CN101177802A - Chitin element and cellulosic composite fiber and method for preparing same - Google Patents
Chitin element and cellulosic composite fiber and method for preparing same Download PDFInfo
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- CN101177802A CN101177802A CNA2007101142086A CN200710114208A CN101177802A CN 101177802 A CN101177802 A CN 101177802A CN A2007101142086 A CNA2007101142086 A CN A2007101142086A CN 200710114208 A CN200710114208 A CN 200710114208A CN 101177802 A CN101177802 A CN 101177802A
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Abstract
The invention relates to a chitin and cellulose sheath core compound fiber which is a functional fiber material and a preparation method thereof. The compound fibers employ the sheath core with a structure of a cortical layer and a core layer; the cellulose is gossypin with a polymerization degree of 400 to 800 and wood cellulose; the chitin is dissolved in diluted sodium hydroxide solution to prepare chitin spinning stock solution; the cellulose is dissolved in the mixed water solution of sodium hydroxide and urea to prepare cellulose spinning stock solution; the two solutions are mixed together to prepare blending cortical layer spinning stock solution. The cellulose spinning stock solution is used as the core layer spinning stock solution, which enters into coagulating bath through the entrance of the core layer of a sheath core compound spinning machine and an entrance and is formed by spinning and then goes through a post treatment process to obtain the chitin and the cellulose sheath core compound fibers of a sheath-core structure. The invention has rational technique procedure, high production efficiency, low cost and remarkable antibacterial effect, which is the ideal raw material of underclothes.
Description
Technical field:
The present invention relates to a kind of functional fiber material chitin and cellulosic composite fiber and preparation method thereof, particularly a kind of chitin with skin-core structure and cellulose composite fiber and preparation method thereof.
Background technology:
Chitin is chitin is handled the back deacetylate through concentrated base a product.Chitin is a kind of natural biological high polymer that refines in the cell membrane by the shell of shrimp, crab etc. and mushroom, algae.The year of occurring in nature chitin the biosynthesis amount more than 10,000,000,000 tons, be a kind of very abundant organic regenerative resource of cellulosic reserves that is only second to.Chitin has excellent biological compatibility, broad spectrum antibacterial and immunity and promotes functions such as activity, biological degradability.China has more than 300 chitin manufacturer at present, has become chitin production and big export country, add the production of the downstream product of chitin and chitin, and China has in fact formed the new industry group that a chitin and chitin are produced.Prior art adopts chitin solution to be spun into fiber, be used for absorbing medical applications such as operation sewing thread and artificial skin, but pure chitin fiber lacks the needed physical and mechanical properties of weaving back processing, cost is very high, cost an arm and a leg, its extensive popularization and application is restricted.
Cellulose fibre is as a kind of recyclability fiber, have advantages such as good sucting wet air permeability, snugness of fit be good, be widely used, in order to satisfy the multi-functional demand of people to fiber textile, can be by in the fibre spinning process, adding the production that some functional components realize the functional fibre cellulose fiber.Conventional viscose is a kind of regenerated celulose fibre, but owing to have a large amount of waste water and waste gas to generate in process of production, seriously polluted.Cellulose carbamate is a kind of cellulose esters, at present is used for weaving as the upgraded product of cellulose sulfonate, and the pollution that has solved environment has realized cellulosic making full use of.
At present, usually prepare and have antibiotic viscose by in the cellulose fibre production process, adding chitin or crust, adopt that composition such as chitin or chitin evenly distributes at fibrous inside in the fiber of this method preparation, as patent CN01126469.1, a kind of health type viscose fiber with high wet modulus, a kind of health type viscose fiber with high wet modulus that contains chitin is disclosed in the Manufacturing approach and use, diluted to a great extent on this fiber outer surface with the concentration of human body contact portion chitin, be difficult to bring into play the biologically active of chitin product, do not reach due sterilization to cause fiber, function such as antibiotic realizes.Patent CN1120198C, chitin/cellulose blending film or fibrous material and method for making thereof and purposes disclose a kind of love and respect shell element and cellulose intermingling material and uses thereof and preparation method, be evenly distributed in fibrous inside by chitin in the blended fiber of this method preparation, it is antibiotic etc., and effect also is subjected to very big influence.End is got up, and existing preparation contains fibre technology of chitin and products thereof and exists antibiotic effect low, and is functional poor, technology of preparing complexity, the outstanding shortcoming of the unreasonable grade of production technology.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that exists in the prior art, seek to provide a kind of chitin and cellulose composite fiber and preparation method thereof, this fiber has the core-skin type composite construction, described cortex is chitin and cellulosic mixture, sandwich layer is a cellulose, has excellent physical and mechanical properties, its composite fibre is owing to adopt core-sheath composite structure, chitin content is higher and have good antibiotic in the cortex, antipruritic, the smelly health care that waits disappears, because the cellulose composition has kept the good textile garment wearability of cellulose fibre itself in the sandwich layer, can be used for preparing various fabrics, especially the underwear health-care textile material with health care; Its preparation method technology is not polluted, and is suitable for people chitin and cellulose composite fiber are produced on a large scale.
To achieve these goals, the core-sheath compound fibre that chitin of the present invention and cellulose composite fiber are made up of chitin and cellulose with cortex and core structure, the weight percentage of chitin is preferably 6-30% than 2-50%; Wherein the sandwich layer of composite fibre is a cellulose, and fiber adopts the core-skin type of cortex and core structure; THE MOLECULAR WEIGHT OF CHITIN is 20-40 ten thousand, and deacetylation is 75%-95%; Described cellulose is a kind of in the gossypin, lignose of degree of polymerization 400-800 or two kinds.
The preparation method of chitin of the present invention and cellulose composite fiber is dissolved in the chitin spinning solution that diluted sodium hydroxide solution is prepared 1-10% concentration with chitin, it is the cellulose spin dope of 4-20% that cellulose is dissolved in NaOH and the urea mixed aqueous solution system preparation concentration, two kinds of solution mixing systems are equipped with blend cortex spinning solution, and cellulose spin dope is as the sandwich layer spinning solution; With the sandwich layer inlet of cellulose spin dope by core-skin composite spinning silk machine, cellulose and the chitin blending cortex spinning solution cortex inlet by core-skin composite spinning silk machine is entered the coagulating bath spinning moulding, and obtain the chitin and the cellulose composite fiber of skin-core structure through postprocessing working procedures; It is that the calcium chloride water of 1%-7% and aqueous sulfuric acid that concentration is 2%-10% solidify for twice that solidifying wherein adopted concentration; Postprocessing working procedures comprises washing, oils, bleaches, oven dry etc.
The preparation of chitin spinning solution: with molecular weight be the chitin of 20-40 ten thousand in 1: 2-1: 10 ratio is immersed in 40% the sodium hydrate aqueous solution, low-temp reaction obtains the chitin that alkalizes, through technologies such as filtration, deaerations, and utilize frozen water to regulate the chitin spinning solution that obtains 1.0-10.0%; Deacetylation is 75%-95%.
The preparation of cellulose spin dope: with the gossypin of degree of polymerization 400-800, in the lignose one or both according to NaOH: urea: cellulose is the cellulose solution that the weight percent proportioning of 3-6: 1-10: 0.5-10 prepares 1-10%, obtains cellulose spin dope through technologies such as low-temp reaction dissolving, filtration, deaerations.
The preparation of blend cortex spinning solution: adopt the chitin spinning solution to be 1-1.5 by volume with cellulose spin dope: 1 mixes and obtains blend cortex spinning solution, and the weight percent content of controlling chitin in the co-blended spinning stoste is 10-80%; NaOH (NaOH) solution and the percentage by weight that with percentage by weight is the chitin of 1-10% be the solution of the cellulosic NaOH of 1-10% and urea according to 1: the weight ratio of 1-10 is mixed, after filtration, deaeration technology makes the cortex spinning solution; The sandwich layer spinning solution is weight percentage to the aqueous solution process of cellulosic NaOH of 1-10% and urea is filtered, deaeration technology makes.
The preparation of chitin and cellulose composite fiber: chitin and cellulose blending cortex spinning solution are delivered to cortex inlet measuring pump, another road then is delivered to cellulose spin dope sandwich layer inlet measuring pump, enter in the coagulating bath through first, second coagulating bath spinning moulding through the core-skin type composite spinning, again through solidify, wash, oil, bleach, post processing such as oven dry, promptly obtain finished product chitin and cellulosic type composite fibre; The cortex sandwich layer compares and the content of chitin than adjusting in the metering of cortex inlet and sandwich layer inlet to adjust cortex and two kinds of spinning solutions of sandwich layer.
The present invention adopts the calcium chloride water of 2-8% as first coagulating bath, and the 4-12% aqueous sulfuric acid is as second coagulating bath, and through washing, oil, bleach, post processing such as oven dry, promptly obtain finished product chitin and cellulosic type composite fibre.
The cortex and the sandwich layer ratio that reach the chitin content in the whole fiber in the cortex of product of the present invention and adjust composite fibre, reduce the content of chitin in whole composite fibre with the content that increases chitin in the composite fibre cortex as much as possible, the chitin that not only has higher concentration in the cortex that just composite fibre is interior with human body contacts, thereby make this composite fibre have stronger chitin bioactive functions and health-care function, effectively raise the biological action of composite fibre, reduced the production cost of composite fibre; Process route of the present invention is reasonable, the production efficiency height, and cost is low, and the product antibacterial action is obvious, is desirable underwear raw material.
The specific embodiment:
The content that the invention is further illustrated by the following examples.
Embodiment 1:
Being 300,000 chitin, 100 grams with molecular weight is immersed in the sodium hydrate aqueous solution of 400 grams 40% in 1: 4 ratio, and low-temp reaction obtains the chitin that alkalizes, through filtration, deaeration technology, and utilize frozen water to regulate to obtain 2% chitin spinning solution.
With gossypin 1000 grams of the degree of polymerization 600, urea 1200 grams, NaOH 1500 grams are dissolved in the 183000 gram deionized waters, through the cellulose spin dope that fully stirs, low-temp reaction obtains 22000 grams 4.5%.
With chitin spinning solution/cellulose spin dope with 1.5: 1.0 (V/V) mixed as the cortex spinning solution, enter cortex inlet measuring pump through prefilter.Cellulose spin dope directly enters sandwich layer inlet measuring pump by prefilter.The rotating speed of cortex inlet measuring pump and sandwich layer inlet measuring pump is 1.0: 1.25.The composite spinning stoste of extruding through the core-skin type composite spinneret enters 35 ℃ of 3% calcium chloride water, the aqueous sulfuric acid that enters 35 ℃ 6% then carries out solidifying for twice, again by wash, oil, bleach, post processing such as oven dry, promptly obtain finished product chitin and cellulosic type composite fibre.
The dried fracture strength of fiber is 1.80cN/dtex, and dried elongation at break is 15.3%, and whiteness is 65.3%, and Chinese People's Anti-Japanese Military and Political College's enterobacteria rate is 99.8%.
Embodiment 2:
Repeat above-mentioned course of dissolution, with chitin spinning solution/cellulose spin dope with 1.4: 1.0 (V/V) mixed as the cortex spinning solution, enter cortex inlet measuring pump through prefilter.Cellulose spin dope directly enters sandwich layer inlet measuring pump by prefilter.The rotating speed of cortex inlet measuring pump and sandwich layer inlet measuring pump is 1.0: 1.25.The composite spinning stoste of extruding through the core-skin type composite spinneret enters 35 ℃ of 3% calcium chloride water, the aqueous sulfuric acid that enters 35 ℃ 6% then carries out solidifying for twice, further by wash, oil, bleach, post processing such as oven dry, promptly obtain finished product chitin and cellulosic type composite fibre.
The dried fracture strength of fiber is 1.92cN/dtex, and dried elongation at break is 16.2%, and whiteness is 66.0%, and Chinese People's Anti-Japanese Military and Political College's enterobacteria rate is 99.8%.
Embodiment 3:
Repeat above-mentioned course of dissolution, with chitin spinning solution/cellulose spin dope with 1.0: 1.0 (V/V) mixed as the cortex spinning solution, enter cortex inlet measuring pump through prefilter.Cellulose spin dope directly enters sandwich layer inlet measuring pump by prefilter.The rotating speed of cortex inlet measuring pump and sandwich layer inlet measuring pump is 1.0: 1.25.The composite spinning stoste of extruding through the core-skin type composite spinneret enters 35 ℃ of 3% calcium chloride water, the aqueous sulfuric acid that enters 35 ℃ 6% then carries out solidifying for twice, further by wash, oil, bleach, post processing such as oven dry, promptly obtain finished product chitin and cellulosic type composite fibre.
The dried fracture strength of fiber is 1.95cN/dtex, and dried elongation at break is 17.0%, and whiteness is 66.1%, and Chinese People's Anti-Japanese Military and Political College's enterobacteria rate is 99.6%.
Comparative examples:
Repeat above-mentioned course of dissolution, with chitin spinning solution/cellulose spin dope with 0: 1.0 (V/V) mixed as the cortex spinning solution, enter cortex inlet measuring pump through prefilter.Cellulose spin dope directly enters sandwich layer inlet measuring pump by prefilter.The rotating speed of cortex inlet measuring pump and sandwich layer inlet measuring pump is 1.0: 1.0.The composite spinning stoste of extruding through the core-skin type composite spinneret enters 35 ℃ of 3% calcium chloride water, the aqueous sulfuric acid that enters same temperature 6% then carries out solidifying for twice, further by wash, oil, bleach, post processing such as oven dry, promptly obtain finished product chitin and cellulosic type composite fibre.
The dried fracture strength of fiber is 2.2cN/dtex, and dried elongation at break is 16.0%, and whiteness is 67.0%, and Chinese People's Anti-Japanese Military and Political College's enterobacteria rate is 0%.
Claims (7)
1. chitin and cellulosic composite fiber is characterized in that the core-sheath compound fibre with cortex and core structure be made up of chitin and cellulose, and the content of chitin is 2-50%; THE MOLECULAR WEIGHT OF CHITIN is 20-40 ten thousand, and deacetylation is 75%-95%; Cellulose is the gossypin of degree of polymerization 400-800, in the lignose one or both.
2. chitin and cellulosic composite fiber preparation method, it is characterized in that chitin is dissolved in the chitin spinning solution that diluted sodium hydroxide solution is prepared 1-10% concentration, it is the cellulose spin dope of 4-20% that cellulose is dissolved in NaOH and the urea mixed aqueous solution system preparation concentration, two kinds of solution mixing systems are equipped with blend cortex spinning solution, and cellulose spin dope is as the sandwich layer spinning solution; With the sandwich layer inlet of cellulose spin dope by core-skin composite spinning silk machine, cellulose and the chitin blending cortex spinning solution cortex inlet by core-skin composite spinning silk machine is entered the coagulating bath spinning moulding, and obtain the chitin and the cellulose composite fiber of skin-core structure through postprocessing working procedures; It is that the calcium chloride water of 1%-7% and aqueous sulfuric acid that concentration is 2%-10% solidify for twice that solidifying wherein adopted concentration; Postprocessing working procedures comprises washing, oils, bleaches, dries.
3. chitin according to claim 2 and cellulosic composite fiber preparation method, it is characterized in that the preparation of chitin spinning solution: with chitin in 1: 2-1: 10 ratio is immersed in 40% the sodium hydrate aqueous solution, low-temp reaction obtains the chitin that alkalizes, and process filtration, deaeration technology also utilize frozen water to regulate the chitin spinning solution that obtains 1.0-10.0%.
4. chitin according to claim 2 and cellulosic composite fiber preparation method, it is characterized in that the preparation of cellulose spin dope: with the gossypin of degree of polymerization 400-800, in the lignose one or both according to NaOH: urea: cellulose is the cellulose solution that the weight percent proportioning of 3-6: 1-10: 0.5-10 prepares 1-10%, obtains cellulose spin dope through low-temp reaction dissolving, filtration, deaeration technology.
5. chitin according to claim 2 and cellulosic composite fiber preparation method, it is characterized in that the preparation of blend cortex spinning solution: adopt the chitin spinning solution to be 1-1.5 by volume with cellulose spin dope: 1 mixes and obtains blend cortex spinning solution, and the weight percent content of controlling chitin in the co-blended spinning stoste is 10-80%; Sodium hydroxide solution and the percentage by weight that with percentage by weight is the chitin of 1-10% be the solution of the cellulosic NaOH of 1-10% and urea according to 1: the weight ratio of 1-10 is mixed, after filtration, deaeration technology makes the cortex spinning solution; The sandwich layer spinning solution is weight percentage to the aqueous solution process of cellulosic NaOH of 1-10% and urea is filtered, deaeration technology makes.
6. chitin according to claim 2 and cellulosic composite fiber preparation method, it is characterized in that the preparation of chitin and cellulose composite fiber: chitin and cellulose blending cortex spinning solution are delivered to cortex inlet measuring pump, cellulose spin dope is delivered to sandwich layer inlet measuring pump, enter in the coagulating bath through first, second coagulating bath spinning moulding through the core-skin type composite spinning, through solidifying, wash, oil, bleach, dry post processing, promptly obtain finished product chitin and cellulosic type composite fibre again; The cortex sandwich layer compares and the content of chitin than adjusting in the metering of cortex inlet and sandwich layer inlet to adjust cortex and two kinds of spinning solutions of sandwich layer.
7. chitin according to claim 2 and cellulosic composite fiber preparation method, the calcium chloride water that it is characterized in that adopting 2-8% is as first coagulating bath, and the 4-12% aqueous sulfuric acid is as second coagulating bath.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748503B (en) * | 2008-12-18 | 2011-11-16 | 中国纺织科学研究院 | Method for preparing chitin/acrylic composite fiber by using ionic liquid as solvent |
| CN101768790B (en) * | 2008-12-29 | 2011-12-28 | 中国纺织科学研究院 | Sheath core composite fibre of chitin and cellulose and preparation method thereof |
| CN101857984B (en) * | 2009-04-13 | 2012-02-29 | 中国纺织科学研究院 | Composite fibre of chitin or derivative thereof and polyvinyl alcohol and manufacturing method thereof |
| CN106175018A (en) * | 2016-07-08 | 2016-12-07 | 华南理工大学 | A kind of degradable disponsable hair care towel and preparation method thereof |
| CN106963981A (en) * | 2017-04-21 | 2017-07-21 | 芜湖扬展新材料科技服务有限公司 | A kind of preparation method of placenta stem-cell composite chitin tissue renovation material |
| CN112111807A (en) * | 2020-08-31 | 2020-12-22 | 浙江理工大学 | Conductive multifunctional fiber with skin-core structure and preparation method thereof |
| CN112127008A (en) * | 2020-09-11 | 2020-12-25 | 嘉兴学院 | Cellulose/starch blend fiber and preparation method thereof |
| CN113882027A (en) * | 2021-11-02 | 2022-01-04 | 冯建国 | Chitin-based product preparation method, product and structure |
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2007
- 2007-11-12 CN CNA2007101142086A patent/CN101177802A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748503B (en) * | 2008-12-18 | 2011-11-16 | 中国纺织科学研究院 | Method for preparing chitin/acrylic composite fiber by using ionic liquid as solvent |
| CN101768790B (en) * | 2008-12-29 | 2011-12-28 | 中国纺织科学研究院 | Sheath core composite fibre of chitin and cellulose and preparation method thereof |
| CN101857984B (en) * | 2009-04-13 | 2012-02-29 | 中国纺织科学研究院 | Composite fibre of chitin or derivative thereof and polyvinyl alcohol and manufacturing method thereof |
| CN106175018A (en) * | 2016-07-08 | 2016-12-07 | 华南理工大学 | A kind of degradable disponsable hair care towel and preparation method thereof |
| CN106963981A (en) * | 2017-04-21 | 2017-07-21 | 芜湖扬展新材料科技服务有限公司 | A kind of preparation method of placenta stem-cell composite chitin tissue renovation material |
| CN112111807A (en) * | 2020-08-31 | 2020-12-22 | 浙江理工大学 | Conductive multifunctional fiber with skin-core structure and preparation method thereof |
| CN112111807B (en) * | 2020-08-31 | 2023-02-17 | 浙江理工大学 | Conductive multifunctional fiber with skin-core structure and preparation method thereof |
| CN112127008A (en) * | 2020-09-11 | 2020-12-25 | 嘉兴学院 | Cellulose/starch blend fiber and preparation method thereof |
| CN112127008B (en) * | 2020-09-11 | 2022-10-14 | 嘉兴学院 | Cellulose/starch blend fiber and preparation method thereof |
| CN113882027A (en) * | 2021-11-02 | 2022-01-04 | 冯建国 | Chitin-based product preparation method, product and structure |
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