A kind of bacteria cellulose and natural polysaccharide blend fiber and preparation method thereof
The present invention relates to the high-tech fiber art, relate in particular to the preparation method of a kind of bacteria cellulose and natural polysaccharide blend fiber and such blended fiber.
Along with the development of society, progress, the growth of population and the continuous expansion of textile fabric Application Areas of science and technology, the demand of textile fabric presents the trend of increase year after year.Because world's cultivated area reduces gradually, the cultivated area of the mulberry treies of many countries beginning compressed cotton, various fiber crops, sericulture etc. and grassland sheep raising utilize area, this will directly have influence on the production and supply amount of traditional natural fabric.The supply of the regeneration chemical fibre of support cotton linter, wood pulp etc. etc. has been tending towards the limit, and the supply of fast growing wood also can't continue to increase.The oil that synthetic fiber rely on is petered out, and can't regenerate in a short time, and petroleum resources is again the main channel of the current energy, and synthetic fiber from now on are difficult to continue to rely on this resource hierarchy again.Therefore, the supply breach of textile fiber material is more and more large.
Bacteria cellulose (Bacterial cellulose is called for short BC) is by the bacteriogenic family macromolecule compound of polysaccharide of part.The chemical composition of bacteria cellulose is identical with plant cellulose with chemical constitution, but its aggregate velocity is faster than plant cellulose, and has the characteristic of following excellence:
(1) high-purity, the degree of polymerization and degree of crystallinity.Compare with plant cellulose, bacteria cellulose does not contain lignin, pectin, hemicellulose and other cell wall constituents, and molecularly oriented is good, the structure homogeneous, and exist with the Single Fiber form, content of cellulose reaches more than 99%.In addition, the degree of crystallinity of bacteria cellulose is about 95%, and the degree of polymerization is about 16000, all is higher than the plant celluloses such as high quality cotton fiber, cotton linter and wood pulp cellulose.
(2) hyperfine network structure.Bacteria cellulose is the fiber silk ribbon that the microfiber bundle by diameter 3～4nm is interconnected to form by hydrogen bond action, and its width is approximately 30～100nm, and thickness is 3～8nm, is intertwined to form flourishing hyperfine network structure.
(3) high-tensile and elastic modelling quantity.Under static culture conditions, the elastic modelling quantity of bacteria cellulose film is that the anti-tear ability of drawing is the polyethylene of same thickness and 6 times of polychloroethylene film more than the several times to ten times of general fiber.After washing, drying, Young's modulus can reach 10MPa, and after hot-pressing processing, Young's modulus can reach 30MPa, and is higher 4 times than the intensity of organic synthetic fibers.
(4) moisture holding capacity is strong.Because the superfine nano structure of bacteria cellulose and molecular memory are at a large amount of hydrophilic radicals, cellulose inside has a lot " duct ", surface area is 300 times of plant cellulose, make it have strong suction and water holding moisture-retaining capacity, generally can absorb 60～700 times to the moisture content of its dry weight.
(5) higher biocompatibility, adaptability and good biodegradability.Bacteria cellulose is comprised of the synthetic pure cellulose nanofiber of acetobacter xylinum, causes hardly foreign matter and inflammatory reaction, has good intensity under hygrometric state, and formed in situ, biocompatibility.Under the conditions such as acidity, microorganism and cellulase catalysis, can directly degrade at nature, free from environmental pollution, environmentally friendly.
(6) Modulatory character during biosynthesis.By regulating condition of culture, can obtain the different bacteria cellulose of chemical property.Can utilize glucose and the synthetic 2-Acetamido-2-deoxy-D-glucose of acetyl grape amine such as acetobacter xylinum, and with 4% ratio 2-Acetamido-2-deoxy-D-glucose is connected on the bacteria cellulose.In addition, take different cultural methods, such as static culture and dynamic cultivation, also can obtain different higher structures and cellulose of different nature.
The natural macromolecular that the aldose that polysaccharide is linked by glycoside bond or ketose form, the polysaccharide that is comprised of a kind of monose is called same glycan, and is called heteroglycan by the polysaccharide that more than one monose forms.Polysaccharide is widely distributed at occurring in nature, and aboundresources all has polysaccharide to exist in higher plant, algae, bacterium class and animal body.According to forming different from structure, the kind of polysaccharide is countless, and up to the present, people just have a hundreds of kind from what occurring in nature extracted.In addition, people study and find that polysaccharose substance has some special biologically actives.Have the effects such as anti-inflammatory, antipruritic, beauty treatment, skin care such as, algal polysaccharides; Chitin has natural antibiotic property, and can promote the growth of SF and epidermal keratinocytes; Hyaluronic acid has the effects such as the scar of elimination, beauty treatment, skin care, moisturizing, smoothing wrinkle; SKGM has the effect such as delay senility.
Therefore, utilize bacteria cellulose and abundant polysaccharide resource to produce textile fabric, not only for alleviating following textile fiber material supply pressure, be of great practical significance; And the blended fiber of preparation has the several functions of bacteria cellulose and polysaccharide concurrently take bacteria cellulose and several polysaccharide as raw material, can satisfy people's consumption demand, raising people's quality of life.
Publication number is the Chinese invention patent of CN 101492837A, disclose a kind of production method of bacteria cellulose fibre with high degree of polymerization: (1) is dissolved in bacteria cellulose in the solvent, is made into mass fraction and is 1～30% bacterial cellulose solution, filters, standing and defoaming gets spinning solution; (2) with step (1) spinning solution curing molding after the spinneret orifice ejection, stretched again, washing is made finished product after the conventional operation of typing and dry these several roads.Preparation method of the present invention is simple, is suitable for suitability for industrialized production; The gained bacteria cellulose fibre is compared with other cellulose fibre, and fracture strength and modulus are high, reaches the level of high strength industrial filament; And biocompatibility, biodegradability, hydrophily and good with the cohesiveness of rubber.
The patent No. is the Chinese invention patent of ZL 200710014403.1, a kind of preparation method of common and functional alginic acid fibre is disclosed: be 3%～8% sodium alginate soln with the water-soluble mass percent of producing of an amount of sodium alginate, and can add suitable functional material in solution; Be 2%～5% calcium chloride solution with an amount of calcium chloride mass percent of producing soluble in water, produce coagulating bath; The sodium alginate soln of producing is produced calcium alginate fibre with wet spinning in the capacity coagulating bath, the extensibility of fiber is 30%～50%.The fiber that said method obtains can be used for making medical adhesive-bonded fabric, also can be used for pure spin or with cotton, viscose glue, bamboo pulp, hair, flax fiber blending manufacturing clothes usefulness and FURNISHING FABRIC.
Publication number is the Chinese invention patent of CN 101613893A, the method for preparing blended fiber take bacteria cellulose and sodium alginate as raw material is disclosed, its technical scheme is that the sodium alginate micro-nano powder is added in the spinning solution of bacteria cellulose, obtains bacteria cellulose and sodium alginate blended fiber by wet spinning technology.
Take bacteria cellulose and natural polysaccharide as the technological difficulties that raw material prepares blended fiber be: the common dissolving technology of bacteria cellulose and multiple natural polysaccharide and supporting blended fiber forming technique, therefore up to the present literature search there is not yet and adopts wet method or dry-wet spinning technique, the report of preparation bacteria cellulose and polysaccharide blend fiber.
Summary of the invention
The present invention adopts a class ion-type solvent, makes bacteria cellulose and natural polysaccharide reach well common dissolving, adopts wet method or dry-wet spinning technique, has prepared bacteria cellulose and natural polysaccharide blend fiber.
The used bacteria cellulose of the present invention is that the degree of polymerization of static state or dynamic cultivation is 1000～16000 self-control or commercially available industrialization product, used natural polysaccharide is a kind of in plant cellulose, alginic acid, chitin, shitosan, carboxymethyl cellulose, SKGM and the hyaluronic acid, also can be that two or more are with the mixture of arbitrary proportion.
One of purpose of the present invention is to provide the blended fiber of a class take bacteria cellulose and natural polysaccharide as raw material.
Two of purpose of the present invention is to provide the preparation method of a kind of bacteria cellulose and natural polysaccharide blend fiber.
For realizing one of purpose of the present invention, its technical solution is:
Bacteria cellulose and natural polysaccharide blend fiber, wherein the quality percentage composition of bacteria cellulose in blended fiber is 5%-95%, surplus is natural polysaccharide.
For realizing two of purpose of the present invention, its technical solution is:
The preparation method of a kind of bacteria cellulose and natural polysaccharide blend fiber comprises the steps:
A is dissolved in the mixture of bacteria cellulose and natural polysaccharide in the ion-type solvent, obtains the quality percentage composition and be 3%～10% bacteria cellulose and the mixed solution of natural polysaccharide;
Behind the solution filter that b produces step a, vacuum deaerator 16～24h or standing and defoaming 24～32h obtain the spinning solution for the preparation of blended fiber;
The spinning solution that c step b produces enters coagulating bath or enters in the coagulating bath through spinning head and after by one section air layer through spinning head under pressure, then through drawing-off, obtain bacteria cellulose and natural polysaccharide blend fiber after washing, oil, drying.
Above-mentioned steps a may further comprise the steps:
A1 takes by weighing respectively a certain amount of bacteria cellulose and natural polysaccharide, in 60～100 ℃ of lower oven dry 0.5～5h, obtains dry spinning material in vacuum drying oven;
A2 is heated to 50～90 ℃ with the ion-type solvent, then adds dry bacteria cellulose and the mixture of natural polysaccharide, mechanical agitation 1～5h, the solution that obtains mixing;
Above-mentioned ion-type solvent is 1-ethyl-3-methylimidazole tetrafluoroborate, 1-vinyl-3-methylimidazole tosilate, 1-butyl-2,3-methylimidazole villaumite, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methylimidazole mesylate, N-octyl group pyridine villaumite, N-hexyl-3-picoline tetrafluoroborate or N-methyl, the butyl pyrrolidine mesylate, tributyl-methyl phosphonium ammonium tetrafluoroborate, N-methyl butyl morpholine bromine salt, ethyl tributylphosphine tetrafluoroborate, in 1-ethoxy-3-methylimidazole villaumite one or more mix the mixture of gained in any proportion.
Among the above-mentioned steps c, gas length is 0～10cm; Coagulating bath is 30～80 ℃ distilled water, and setting time is 1～4min; Be stretched as the syllogic drawing process, every section draw ratio is 1.5～2.5 times; Bake out temperature is 70～90 ℃.
Bacteria cellulose of the present invention and natural polysaccharide blend fiber have excellent physical-mechanical property, dyeability, hygroscopicity, biocompatibility, biocidal property and other biologically active, human body skin are had the effects such as anti-inflammatory, antipruritic, beauty treatment.The medical dressing, hemostatic gauze and the operation suture thread that can be used for the production high added value, and the facial treatment mask that is used for beauty treatment and health care; Also can be used for pure spin or with the fiber blends such as cotton, viscose glue, bamboo pulp, hair, fiber crops exploitation high-grade fabric and fabrics for industrial use etc.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1: 100 ℃ of lower oven dry 0.5h in vacuum drying oven with bacteria cellulose and alginic acid; With 970 gram-ion type solvents (1-ethyl-3-methylimidazole tetrafluoroborate 600 grams; 1-butyl-2,3-methylimidazole villaumite 220 grams; 1-butyl-3-methylimidazole mesylate 150 grams) be heated to 90 ℃ in oil bath, then add the dry bacteria celluloses of 28.5 grams and the dry alginic acid of 1.5 grams, mechanical agitation 1h obtains mass percent concentration and is 3% spinning solution; Standing and defoaming 24h, then with spinning solution in spinning head is squeezed into 30 ℃ distilled water coagulating bath, solidify 4min, then adopt the syllogic drawing process, every section draw ratio is 1.5～2.5 times, and the rear 70 ℃ of dryings of washing, oil obtain bacteria cellulose/alginic acid blended fiber.
Embodiment 2: 90 ℃ of oven dry 2h in vacuum drying oven with bacteria cellulose and shitosan; With 950 gram-ion type solvents (1-vinyl-3-methylimidazole tosilate 500 grams; 1-ethoxy-3-methylimidazole villaumite 280 grams; N-methyl, butyl pyrrolidine mesylate 170 gram) be heated to 80 ℃ in oil bath, then add the dry bacteria celluloses of 45 grams and the dry shitosan of 5 grams, mechanical agitation 2h obtains mass percent concentration and is 5% spinning solution; Vacuum deaerator 16h, then with spinning solution in spinning head is squeezed into 50 ℃ distilled water coagulating bath, solidify 3min, then adopt the syllogic drawing process, every section draw ratio is 1.5～2.5 times, and the rear 90 ℃ of dryings of washing, oil obtain bacteria cellulose/chitosan blend fiber.
Embodiment 3: 80 ℃ of lower oven dry 3h in vacuum drying oven with bacteria cellulose and carboxymethyl cellulose; With 930 gram-ion type solvents (1-butyl-3-methylimidazole mesylate 530 grams; Tributyl-methyl phosphonium ammonium tetrafluoroborate 200 grams; Ethyl tributylphosphine tetrafluoroborate 200 gram) be heated to 70 ℃ in oil bath, then add the dry bacteria celluloses of 35 grams and the dry carboxymethyl cellulose of 35 grams, mechanical agitation 3h obtains mass percent concentration and is 7% spinning solution; Vacuum deaerator 20h, then spinning solution is extruded through spinning head, enter into 60 ℃ distilled water coagulating bath through behind the air layer of 4cm, solidify 3min, then adopt the syllogic drawing process, every section draw ratio is 1.5～2.5 times, and the rear 80 ℃ of dryings of washing, oil obtain bacteria cellulose/carboxymethyl cellulose blended fiber.
Embodiment 4: with bacteria cellulose, alginic acid and shitosan 70 ℃ of lower oven dry 4h in vacuum drying oven; With 920 gram-ion type solvents (1-butyl-3-methyl imidazolium tetrafluoroborate 420 grams; The N-methyl, butyl morpholine bromine salt 200 grams; The N-methyl, butyl pyrrolidine mesylate 200 grams; Ethyl tributylphosphine tetrafluoroborate 100 grams) in oil bath, be heated to 60 ℃, then add the dry bacteria cellulose of 24 grams, dry alginic acid and the dry shitosan of 23 grams of 33 grams, mechanical agitation 4h obtains mass percent concentration and is 8% spinning solution; Standing and defoaming 32h, then spinning solution is extruded through spinning head, enter into 60 ℃ distilled water coagulating bath through behind the air layer of 8cm, solidify 3min, then adopt the syllogic drawing process, every section draw ratio is 1.5～2.5 times, and the rear 80 ℃ of dryings of washing, oil obtain bacteria cellulose/alginic acid/chitosan blend fiber.
Embodiment 5: with bacteria cellulose, hyaluronic acid and SKGM 60 ℃ of lower oven dry 5h in vacuum drying oven; With 900 gram-ion type solvents (1-butyl-2,3-methylimidazole villaumite 300 grams; 1-butyl-3-methylimidazole mesylate 200 grams; N-hexyl-3-picoline tetrafluoroborate 150 grams; N-octyl group pyridine villaumite 150 grams; 1-ethoxy-3-methylimidazole villaumite 100 grams) in oil bath, is heated to 50 ℃, then add the dry bacteria cellulose of 5 grams, dry hyaluronic acid and the dry SKGM of 25 grams of 70 grams, mechanical agitation 5h obtains mass percent concentration and is 10% spinning solution; Vacuum deaerator 24h, then spinning solution is extruded through spinning head, enter into 80 ℃ distilled water coagulating bath through behind the air layer of 10cm, solidify 1min, then adopt the syllogic drawing process, every section draw ratio is 1.5～2.5 times, and the rear 90 ℃ of dryings of washing, oil obtain bacteria cellulose/hyaluronic acid/SKGM blended fiber.
The physical-mechanical property of embodiment 1,2,3,4,5 gained bacteria celluloses and natural polysaccharide blend fiber is as shown in table 1.With reference to the line density of " GB/T 14335-2008 man-made staple fibres dimension line density test method " test fiber, with reference to fracture strength and the fracture elongation of " GB/T14337-2008 man-made staple fibres Wella is stretched method for testing performance " test fiber.
The physical-mechanical property of table 1 bacteria cellulose and natural polysaccharide blend fiber
It is important to point out; above-described embodiment is only for the present invention is further illustrated; can not be interpreted as limiting the scope of the invention; be engaged in the person skilled in art according to the guidance of foregoing invention content, the improvement of some non-intrinsically safes that the present invention is made and adjust and still belong to protection scope of the present invention.