CN110791837A - Composite pregelatinized starch, dextrin and polyvinyl alcohol fiber and preparation method thereof - Google Patents
Composite pregelatinized starch, dextrin and polyvinyl alcohol fiber and preparation method thereof Download PDFInfo
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- CN110791837A CN110791837A CN201911010354.3A CN201911010354A CN110791837A CN 110791837 A CN110791837 A CN 110791837A CN 201911010354 A CN201911010354 A CN 201911010354A CN 110791837 A CN110791837 A CN 110791837A
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- dextrin
- polyvinyl alcohol
- pregelatinized starch
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/123—Polyaldehydes; Polyketones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
Abstract
The invention relates to a composite pregelatinized starch, dextrin and polyvinyl alcohol fiber, which comprises the following components in percentage by mass: 10-70% of pregelatinized starch, 10-70% of dextrin and 10-80% of polyvinyl alcohol, wherein the preparation method of the composite pregelatinized starch, dextrin and polyvinyl alcohol fiber is that the pregelatinized starch and the dextrin are dissolved in advance according to a ratio, then the polyvinyl alcohol is added for dissolution, and blending copolymerization modification is carried out to obtain a spinning stock solution; preparing composite pre-gelatinized starch and dextrin/polyvinyl alcohol fiber through wet spinning, acetalation treatment and other processes; the invention is characterized in that the degradable composite pregelatinized starch, dextrin and polyvinyl alcohol fiber with excellent mechanics is manufactured by blending, copolymerizing and modifying the pregelatinized starch, the dextrin and the polyvinyl alcohol.
Description
Technical Field
The invention belongs to the technical field of textile industry, relates to preparation of novel textile pregelatinized starch, dextrin and polyvinyl alcohol fibers, and particularly relates to pregelatinized starch, dextrin and polyvinyl alcohol fibers which take pregelatinized starch, dextrin and polyvinyl alcohol as raw materials and a manufacturing method thereof.
Background
Textile fibers are divided into natural fibers and synthetic fibers, wherein the natural fibers are excellent in moisture absorption and air permeability, comfortable to wear, but low in yield and insufficient in strength; although the synthetic fiber has the advantages of high strength, large yield and the like, the synthetic fiber has great defects in the aspects of wearing comfort, health and the like, and the dyeing property is poor; because people have higher and higher requirements on the clothing fiber and pursue the natural, comfortable, healthy and colorful conditions, how to compound the natural fiber and the synthetic fiber is necessary to obtain the novel fiber with high performance and high quality; therefore, it is very necessary to mix or copolymerize and modify pregelatinized starch, dextrin and polyvinyl alcohol to make full use of their advantages and produce composite pregelatinized starch, dextrin and polyvinyl alcohol fibers with excellent usability.
The natural starch is a polysaccharide composed of glucose, which is a homopolymer, and starch is mainly composed of amylose and amylopectin, and it is generally considered that amylose is a linear polymer, which is a chain-shaped molecule formed by connecting α glucose through α -1, 4 glycosidic bonds, and has only a few branches present, and the molecule has a helical structure, amylopectin is a highly branched polymer, and branches are branched from the backbone, and the backbone is composed of α -1, 4 glycosidic bonds among glucose units, and the branches are connected to the backbone through α -1, 6 glycosidic bonds, and α -1, 6 glycosidic bonds at the branching points account for about 5% of the total glycosidic bonds, and the semicrystalline property is one of the important properties of the natural starch.
Starch (native starch) directly extracted from plants has the defects of cold water insolubility, poor paste heat stability, low shearing resistance, easy dehydration after cooling, poor aging and film forming properties, lack of water resistance and emulsifying capacity and the like, so that the application field of the starch is limited, people begin to artificially synthesize starch fibers in order to overcome the defects of the native starch, the preparation of the starch fibers can be traced back to 70 years in the 20 th century, and the prepared starch fibers are prepared by a wet method and a melting method which are respectively reported by the company of ham-pion Internatioml in the U.S. and the Ministry of agricultural and economic development of Alaska, and although the performance of the prepared fibers is not the best, the starch can be formed into fibers after all; in recent years, in the united states, japan and western europe, research has been conducted on how to obtain starch fibers having good application properties, and the research and development of starch fibers have been mainly focused on the fields of paper making, nonwoven fabrics, apparel, medical and sanitary materials, and the like.
The research on the application of starch fiber to clothes is the matter of 10 years recently, the utilization space of the starch fiber is greatly expanded, and the research and development direction of the starch fiber is also the main development direction of the starch fiber, the spinning of acrylonitrile grafted starch copolymer is carried out in Japan, and the report of the fiber (1.59cN/dtex) with higher strength is obtained, and the fiber has soft hand feeling and the texture of clothing material, and is expected to become the fiber for clothes; the American Maheras and the like blend starch acetate and cellulose acetate with high substitution degree to prepare fiber products; thermoplastic starch can be blended with other polymers, including polyolefin (such as PE, PP, and the like), polyester (such as PLA, PCL, PHA, and the like), cellulose fiber, and the like, the mechanical property and the water resistance of the blends are greatly improved, but the poor compatibility between the starch, the polyolefin and the polyester becomes a negative factor influencing the performance of products, and the problems of how to improve the compatibility of the blending components into a single homogeneous phase, how to balance the hydrophilicity and improve the thermoplasticity of the blends need to be solved.
The fiber has excellent performance, and is produced by polymerizing lactic acid obtained by fermenting corn starch and melt spinning to produce polylactic acid fiber, also called PIA fiber (LACTRON) or corn fiber, which can be biochemically decomposed to generate low combustion heat and no nitrogen oxide and other gas, and the used waste can be buried in soil or put in water and decomposed by microorganism to form carbonic acid and water, and under the action of photosynthesis, can produce starch as starting material, and is an ecological fiber with great development potential, The wool is blended to produce T-shirts, jackets, stockings, evening dresses and the like with silky appearances.
In addition to PLA fibers, dupont, usa recently produced a completely new polymeric compound product, "soliana" (So mna). The polyester compound has many excellent characteristics like nylon, and the product has the advantages of comfort, wear resistance, wrinkle resistance, elasticity, protection and the like, the most important advantage is that the polyester compound can be recycled, and the raw material of So _ rom is corn starch.
However, because the fiber has complex raw material extraction process and large investment, the produced fiber has high production cost, and the spinning solution prepared by the method disclosed by the invention has poor stability, poor fiber forming property and low comprehensive performance; in order to overcome the defects of the original starch, the pregelatinized starch and the dextrin are added with polyvinyl alcohol for dissolution, and are subjected to blending copolymerization modification to prepare the composite pregelatinized starch, the dextrin and the polyvinyl alcohol fiber, which have excellent hand feeling, low price, simple process and degradability.
Disclosure of Invention
The invention aims to provide degradable composite pregelatinized starch, dextrin and polyvinyl alcohol fibers which are low in price and simple in process and a preparation method thereof.
The purpose of the invention is realized as follows: a composite pregelatinized starch, dextrin and polyvinyl alcohol fiber comprises the following components in percentage by mass: 10-70% of pregelatinized starch, 10-70% of dextrin and 10-80% of polyvinyl alcohol.
The polymerization degree of the polyvinyl alcohol is 1750 +/-50.
A preparation method of composite pregelatinized starch, dextrin and polyvinyl alcohol fiber comprises the following steps:
step (1), preparing a spinning solution: respectively adding a proper amount of pregelatinized starch and dextrin into water, continuously stirring to completely dissolve the pregelatinized starch and the dextrin, then adjusting the pH value of the solution to 8-10, continuously adding polyvinyl alcohol under a stirring state until the polyvinyl alcohol is completely dissolved, adjusting the pH value of the solution to 4-12, finally adding a proper amount of initiator, and after polymerization, filtering, standing and defoaming to prepare a spinning solution;
step (2), wet spinning: spinning the defoamed spinning stock solution, and performing the processes of drafting, drying and heat setting to obtain a semi-finished fiber;
and (3) after-finishing of the semi-finished fiber: adjusting the pH value, performing acetalation treatment on the semi-finished fiber, and then performing washing, drying, oiling, cutting and the like to finally obtain the composite pre-gelatinized starch, dextrin and polyvinyl alcohol fiber.
The temperature of the pregelatinized starch and dextrin in the step (1) is 40-80 ℃ in the dissolving process, the temperature of the solution is gradually increased to 50-100 ℃ in the dissolving process of the polyvinyl alcohol, and the concentration of the spinning solution prepared in the step (1) is 10-30%.
The acid used for adjusting the pH value in the step (1) and the step (3) is one or two of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, formic acid, acetic acid, acrylic acid, methacrylic acid, polyacrylic acid, polymethacrylic acid and ascorbic acid.
And (3) adjusting the pH value in step (1) and step (3) by using one or two of sodium hydroxide, potassium hydroxide, diethanolamine, triethanolamine, sodium ethanol sulfonate and disodium ethylene diamine tetraacetate.
The initiator in the step (1) is one or two of potassium persulfate, ammonium persulfate, benzoyl peroxide and ceric ammonium nitrate.
The dosage of the initiator in the step (1) is 0.15 to 3 percent of the dosage of the added pregelatinized starch and dextrin; the addition condition of the initiator in the step (1) is that the pH value is 4-12; the polymerization reaction time in the step (1) is 1-12 hours, and the standing and defoaming time is 3-10 hours.
And (3) aldehyde used in acetalization treatment of the semi-finished fiber in the step (3) is one of formaldehyde, acetaldehyde, methyl acetaldehyde, propionaldehyde, glyoxal, malonaldehyde, succinaldehyde or glutaraldehyde.
The acetalization treatment conditions in the step (3) are as follows: the PH value is 4-6, the temperature is 55-95 ℃, and the acetalization time is 5-200 minutes.
The invention has the beneficial effects that: the degradable pregelatinized starch and the dextrin/polyvinyl alcohol fiber with excellent mechanics are manufactured by blending, copolymerizing and modifying the pregelatinized starch, the dextrin and the polyvinyl alcohol; moreover, the pregelatinized starch and dextrin have wide raw material sources and low price, the industrial production can be realized by utilizing the existing equipment for producing the polyvinyl alcohol fiber, the process is simple, and the production cost can be effectively reduced; the pre-gelatinized starch and dextrin/polyvinyl alcohol fibers manufactured by the invention can be used for clothing textiles, and tests show that the titer of the pre-gelatinized starch and the dextrin/polyvinyl alcohol fibers is 1-5 dtex, the dry breaking strength is 4-8 cN/dtex, the dry breaking elongation is 12-40%, the initial modulus reaches 80-110 cN/dtex, the softening point in water is more than or equal to 110 ℃, the moisture regain is 4-8%, and the content of the pre-gelatinized starch and the dextrin in the fibers is more than or equal to 20%.
Detailed Description
The present invention is further described with reference to the following examples, which are intended to be illustrative only and should not be construed as limiting the scope of the invention, which are not to be construed as being limited thereby, but rather as being modified in light of the above teachings.
Example 1
Weighing 15kg of pregelatinized starch and 15kg of dextrin, adding into enough water, fully stirring and mixing, adding NaOH solution, adjusting the pH value to 8, heating to 65 ℃, and stirring until the pregelatinized starch and the dextrin are completely dissolved; then 100kg of polyvinyl alcohol is added, the temperature is raised to 95 ℃, and the mixture is stirred until the mixture is completely dissolved; adding 300g of initiator potassium persulfate, adjusting the pH value to 5 by using hydrochloric acid, carrying out thermal polymerization reaction for 2 hours, heating to 90 ℃, filtering, standing and defoaming for 6 hours to prepare spinning stock solution with the concentration of 16%; spinning by adopting a polyvinyl alcohol fiber wet spinning process, wherein the temperature of a coagulation bath is 40 ℃, the pH value is 8, and obtaining a semi-finished fiber after drafting, drying and heat setting; adjusting the pH value to 4.5 by hydrochloric acid, adjusting the acetalization temperature to 65 ℃, and performing acetalization treatment on the semi-finished fiber by formaldehyde for 100 minutes; after acetalization, the raw materials are washed, dried, oiled and cut to prepare pre-gelatinized starch and dextrin/polyvinyl alcohol fibers.
Example 2
Weighing 20kg of pregelatinized starch and 20kg of dextrin, adding into enough water, fully stirring and mixing, adding NaOH solution, adjusting the pH value to 8, heating to 65 ℃, and stirring until the pregelatinized starch and the dextrin are completely dissolved; then 100kg of polyvinyl alcohol is added, the temperature is raised to 95 ℃, and the mixture is stirred until the mixture is completely dissolved; adding 300g of initiator potassium persulfate, adjusting the pH value to 5 by using hydrochloric acid, carrying out thermal polymerization reaction for 2 hours, heating to 90 ℃, filtering, standing and defoaming for 6 hours to prepare spinning stock solution with the concentration of 16%; spinning by adopting a polyvinyl alcohol fiber wet spinning process, wherein the temperature of a coagulation bath is 40 ℃, the pH value is 8, and obtaining a semi-finished fiber after drafting, drying and heat setting; adjusting the pH value to 4.5 by hydrochloric acid, adjusting the acetalization temperature to 65 ℃, and performing acetalization treatment on the semi-finished fiber by formaldehyde for 100 minutes; after acetalization, the raw materials are washed, dried, oiled and cut to prepare pre-gelatinized starch and dextrin/polyvinyl alcohol fibers.
Example 3
Weighing 25kg of pregelatinized starch and 25kg of dextrin, adding into enough water, fully stirring and mixing, adding NaOH solution, adjusting the pH value to 8, heating to 65 ℃, and stirring until the pregelatinized starch and the dextrin are completely dissolved; then 100kg of polyvinyl alcohol is added, the temperature is raised to 95 ℃, and the mixture is stirred until the mixture is completely dissolved; adding 300g of initiator potassium persulfate, adjusting the pH value to 5 by using hydrochloric acid, carrying out thermal polymerization reaction for 2 hours, heating to 90 ℃, filtering, standing and defoaming for 6 hours to prepare spinning stock solution with the concentration of 16%; spinning by adopting a polyvinyl alcohol fiber wet spinning process, wherein the temperature of a coagulation bath is 40 ℃, the pH value is 8, and obtaining a semi-finished fiber after drafting, drying and heat setting; adjusting the pH value to 4.5 by hydrochloric acid, adjusting the acetalization temperature to 65 ℃, and performing acetalization treatment on the semi-finished fiber by formaldehyde for 100 minutes; after acetalization, the raw materials are washed, dried, oiled and cut to prepare pre-gelatinized starch and dextrin/polyvinyl alcohol fibers.
The composite pregelatinized starch, dextrin and polyvinyl alcohol fiber obtained in example 1, example 2 and example 3 were respectively subjected to performance tests, and the test results were compared with those of a single polyvinyl alcohol fiber (comparative example), and the results are shown in the following table:
TABLE 1 comparison of the Properties of the composite pregelatinized starch, dextrin, polyvinyl alcohol fiber and the Single polyvinyl alcohol fiber of the examples
| Comparative example | Example 1 | Example 2 | Example 3 | |
| Fineness/dtex | 1.50 | 1.50 | 1.53 | 1.51 |
| Dry breaking Strength/cN/dtex | 4.46 | 4.85 | 4.62 | 4.08 |
| Elongation at break/% | 14.6 | 16.32 | 15.42 | 14.41 |
| Softening point in water/. degree.C | 110 | 115 | 115 | 115 |
| Moisture regain/% | 2.46 | 4.9 | 5.2 | 5.6 |
| Modulus cN/dtex | 85 | 110 | 92 | 90 |
| Content of pregelatinized starch% | / | 11.5 | 14.3 | 16.7 |
| Content of dextrin% | / | 11.5 | 14.3 | 16.7 |
| Degradability | 900 | 280 | 250 | 210 |
From the above table, it can be seen that the properties of the pregelatinized starch and dextrin/polyvinyl alcohol fibers produced by the method of the present invention are superior to those of single polyvinyl alcohol fibers.
Claims (10)
1. A composite pregelatinized starch, dextrin and polyvinyl alcohol fiber is characterized in that: the paint comprises the following components in percentage by mass: 10-70% of pregelatinized starch, 10-70% of dextrin and 10-80% of polyvinyl alcohol.
2. The composite pregelatinized starch, dextrin, polyvinyl alcohol fiber of claim 1, wherein: the polymerization degree of the polyvinyl alcohol is 1750 +/-50.
3. A preparation method of composite pregelatinized starch, dextrin and polyvinyl alcohol fiber is characterized by comprising the following steps: it comprises the following steps:
step (1), preparing a spinning solution: respectively adding a proper amount of pregelatinized starch and dextrin into water, continuously stirring to completely dissolve the pregelatinized starch and the dextrin, then adjusting the pH value of the solution to 8-10, continuously adding polyvinyl alcohol under a stirring state until the polyvinyl alcohol is completely dissolved, adjusting the pH value of the solution to 4-12, finally adding a proper amount of initiator, and after polymerization, filtering, standing and defoaming to prepare a spinning solution;
step (2), wet spinning: spinning the defoamed spinning stock solution, and performing the processes of drafting, drying and heat setting to obtain a semi-finished fiber;
and (3) after-finishing of the semi-finished fiber: adjusting the pH value, performing acetalation treatment on the semi-finished fiber, and then performing washing, drying, oiling, cutting and the like to finally obtain the composite pre-gelatinized starch, dextrin and polyvinyl alcohol fiber.
4. The method for preparing the composite pregelatinized starch, dextrin and polyvinyl alcohol fiber according to claim 3, characterized in that: the temperature of the pregelatinized starch and dextrin in the step (1) is 40-80 ℃ in the dissolving process, the temperature of the solution is gradually increased to 50-100 ℃ in the dissolving process of the polyvinyl alcohol, and the concentration of the spinning solution prepared in the step (1) is 10-30%.
5. The method for preparing the composite pregelatinized starch, dextrin and polyvinyl alcohol fiber according to claim 3, characterized in that: the acid used for adjusting the pH value in the step (1) and the step (3) is one or two of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, formic acid, acetic acid, acrylic acid, methacrylic acid, polyacrylic acid, polymethacrylic acid and ascorbic acid.
6. The method for preparing the composite pregelatinized starch, dextrin and polyvinyl alcohol fiber according to claim 3, characterized in that: and (3) adjusting the pH value in step (1) and step (3) by using one or two of sodium hydroxide, potassium hydroxide, diethanolamine, triethanolamine, sodium ethanol sulfonate and disodium ethylene diamine tetraacetate.
7. The method for preparing the composite pregelatinized starch, dextrin and polyvinyl alcohol fiber according to claim 3, characterized in that: the initiator in the step (1) is one or two of potassium persulfate, ammonium persulfate, benzoyl peroxide and ceric ammonium nitrate.
8. The method for preparing the composite pregelatinized starch, dextrin and polyvinyl alcohol fiber according to claim 3, characterized in that: the dosage of the initiator in the step (1) is 0.15 to 3 percent of the dosage of the added pregelatinized starch and dextrin; the addition condition of the initiator in the step (1) is that the pH value is 4-12; the polymerization reaction time in the step (1) is 1-12 hours, and the standing and defoaming time is 3-10 hours.
9. The method for preparing the composite pregelatinized starch, dextrin and polyvinyl alcohol fiber according to claim 3, characterized in that: and (3) aldehyde used in acetalization treatment of the semi-finished fiber in the step (3) is one of formaldehyde, acetaldehyde, methyl acetaldehyde, propionaldehyde, glyoxal, malonaldehyde, succinaldehyde or glutaraldehyde.
10. The method for preparing the composite pregelatinized starch, dextrin and polyvinyl alcohol fiber according to claim 3, characterized in that: the acetalization treatment conditions in the step (3) are as follows: the PH value is 4-6, the temperature is 55-95 ℃, and the acetalization time is 5-200 minutes.
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| CN113249820A (en) * | 2021-06-04 | 2021-08-13 | 东华大学 | Preparation method of cellulose/starch composite fiber |
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