CN101768790B - Sheath core composite fibre of chitin and cellulose and preparation method thereof - Google Patents
Sheath core composite fibre of chitin and cellulose and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sheath core composite fibre of chitin and cellulose and a preparation method thereof. The dry breaking strength of the sheath core composite fibre provided by the invention is 2.5-5.5 cN/dtex, wet breaking strength is 2.2-5.2 cN/dtex, and dry elongation at break is 4-20 %. The preparation method is as follows: taking ionic liquid as solvent to prepare a chitin solution, cellulose solution or the mixed solution of chitin and cellulose; preparing the sheath core composite fibre with solution by the steps of defoaming, filtering, yielding silk, drawing, solidifying, cleaning, drafting, drying and the like. The technical route protects environment and saves energy, and the obtained product has high cost, high additional value and excellent performance, and the strength is improved by more than one time compared with that of the sheath core composite fibre of chitin and cellulose prepared with the common method, and practical value is high.
Description
Technical field
The present invention relates to a kind of chitosan and cellulosic core-sheath compound fibre and manufacture method thereof, specifically adopting ionic liquid is that solvent prepares chitosan---method of cellulosic type composite fibre and products thereof.
Background technology
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.
Chitosan 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 and chitin are respectively the first and second big renewable natural resourcess on the earth, estimate of the speed regeneration of the cellulose of occurring in nature with 40,000,000,000 tons of every year, nearly 10,000,000,000 tons of the annual biosynthetic chitins of nature, chitin also are the nitrogenous natural organic-compounds of the outer quantity maximum of isolating protein on the earth.Oil annual output in the whole world is about 5,000,000,000 tons, and proved reserves can be exploited about 50 years.How effectively, the to utilize cellulose and the chitin of environmental protection become one of focus of paying close attention to the world today.
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 chitosan 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 that contains chitin is disclosed in a kind of health type viscose fiber with high wet modulus, the Manufacturing approach and use, this fiber still adopts traditional adhering process, pollution problem is inevitable, and properties of product such as strength and elongation etc. are far away from cellulose fiber by solvent method simultaneously.Patent CN1318583 discloses a kind of chitin and cellulose intermingling material and uses thereof and preparation method.This material basic composition is chitin and cellulose.Its method for making is, and to be solvent with the NaOH/ thiourea solution carry out knifing, wire drawing with after chitin and the cellulosic different proportioning blend, solidifies in calcium chloride water, and regenerate in aqueous sulfuric acid, and drying obtains above-mentioned intermingling material then.Effects such as the blended fiber intensity by the preparation of this method is low, and chitin wherein is evenly distributed in fibrous inside, and it is antibiotic also have been subjected to very big influence.
Core-sheath compound fibre has irreplaceable effect aspect outstanding multicomponent fibre functional, not only drawn skin, core material advantage separately, also obtained the specific function that the core-skin type morphosis is given, simultaneously outstanding functional component---chitosan price condition with higher has more cost-effective effect for having.
Application number is that 200710114208.6 Chinese patent application discloses a kind of functional fiber material chitin and cellulosic composite fiber and preparation method thereof, and composite fibre adopts the core-skin type of cortex and core structure; Cellulose is gossypin, the lignose of degree of polymerization 400-800, chitin is dissolved in diluted sodium hydroxide solution prepares the chitin spinning solution, cellulose is dissolved in NaOH and the urea mixed aqueous solution system and prepares cellulose spin dope, two kinds of solution mixing systems are equipped with blend cortex spinning solution, and cellulose spin dope is as the sandwich layer spinning solution; Sandwich layer inlet and inlet by core-skin composite spinning silk machine enter the coagulating bath spinning moulding, and obtain the chitin and the cellulose composite fiber of skin-core structure through postprocessing working procedures.
Application number is that 200710014605.6 Chinese patent application discloses a kind of chitin and cellulose composite fiber and manufacture method thereof, the core-sheath compound fibre of forming by chitin and cellulose with cortex and core structure, the weight content ratio 3～80% of chitin, wherein the sandwich layer of composite fibre is a cellulose, and it is chitin and the cellulose composite fiber that adopts the skin-core structure that the core-skin composite spinning silk makes with cellulose spin dope, chitin spinning solution or chitin and cellulose blending spinning solution.
The disclosed chitin of above-mentioned CN200710114208.6 and CN200710014605.6 and cellulosic composite fiber and preparation method thereof, all be that chitin is dissolved in the diluted sodium hydroxide solution, its complicated process of preparation, can roughly be classified as a class with viscose technology, this technology is not as good as the environmental protection of cellulose made by soloent process technology, and its dissolving relates to the refrigerating process process, in order to dissolve the destruction that the refrigerating process that needs may cause cellulose crystal and macromolecular chain, finally cause the intensity of shaped article to reduce greatly, this is different from mechanism and effect does not need the freezing just directly NMMO of dissolving cellulos and ion liquid solvent method, and resulting properties of product are also not as good as the solvent method fiber superior performance.
In addition, owing to be rich in hydrogen bond in cellulose and the chitin molecule, generally show insoluble not molten characteristic, people are difficult on the big molecule aspect its modification processing.At present, make the field at fiber, the process route of one of cellulosic typical application product---viscose has the characteristic of high energy consumption, high pollution, faces huge survival pressure today at energy-intensive; Another route---lyocell fiber route belongs to cellulose made by soloent process preparation technology, have the characteristic of energy-saving and environmental protection, but output is relatively low, domesticly is in industrialization early stage.Chitin never is suitable for industrialized solvent and occurs, and product development at present is subjected to many-sided restrictions such as cost, technology, application.
Ionic liquid is one of focus of research at present, wherein some ionic liquids of imidazoles have been proved to be able to effective dissolving cellulos and have been used to prepare cellulose fibre, and disclosing with the ionic liquid as patent US6824599, CN1417407, CN1491974, CN1851063C, WO2006000197 etc. is the method for dissolution with solvents and processing of cellulose.
Chitin process deacetylation obtains having the chitosan of certain deacetylation, and with respect to chitin, the effect of chitosan intermolecular hydrogen bonding is less, and strand is easy to open, so be soluble in the number acid kind solvent; Simultaneously, ionic liquid also has strong or weak solvability for the chitosan with certain deacetylation, and this is by aspects such as the deacetylation decision of ion liquid kind and chitosan.
Application number is that to disclose a kind of be the preparation and the application of the cellulose blending fibre of solvent with the ionic liquid for 200710043563.9 Chinese patent application.
The manufacture method of core-sheath compound fibre is according to component kind and character, have solvent-free, solvent species, melting method, solution methods, dry method, wet method, the dried differences such as method that squirt have a variety of, though disclose chitin and cellulosic core-sheath compound fibre in the prior art, but dicyandiamide solution that is adopted and technology fall behind, adopt the one-component fiber of its prepared still not have practicality, the adding of second component, make fibre structure more loose, cause intensity very low, cortex is easier to wearing and tearing, fiber post processing and difficulty of weaving are very big, are difficult to drop into practical application.Therefore its described skin-core structure product and core-skin manufacturing technique do not have actual application value.
Prior art also discloses the method that adopts ion liquid dissolving cellulose and/or crust usually to prepare the blend composite fiber of spinning solution, still, does not announce for the chitosan and the cellulosic composite fibre that adopt the ionic liquid preparation to have skin-core structure.And for composite fibre with skin-core structure, cortex and sandwich layer can evenly be orientated together, shrink, solidify is the key of preparation core-sheath compound fibre, and want to make cortex and sandwich layer together evenly orientation and evenly shrinking just need make the spinning solution of cortex and sandwich layer can be compatible well, cortex and sandwich layer spinnability are all very good, this except needs are selected good solvent, also need to select to control the degree of polymerization of chitosan and deacetylation, the cellulosic degree of polymerization, each component original liquid concentration and with the mutual coupling of spinning technique etc.Concentration is irregular, inhomogeneous all can causing of viscosity differences, degree of polymerization difference, deacetylation be difficult for dissolving, causes difficulty in spinning, is difficult to make the fiber of function admirable.
As seen, only in conjunction with prior art disclosed employing ion liquid dissolving cellulose and/or crust usually prepare enlightenment that spinning solution and chitin and cellulose can be prepared into core-sheath compound fibre be can not prepare have excellent compatibility, the chitosan of stable skin-core structure, good mechanical property and anti-microbial property and cellulosic type composite fibre.Have excellent compatibility for how to prepare, the chitosan and the cellulosic type composite fibre of stable skin-core structure, good mechanical property and anti-microbial property, prior art does not provide more enlightenment.
The inventor is in the product manufacturing of carrying out chitosan and cellulosic core-sheath compound fibre and technical study, by research to product composition, structural design and technology, good mechanical performance, the lasting chitosan-cellulosic composite fibers of antibacterial effect such as the skin-core structure that has obtained having Practical Performance is stable, do, wet breaking strength height.
Summary of the invention
First purpose of the present invention is to provide a kind of chitosan and cellulosic core-sheath compound fibre, this core-sheath compound fibre has excellent physical and mechanical properties, dried fracture strength is 2.5～5.5cN/dtex, the common composite fibre of strength ratio doubles above, its good mechanical performance, functional and the cellulosic intensity and the hygroscopicity of chitosan can be combined, the individual style and multiple biological health and the medical functions that have biological fiber have simultaneously given play in actual applications that function is outstanding, the characteristic of economy and durability, environmental protection.
Second purpose of the present invention is to provide the preparation method of a kind of chitosan and cellulosic core-sheath compound fibre, and this method is the solvent method combination process, is different from general viscose process combination process.Method technology of the present invention is simple, environmental protection, and production cost is low, is fit to large-scale production.
For realizing first purpose of the present invention, the present invention adopts following technical scheme:
A kind of chitosan and cellulosic core-sheath compound fibre, the dried fracture strength of wherein said core-skin composite fiber is 2.5～5.5cN/dtex, and wet breaking strength is 2.2～5.2, and dried elongation at break is 4-20%.
Among the present invention, the sandwich layer of described core-sheath compound fibre is a cellulose, and the content of chitosan is 3%～100% in the cortex, and cellulosic content is 0～97% in the cortex.
Among the present invention, described cellulose is one or more in the cellulose of cotton pulp, wood pulp, bamboo pulp, straw pulp preparation; The deacetylation of described chitosan is 35～99%.
For realizing second purpose of the present invention, the present invention adopts following technical scheme:
A kind of method for preparing core-sheath compound fibre of the present invention, this method comprises the steps:
1) adopting ionic liquid is solvent, and dissolving cellulos makes cellulose solution, and cellulosic mass content is 4%～25% in the described cellulose solution;
2) adopting ionic liquid is solvent, and the superfine powder of dissolving chitosan or chitosan makes chitosan solution, and the content of chitosan is 5%～20% in the described chitosan solution;
3) described chitosan solution of blend and described cellulose solution, making chitosan described in the blend solution and described cellulosic mass ratio is 3: 97～100: 0;
4) with described cellulose solution and described blend solution or the deaeration of chitosan solution, filtration, with described blend solution or chitosan solution process cortex measuring pump, and with described cellulose solution process sandwich layer measuring pump, enter the core-skin type composite spinneret then, by spray silk, solidify, drawing-off, washing, drying steps make described composite fibre.
According to foregoing preparation method, described ionic liquid is by anion and cation composition;
Described anion is one or more in halide ion, thiocyanate ion, hydroxide ion, nitrate ion, phosphate anion or the carboxylic acid ion;
Described CATION has following structure:
Wherein: R1 and R2 are identical or different, are C
1～C
8Alkyl, allyl, vinyl, benzyl or H in one or more.
According to foregoing preparation method, described coagulating bath of solidifying is a concentration 0～80%, the ionic liquid aqueous solution that temperature is 25 ℃～80 ℃.
According to foregoing preparation method, step 2) described in the particle size range of superfine powder at 100nm～1000nm.
According to foregoing preparation method, measuring pump of cortex described in the step 4) and sandwich layer measuring pump volume flow ratio are 10: 90～70: 30;
According to foregoing preparation method, the multiple of drawing-off described in the step 4) is 2～15 times.
Below be detailed description of the present invention:
The dried fracture strength of chitosan provided by the present invention and cellulosic core-sheath compound fibre is 2.5～5.5cN/dtex, and wet breaking strength is 2.2～5.2, and dried elongation at break is 4-20%.
Application number is that 200710114208.6 Chinese patent application discloses a kind of chitin and its dried fracture strength of cellulosic composite fiber is up to 2.2cN/dtex, and intensity is low, is difficult to satisfy its application demand.Its dried fracture strength of chitin provided by the present invention and cellulosic composite fiber can reach 5.5cN/dtex, intensity than general chitin and cellulosic composite fiber doubles above, skin-core structure is stable, and its performance is more superior, can satisfy application demand better.
The preparation method of chitin provided by the present invention and cellulosic core-skin composite fiber comprises the steps:
1) adopting ionic liquid is solvent, and dissolving cellulos makes cellulose solution, and cellulosic mass content is 4%～25% in the described cellulose solution;
2) adopting ionic liquid is solvent, and the superfine powder of dissolving chitosan or chitosan makes chitosan solution, and the content of chitosan is 5%～20% in the described chitosan solution;
3) described chitosan solution of blend and described cellulose solution, making chitosan described in the blend solution and described cellulosic mass ratio is 3: 97～100: 0;
4) with described cellulose solution and described blend solution or the deaeration of chitosan solution, filtration, with described blend solution or chitosan solution process cortex measuring pump, and with described cellulose solution process sandwich layer measuring pump, enter the core-skin type composite spinneret then, by spray silk, solidify, drawing-off, washing, drying steps make described composite fibre.
Because the big molecule of chitin is the rigid chain with circulus, between the big molecule stronger hydrogen bond action is arranged again, and also its degree of crystallinity height, relative molecular weight is big, so its solubility property is poor, and the viscosity height of dissolving back stoste.For this reason, the spinning solution that make good spinning property must be selected a kind of good solvent and suitable original liquid concentration.
Application number is that 200710114208.6 Chinese patent application and application number are that 200710014605.6 Chinese patent application all discloses a kind of chitin and cellulosic composite fiber and preparation method thereof, but all be that chitin is dissolved in the diluted sodium hydroxide solution, its complicated process of preparation, can roughly be classified as a class with viscose technology, this technology is not as good as the environmental protection of cellulose made by soloent process technology, and its dissolving relates to the refrigerating process process, in order to dissolve the destruction that the refrigerating process that needs may cause cellulose crystal and macromolecular chain, finally cause the intensity of shaped article to reduce greatly, this is different from mechanism and effect does not need the freezing just directly NMMO of dissolving cellulos and ion liquid solvent method, and resulting properties of product are also not as good as the solvent method fiber superior performance.
In addition, because cellulose macromolecule has stable circulus and strong hydrogen bonding effect, make it water insoluble, diluted acid, diluted alkaline and general organic solvent, when cellulosic when containing urea liquid and mixing mutually with the diluted sodium hydroxide solution of chitin, because the solvent difference of two kinds of solution can cause the dissolubility of two kinds of components to reduce, visible application number is that 200710114208.6 Chinese patent application and application number are in 200710014605.6 all disclosed a kind of chitin of Chinese patent application and cellulosic composite fiber and preparation method thereof chitin to be dissolved in that diluted sodium hydroxide solution prepares chitin and spinning of cellulose stoste can not obtain certain density stabilizing solution.
And the priority reactivity that the preparation method of disclosed chitin and cellulosic composite fiber also needs to carry out two kinds of coagulating baths in the above-mentioned patent application is solidified, with the generation of chemical reaction and mass exchange, resulting fiber structurally mostly is loose undefined structure in the orientation process; Because it is insufficient that existence is solidified with mass exchange, its postprocessing working procedures is also more loaded down with trivial details.Therefore this method complicated process of preparation not only, and the intensity of prepared chitin and cellulosic core-sheath compound fibre is low, is difficult to satisfy application demand.
Among the present invention, when preparation chitosan and cellulosic core-sheath compound fibre, adopting on the one hand simultaneously, the ionic liquid of dissolving cellulos and chitosan is a solvent, the dissolving ability of regulation and control is strong, can obtain the solution of variable concentrations, viscosity, and, make technical process environmental protection more because this type of ionic liquid do not have corrosivity and volatility.The ionic liquid of general dissolved cellulose and chitosan can be considered to adopt, and as imidazoles chloro salt, imidazoles acetate etc., specifically will consider the influence of factors such as used ion liquid solubility property difference and cost in the actual production.On the other hand, method technology of the present invention is simple, fibre structure only needs a step coagulating bath process just can finalize the design, process of setting does not exist course of reaction and mass exchange, coagulating bath is consistent with solvent, and is recyclable, the intensity height of prepared chitosan and cellulosic core-sheath compound fibre, skin-core structure is stable, has significant using value.
Though it is the method for dissolution with solvents and processing of cellulose that patent US6824599, CN1417407, CN1491974, CN1851063C, WO2006000197 etc. disclose with the ionic liquid; Though also to disclose a kind of be the preparation and the application of the cellulose blending fibre of solvent with the ionic liquid and application number is 200710043563.9 Chinese patent application, and to be specifically related to the ionic liquid be the method for dissolution with solvents chitin, but for composite fibre with skin-core structure, cortex and sandwich layer can evenly be orientated together, shrink, solidifying is the key of preparation core-sheath compound fibre, and want to make cortex and sandwich layer together evenly orientation and evenly shrinking just need make the spinning solution of cortex and sandwich layer can be compatible well, cortex and sandwich layer spinnability are all very good, this also needs to select to control the degree of polymerization and the deacetylation of chitosan except needs are selected good solvent, the cellulosic degree of polymerization, each component original liquid concentration and with the mutual coupling of spinning technique etc.Concentration is irregular, inhomogeneous all can causing of viscosity differences, degree of polymerization difference, deacetylation be difficult for dissolving, causes difficulty in spinning, is difficult to make the fiber of function admirable.Among the present invention, cellulosic mass content in the cellulose spinning solution is controlled at 4%～25%, the mass content of chitosan is controlled at 5%～20% in the chitosan spinning solution, coupling cellulose and the degree of polymerization of chitosan and the deacetylation of chitosan can make cortex and sandwich layer well compatible, evenly are orientated together, contraction, coagulation forming.
In the method for the present invention, wherein:
Described ionic liquid is by anion and cation composition;
Described anion is one or more in halide ion, thiocyanate ion, hydroxide ion, nitrate ion, phosphate anion or the carboxylic acid ion;
Described CATION has following structure:
Wherein: R1 and R2 are identical or different, are C
1～C
8Alkyl, allyl, vinyl, benzyl or H in one or more.
Employing contains the ion liquid dissolving cellulose and the chitosan of these groups or ion, can widerly widen temperature, the concentration of formulations prepared from solutions, regulate the condensed state structure of fiberizing, mold the core-skin composite fiber of different structure and performance, thereby widen the field that this composite fibre is used biglyyer; And, make technical process environmental protection more because this type of ionic liquid do not have corrosivity and volatility.
In the said method, the coagulating bath aqueous solution that solidifies described in the step 4) or the ion liquid aqueous solution, preferred concentration 0～80%, the ionic liquid aqueous solution that temperature is 25 ℃～80 ℃.
Select suitable coagulating bath to help obtaining the core-sheath compound fibre of good mechanical properties.Chitosan solidifies and assembles more violently if chitosan is macromolecular in the wet spinning process, and irregular shape will appear in the fibre section.Improve spinning technique, chitosan is evenly shunk with sandwich layer with the cortex of cellulose fibre, can obtain the core-sheath compound fibre of good mechanical performance.The configuration of surface of chitosan fiber may be relevant with the post processing of coagulating bath concentration, fiber.Concentration as coagulating bath is too low, and the solidification forming of fiber is slower, and fiber surface is more smooth, and a spot of micropore is only arranged; Otherwise the concentration of coagulating bath is too high, and it is too violent to cause fiber to solidify, and will form more hole in the fiber.So, be according to the concentration of different requirement control coagulating baths.The ionic liquid aqueous solution of preferred concentration 0～80% is chitosan and the cellulosic core-sheath compound fibre that coagulating bath can access good mechanical performance among the present invention.
The particle size range of the superfine powder among the above-mentioned preparation method, step 2) is at 100nm～1000nm.
Owing to have a large amount of amino and hydroxyl, though make its solubility property be better than chitin greatly, the dissolving of chitosan is not too even in the chitosan molecule, and easily produces frozen glue in the slurries.Among the present invention, chitosan is prepared into superfine powder, can makes chitosan better, be dissolved in the ionic liquid more equably, thereby prepare the good spinning solution of spinning property.
In the said method, measuring pump of cortex described in the step 4) and sandwich layer measuring pump volume flow ratio are 10: 90～70: 30.
Recently control core/sheath ratio by the volume flow of control cortex measuring pump and sandwich layer measuring pump among the present invention.
In the said method, the multiple of drawing-off described in the step 4) is 2～15 times.
The as-spun fibre that just goes out coagulating bath is carried out suitable drawing-off, can reduce even eliminate defectives such as the hole that exists in the fiber that causes owing to spinning technique, slit, make fiber trend towards densification, help improving the regularity of big molecules align in the fiber, thereby the tensile strength of fiber is increased to some extent.
Among the present invention,, can make its prepared finished fiber with 2～15 times of its drawing-offs---the intensity of chitosan and cellulosic core-sheath compound fibre improves.
Chitosan has multiple functional, have wide range of applications, cost is also higher relatively, adopts core-skin composite spinning silk technology of the present invention, functional and the cellulosic intensity of chitosan can be combined, given play in actual applications that function is outstanding, the characteristic of economy and durability, environmental protection.
Compared with prior art, the present invention has following advantage:
(1) chitosan provided by the present invention and cellulosic core-sheath compound fibre have excellent physical and mechanical properties, dried fracture strength is 2.5～5.5cN/dtex, its intensity doubles above than general fibre, good mechanical performance, functional and the cellulosic intensity and the hygroscopicity of chitosan can be combined, the individual style and multiple biological health and the medical functions that have biological fiber have simultaneously given play in actual applications that function is outstanding, the characteristic of economy and durability, environmental protection;
(2) preparation method of chitosan provided by the present invention and cellulosic core-sheath compound fibre, cortex is evenly shunk with sandwich layer, skin-core structure is stable, thereby the functional and cellulosic intensity and the hygroscopicity of chitosan are combined, make the fiber of its preparation have advantages such as biological health function, hygroscopicity are strong, good permeability, good mechanical performance, have significant practicality;
(3) to adopt ion liquid solvent be system in the present invention, not only simultaneously dissolving cellulos and chitin, its dissolving ability of regulation and control is strong, can obtain the solution of variable concentrations, viscosity, and, make technical process environmental protection more because this type of ionic liquid do not have corrosivity and volatility;
(4) preparation method of chitosan provided by the present invention and cellulosic core-sheath compound fibre, technology is simple, and the intensity height of prepared chitosan and cellulosic core-sheath compound fibre has significant using value.
The specific embodiment
Below be the specific embodiment of the present invention, described embodiment is in order to further describe the present invention, rather than restriction the present invention.
Embodiment 1
(1) 11.7 parts of celluloses that derive from bamboo pulp is added in 78.3 parts of acetic acid 1-ethyl-3-methylimidazoles (all branch number average representation quality marks), make cellulose solution; Again 0.6 part of chitosan is added in 9.4 parts of acetic acid 1-ethyl-3-methylimidazole ion liquid solvents, make chitosan solution; Respectively described cellulose solution and described chitosan solution are heated up, 80 ℃ with the preparation chitosan solution and cellulose solution respectively as cortex and sandwich layer stoste, through cortex measuring pump and sandwich layer measuring pump, the flow proportional of cortex measuring pump and sandwich layer measuring pump is 1: 9, then they are entered the core-skin type composite spinneret jointly, metering output, wire vent is stretched to enter drawing-off coagulation forming in 10% acetic acid 1-ethyl-ion liquid aqueous solution of 3-methylimidazole, through washing, drying, obtaining intensity is 3.8cN/dtex, extension at break is 9.6% core-sheath compound fibre.
Embodiment 2
18.2 parts of celluloses that derive from cotton pulp are added in 121.8 parts of acetic acid 1-ethyl-3-methylimidazoles (all branch number average representation quality marks), make cellulose solution; Again 4.8 parts of chitosan are added in 55.2 parts of acetic acid 1-ethyl-3-methylimidazole ion liquid solvents, make chitosan solution; Respectively described cellulose solution and described chitosan solution are heated up, at 80 ℃ these two kinds of solution are mixed, stir, deaeration, obtain even mixed solution, with the preparation mixed solution and cellulose solution respectively as cortex and sandwich layer stoste, through cortex measuring pump and sandwich layer measuring pump, the flow proportional of cortex measuring pump and sandwich layer measuring pump is 3: 7, then they are entered the core-skin type composite spinneret jointly, metering output, wire vent is stretched to enter drawing-off coagulation forming in 30% acetic acid 1-ethyl-ion liquid aqueous solution of 3-methylimidazole, through washing, drying, obtaining intensity is 3.5cN/dtex, extension at break is 11.6% core-sheath compound fibre.
Embodiment 3
8 parts of celluloses that derive from cotton pulp are added in 72 parts of chloro 1-butyl-3-methylimidazoles, make cellulose solution; Again 0.8 part of chitosan is added in 19.2 parts of chloro 1-butyl-3-methylimidazole ion liquid solvents, make chitosan solution; Respectively described cellulose solution and described chitosan solution are heated up, at 130 ℃ these two kinds of solution are mixed, stir, deaeration, obtain even mixed solution, filtering solution, with the preparation mixed solution and cellulose solution respectively as cortex and sandwich layer stoste, through cortex measuring pump and sandwich layer measuring pump, the flow proportional of cortex measuring pump and sandwich layer measuring pump is 6: 4, then they are entered the core-skin type composite spinneret jointly, metering output, wire vent enters drawing-off coagulation forming in 60% chloro 1-butyl-ion liquid aqueous solution of 3-methylimidazole, through washing, drying, obtaining intensity is 3.4cN/dtex, extension at break is 12.7% core-sheath compound fibre.
Embodiment 4
The ionic liquid of using among this embodiment is chloro 1-butyl-3-methylimidazole, and concrete steps are as follows:
(1) adopting ionic liquid is solvent, 4 parts of celluloses that derive from wood pulp is added in 96 parts of ionic liquids dissolve, and makes cellulose solution, and wherein ionic liquid is chloro 1-butyl-3-methylimidazole;
(2) adopt the special-purpose pulverizer of chitosan that chitosan is ground into the superfine powder that particle diameter is 100nm earlier, adopting ionic liquid again is solvent, get in 5 parts of above-mentioned 95 parts of ionic liquids of superfine powders adding that obtain and dissolve, make chitosan solution, wherein ionic liquid is chloro 1-butyl-3-methylimidazole, and the deacetylation of chitosan is 45%;
(3) described chitosan solution of blend and described cellulose solution obtain blend solution;
(4) with described cellulose solution and described blend solution deaeration, filter, with described blend solution or chitosan solution process cortex measuring pump, and with described cellulose solution process sandwich layer measuring pump, enter the core-skin type composite spinneret then, by the spray silk, solidify, drawing-off, washing, drying steps makes and does fracture strength is 5cN/dtex, wet breaking strength is 4.0cN/dtex, dried elongation at break is 18% composite fibre, its mediopellis measuring pump and sandwich layer measuring pump volume flow ratio are 70: 30, the coagulating bath of solidifying is a concentration 60%, the chloro 1-butyl that temperature the is 70 ℃-3-methylimidazole aqueous solution, the multiple of drawing-off is 8 times.
Below be embodiment 5-7, concrete processing step is with embodiment 4, and differences such as the kind of raw material and consumption and technological parameter thereof are shown in Table 1, and wherein ion liquid CATION has following structure:
Table 1
Below be embodiment 8-10, concrete processing step is with embodiment 4, and differences such as the kind of raw material and consumption and technological parameter thereof are shown in Table 2, and wherein ion liquid CATION has following structure:
Table 2
Below be embodiment 11-13, concrete processing step is with embodiment 4, and differences such as the kind of raw material and consumption and technological parameter thereof are shown in Table 3, and wherein ion liquid CATION has following structure:
Table 3
Claims (9)
1. a chitosan and cellulosic core-sheath compound fibre, it is characterized in that: the dried fracture strength of described core-sheath compound fibre is 2.5～5.5cN/dtex, and wet breaking strength is 2.2～5.2cN/dtex, and dried elongation at break is 4-20%; Described chitosan and cellulosic core-sheath compound fibre adopt following method preparation:
1) adopting ionic liquid is solvent, and dissolving cellulos makes cellulose solution, and cellulosic mass content is 4%～25% in the described cellulose solution;
2) adopting ionic liquid is solvent, and the superfine powder of dissolving chitosan or chitosan makes chitosan solution, and the content of chitosan is 5%～20% in the described chitosan solution;
3) described chitosan solution of blend and described cellulose solution, making chitosan described in the blend solution and described cellulosic mass ratio is 3: 97～100: 0;
4) with described cellulose solution and described blend solution or the deaeration of chitosan solution, filtration, with described blend solution or chitosan solution process cortex measuring pump, and with described cellulose solution process sandwich layer measuring pump, enter the core-skin type composite spinneret then, by spray silk, solidify, drawing-off, washing, drying steps make described composite fibre.
2. core-sheath compound fibre according to claim 1 is characterized in that: the sandwich layer of described core-sheath compound fibre is a cellulose; Cortex is chitosan and cellulosic mixture, and wherein the content of chitosan is 3%～100%, and cellulosic content is 0～97%.
3. core-sheath compound fibre according to claim 1 is characterized in that: described cellulose is one or more in the cellulose of cotton pulp, wood pulp, bamboo pulp, straw pulp preparation; The deacetylation of described chitosan is 35～99%.
4. method for preparing any described core-sheath compound fibre of claim 1-3, it is characterized in that: described method comprises the steps:
1) adopting ionic liquid is solvent, and dissolving cellulos makes cellulose solution, and cellulosic mass content is 4%～25% in the described cellulose solution;
2) adopting ionic liquid is solvent, and the superfine powder of dissolving chitosan or chitosan makes chitosan solution, and the content of chitosan is 5%～20% in the described chitosan solution;
3) described chitosan solution of blend and described cellulose solution, making chitosan described in the blend solution and described cellulosic mass ratio is 3: 97～100: 0;
4) with described cellulose solution and described blend solution or the deaeration of chitosan solution, filtration, with described blend solution or chitosan solution process cortex measuring pump, and with described cellulose solution process sandwich layer measuring pump, enter the core-skin type composite spinneret then, by spray silk, solidify, drawing-off, washing, drying steps make described composite fibre.
5. method according to claim 4 is characterized in that:
Described ionic liquid is by anion and cation composition;
Described anion is one or more in halide ion, thiocyanate ion, hydroxide ion, nitrate ion, phosphate anion or the carboxylic acid ion;
Described CATION has following structure:
Wherein: R1 and R2 are identical or different, are C
1～C
8Alkyl, allyl, vinyl, benzyl or H in one or more.
6. method according to claim 4 is characterized in that: described coagulating bath of solidifying is a concentration 0～80%, the ionic liquid aqueous solution that temperature is 25 ℃～80 ℃.
7. method according to claim 4 is characterized in that: step 2) described in the particle size range of superfine powder at 100nm～1000nm.
8. method according to claim 4 is characterized in that: measuring pump of cortex described in the step 4) and sandwich layer measuring pump volume flow ratio are 10: 90～70: 30.
9. method according to claim 4 is characterized in that: the multiple of drawing-off described in the step 4) is 2～15 times.
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| CN101899171B (en) * | 2010-08-20 | 2011-11-30 | 厦门大学 | Method for preparing chitosan/cellulose composite material |
| CN103352266B (en) * | 2013-06-19 | 2015-05-13 | 东华大学 | Preparation method for cellulose and thermoplastic polymer skin-core type composite fiber |
| CN103352267B (en) * | 2013-06-19 | 2015-05-13 | 东华大学 | Preparation method for new type fully-degradable cellulose composite fiber with skin-core structures |
| CN104447560B (en) * | 2013-09-13 | 2017-10-13 | 中国科学院大连化学物理研究所 | A kind of imidazolium ionic liquid and its application in alkaline anion-exchange membrane |
| CN115531598B (en) * | 2022-10-28 | 2023-06-30 | 南京农业大学 | 3D printing madecassoside cellulose aerogel and preparation method and application thereof |
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