying out copolymerization reaction on the fiber acrylic ester prepared in the step 1), a grafting monomer and a trifunctional branching monomer to obtain a branched modified fiber, and filtering and washing;
3) hydrophilic treatment: carrying out metal ion exchange on the branched modified fiber, wherein the exchange degree is 60-80%;
4) dissolving pulp and spinning: preparing the fiber after hydrophilic treatment into filamentous long fiber;
5) drying and fixing the filamentous long fibers, and carrying out surface treatment and heat treatment on the filamentous long fibers;
6) carrying out airflow drying and carding on the fibers after the heat treatment;
the organic titanium catalyst comprises more than one of tetra-n-butyl titanate, isooctyl titanium, poly-n-butyl titanate and tetra-isopropyl titanate;
the grafting monomer comprises more than one of acrylic acid, acrylamide, allyl polyethylene glycol, methallyl polyethylene glycol and allyloxy polyoxyethylene ether;
the trifunctional branched monomer comprises one of trimethylolpropane triacrylate, nonamethylol propane triacrylate and pentadecamethylol propane triacrylate.
2. The method for preparing the hyperbranched structure superabsorbent fiber of claim 1, wherein the natural fiber of step 1) comprises one or more of cotton fiber, bagasse fiber, and wood pulp fiber.
3. The method for preparing the hyperbranched structure superabsorbent fiber of claim 1, wherein the step 3) is to add sodium hydroxide or potassium hydroxide to the branched modified fiber to perform sodium ion or potassium ion exchange.
4. A super-branched structure high water absorption fiber, which is prepared according to the preparation method of claim 1, has a super-branched structure, and has a water absorption rate of more than 360 g/g.
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| CN1743542A (en) * | 2005-09-30 | 2006-03-08 | 中国石油化工股份有限公司 | High water-absorption fiber and its preparing method |
| CN102838714A (en) * | 2012-10-15 | 2012-12-26 | 成都理工大学 | Preparation method of straw composite super absorbent resin |
| CN105392805A (en) * | 2013-08-01 | 2016-03-09 | 株式会社Lg化学 | Super absorbent polymer |
| CN106222783A (en) * | 2016-08-30 | 2016-12-14 | 江苏亨威实业集团有限公司 | The preparation method of ventilative water-absorption fiber |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06237952A (en) * | 1993-02-19 | 1994-08-30 | Kanebo Ltd | Absorbent material for incontinence pad |
| CN1743542A (en) * | 2005-09-30 | 2006-03-08 | 中国石油化工股份有限公司 | High water-absorption fiber and its preparing method |
| CN102838714A (en) * | 2012-10-15 | 2012-12-26 | 成都理工大学 | Preparation method of straw composite super absorbent resin |
| CN105392805A (en) * | 2013-08-01 | 2016-03-09 | 株式会社Lg化学 | Super absorbent polymer |
| CN106222783A (en) * | 2016-08-30 | 2016-12-14 | 江苏亨威实业集团有限公司 | The preparation method of ventilative water-absorption fiber |
Non-Patent Citations (5)
| Title |
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| 改性剑麻纤维接枝高吸水性树脂的合成与性能研究;朱荣华;《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》;20030615(第02期);第B016-30页 * |
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| 谢娜纯.蔗渣丙烯酸高吸水树脂的制备与表征.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2013,(第S2期),第B016-171页. * |
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