CN101985779A - Alga and cellulose composite fiber and manufacturing method therefor - Google Patents
Alga and cellulose composite fiber and manufacturing method therefor Download PDFInfo
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- CN101985779A CN101985779A CN2010105110230A CN201010511023A CN101985779A CN 101985779 A CN101985779 A CN 101985779A CN 2010105110230 A CN2010105110230 A CN 2010105110230A CN 201010511023 A CN201010511023 A CN 201010511023A CN 101985779 A CN101985779 A CN 101985779A
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- cellulose
- alginate
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- composite fiber
- spinning solution
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- 239000000835 fiber Substances 0.000 title claims abstract description 111
- 229920002678 cellulose Polymers 0.000 title claims abstract description 102
- 239000001913 cellulose Substances 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 238000009987 spinning Methods 0.000 claims abstract description 112
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 56
- 229920000615 alginic acid Polymers 0.000 claims abstract description 56
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229940072056 alginate Drugs 0.000 claims abstract description 54
- 229920000297 Rayon Polymers 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 235000010980 cellulose Nutrition 0.000 claims description 73
- 239000002964 rayon Substances 0.000 claims description 38
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- 230000001112 coagulating effect Effects 0.000 claims description 22
- 238000007872 degassing Methods 0.000 claims description 16
- 230000035800 maturation Effects 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 13
- 235000011152 sodium sulphate Nutrition 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000701 coagulant Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000003398 denaturant Substances 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- SJRXVLUZMMDCNG-UHFFFAOYSA-N Gossypin Natural products OC1C(O)C(O)C(CO)OC1OC1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=C(O)C2=O SJRXVLUZMMDCNG-UHFFFAOYSA-N 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 240000000111 Saccharum officinarum Species 0.000 claims description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- SJRXVLUZMMDCNG-KKPQBLLMSA-N gossypin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=C(O)C2=O SJRXVLUZMMDCNG-KKPQBLLMSA-N 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 230000036541 health Effects 0.000 abstract description 9
- 241000195493 Cryptophyta Species 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract 4
- 239000012792 core layer Substances 0.000 abstract 3
- 230000015271 coagulation Effects 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 47
- 239000000661 sodium alginate Substances 0.000 description 47
- 235000010413 sodium alginate Nutrition 0.000 description 47
- 229940005550 sodium alginate Drugs 0.000 description 47
- 239000000243 solution Substances 0.000 description 32
- 239000000126 substance Substances 0.000 description 9
- 229920001282 polysaccharide Polymers 0.000 description 8
- 239000005017 polysaccharide Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 238000004061 bleaching Methods 0.000 description 7
- 239000000648 calcium alginate Substances 0.000 description 7
- 235000010410 calcium alginate Nutrition 0.000 description 7
- 229960002681 calcium alginate Drugs 0.000 description 7
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000004804 polysaccharides Chemical class 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 239000004753 textile Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 241001474374 Blennius Species 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 150000001767 cationic compounds Chemical class 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- -1 amino, carboxyl Chemical group 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 229920000715 Mucilage Polymers 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-BYIBVSMXSA-N alpha-L-gulose Chemical compound OC[C@@H]1O[C@@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-BYIBVSMXSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 229940127219 anticoagulant drug Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WQZGKKKJIJFFOK-RWOPYEJCSA-N beta-D-mannose Chemical compound OC[C@H]1O[C@@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-RWOPYEJCSA-N 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- SCFPVYOJLXCMHM-UHFFFAOYSA-L dicalcium;dichloride Chemical compound [Ca+2].Cl[Ca]Cl SCFPVYOJLXCMHM-UHFFFAOYSA-L 0.000 description 1
- 239000007884 disintegrant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 235000013402 health food Nutrition 0.000 description 1
- 230000002218 hypoglycaemic effect Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
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- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- 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
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/04—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of alginates
Abstract
The invention relates to an alga and cellulose composite fiber, a core-skin type composite fiber consists of alginate and cellulose and is in the structure with a skin layer and a core layer, the core layer of the composite fiber is constituted by the cellulose, the skin layer of the composite fiber consists of the alginate or the alginate and the cellulose, cellulose viscose spinning solution is taken as the spinning solution of the core layer, alginate spinning solution or blend spinning solution after mixing the alginate spinning solution with the cellulose viscose spinning solution is taken as the spinning solution of the skin layer, skin-core composite spinning is adopted, and spinning and forming are carried out in a coagulation bath, thereby obtaining the formed composite fiber with the core-skin structure, ensuring that the alginate only exists in the skin layer which is contact with a human body, reducing the quantity of algae which are in contact with the human body, and ensuring that the composite fiber has better biological active functions of the algae and the health care role.
Description
Technical field
The present invention relates to a kind of functional complex fiber material, specifically, relate to a kind of marine alga and cellulose composite fiber and manufacture method thereof, belong to chemical technology field with core-sheath composite structure.
Background technology
Sodium alginate (Sodium alginate, SAL) be the sodium salt of a kind of polyanionic polysaccharide that from natural brown alga, extracts (alginic acid), the natural polymer (Fig. 1) that the linear copolymer that is linked by β-D mannose hydrochlorate and α-L gulose hydrochlorate (1-4) is formed, because of its unique physical and chemical properties and excellent biological compatibility, be widely used in fields such as pharmaceutical preparation, organizational project, clinical treatment, cellular incubation, food processing.In field of pharmaceutical preparations, SAL is commonly used for thickener, suspending agent and disintegrant, also can be used as the cold-resistant protective agent of microencapsulation material and cell, also has effects such as hypoglycemic, anti-oxidant, enhance immunity activity.Studies show that, sodium alginate is a class high-performance bio adsorbent, can enrichment various trace elements, can be widely used in development, purification of water quality and the sewage disposal etc. of medical-care health food, aspects such as the recovery of rare, precious metal and radioactive substance, trace, ultratrace element analysis.In the biological concentration process of algae, owing to all contain multiple polysaccharide in alga cells and the cell membrane, and these polysaccharide can provide functional groups such as amino, carboxyl, aldehyde radical and sulfate radical, thereby stronger network platform ability is arranged with metal ion, can carry out biology absorption trace element by complexing and ion-exchange.Studies show that, as metal ion exchanged agent, algal polysaccharides can with Ni in the waste water
2+, Co
2+, Cr
2+, Cd
2+Plasma is had an effect, and alginate in the polysaccharide and sulfate group polysaccharide have significant ion-exchange capacity.The alginate structural formula is as follows:
In recent years, people recognized the potential function of algal polysaccharides as medicine and pharmaceutical intermediate gradually, and promptly algal polysaccharides shows anticoagulant active, antitumor activity and antiviral activity etc.Simultaneously, because " the wet healing " theoretical foundation, the scope of its application and quantity are also increasing greatly.The high-hygroscopicity that produces wet treatment environment and take place thereupon on the wound original position is two outstanding performances, and this makes marine alga dressing become a kind of outstanding medical dressing, and its market demand increases rapidly.In recent years, along with the development of bio-medical material and the exploitation of novel pharmaceutical formulation, SAL is as the gel rubber material of a kind of bioadhesive polymer efficiently and pH sensitiveness, and its application study is also increasing.
Along with the raising of living standards of the people and social economy, development of science and technology, that people pursue is comfortable, health care, high-grade, nature and environmental protection requirement are more and more urgent, gives specific functions such as daily textiles health and the health care development trend that becomes international gradually.Sodium alginate is applied to field of textiles, can makes textiles have the specific function summary of the invention of health and health care.
At present, multiple marine alga composite fibre and preparation method have appearred, be 2007100144031, open day be the Chinese patent of 2007.9.12 as application number, a kind of preparation method of common calcium alginate fibre is disclosed, with the water-soluble sodium alginate soln of producing of sodium alginate,, produce coagulating bath with the calcium chloride calcium chloride solution of producing soluble in water, sodium alginate soln through swelling, filtration, vacuum deaerator, is produced calcium alginate fibre with wet spinning in coagulating bath.The calcium alginate fibre of this method preparation, belong to and take place that precipitate gel makes behind the metal ion calcium ion that sodium alginate runs into divalence, belong to pure alginate fiber, the dried rate of stretching of this fibrid is on the low side, and the active ingredient of fibrous inside can not can not well be brought into play its functional effect with extraneous contact, utilization rate is low, and cost an arm and a leg, up to 1,000,000/ton, be difficult to obtain promote.
Application number is 200310110168X, open day to be the Chinese patent of 2004.11.10, a kind of viscose glue active alga fiber and production method thereof are disclosed, the percentage by weight of marine alga and fiber is 1-8%, sodium alginate powder is dissolved in the NaoH solution, above-mentioned algin liquid solution separated in the process in the liposoluble of fiber yellow acid add in the viscose glue equably, through mixing, grind to form the spinning solution that contains active alga, with the above-mentioned seaweed mucilage spinning solution that contains, after filtration, carry out spinning at the long filament machine, obtain viscose glue active alga fiber filament through washing, oven dry again.This kind production method owing to adopted marine alga and cellulose complex technique, makes that production cost has obtained significantly reducing, but because the marine alga of fiber internal layer can not be with the contact of external environments such as skin, can not bring into play fully that it is functional, causes the utilization rate reduction.
Application number is 2008101572676, open day is the Chinese patent of 2009.3.11, a kind of manufacture method of antimicrobial calcium alginate fiber is disclosed, as spinning solution, in the coagulating bath that contains antiseptic, adopt wet spinning technology to obtain antimicrobial calcium alginate fiber with sodium alginate soln; Feature is that described antiseptic is a cationic compound, and cationic compound combines with ionic bond with the big molecule of calcium alginate fibre.The antimicrobial calcium alginate fiber of this method preparation, belong to and take place that precipitate gel makes behind sodium alginate runs into divalence in the coagulating bath that contains cationic compound the metal ion calcium ion, belong to pure alginate fiber, the dried rate of stretching of this fibrid is on the low side, and the active ingredient of fibrous inside can not can not well be brought into play its functional effect with extraneous contact, utilization rate is low, and cost an arm and a leg, up to 1,000,000/ton, be difficult to obtain promote.
Application number is 2008101972753, open day is the Chinese patent of 2009.3.11, a kind of nano Ag antibacterial fiber is disclosed, form by alginate and carboxylic butyryl shitosan and nano silver dispersion feedstock production, with alginate and carboxylic butyryl shitosan mixing, mixed solution; Add nano silver dispersion to mixed solution, and behind stirring, filtration and vacuum deaerator, get semi-finished product solution; Adopt solution spinning, semi-finished product solution is made described fiber under room temperature; In the solvent spinning process, the solidification liquid of employing is CaCl
2The aqueous solution.
The active principle of the disclosed alginate fibre of above file inside can not can't bring into play the effect of inner active principle, so utilization rate is low, has improved production cost, and the dried rate of stretching of gained fiber be on the low side with extraneous contact.
Summary of the invention
Technical problem to be solved by this invention is at above problem, a kind of marine alga and cellulose composite fiber and manufacture method thereof are provided, this composite fibre has skin-core structure, sandwich layer is made with cellulose, cortex is used by alginate or alginate and cellulose and is formed, reduced the consumption of alginate, thereby reduced production cost, and increased in the fiber and human body contact portion alginate concentration and marine alga quantity, improved the biological action of composite fibre effectively, the present invention adopts viscose process and marine alga and cellulose complex technique to prepare cellulose fibre, makes that production cost has obtained significantly reducing.
For solving above technical problem, technical scheme of the present invention is as follows: marine alga and cellulose composite fiber, it is characterized in that: the core-sheath compound fibre with cortex and core structure that described composite fibre is made up of alginate and cellulose, the sandwich layer of composite fibre is made up of cellulose.
As further improvement in the technical proposal:
The cortex of described composite fibre is made up of alginate or alginate and cellulose.
Adopt above technical scheme, can guarantee that alginate only is present in the cortex of human body contact, reduced the use amount of alginate, reduced the production cost of fiber, improved the content of marine alga in the cortex, improved the quantity of the marine alga that contacts with human body, guaranteed that composite fibre has seaweed bio active function and health-care function preferably.
Described alginate accounts for 3～80% of composite fibre weight.
The preparation method of marine alga and cellulose composite fiber is characterized in that: described preparation method may further comprise the steps:
A, make cellulose rayon spinning stoste with cellulose;
B, make the alginate spinning solution with alginate;
C, be the sandwich layer spinning solution with cellulose rayon spinning stoste, with alginate spinning solution or alginate spinning solution and the mixed co-blended spinning stoste of cellulose rayon spinning stoste is the cortex spinning solution, adopt the core-skin composite spinning silk through the coagulating bath spinning moulding, obtain the skin-core structure composite fibre of moulding.
Described preparation method may further comprise the steps:
Skin-core structure composite fibre after the moulding obtains finished product alginate and cellulose composite fiber through refining, baking operation.
Among the step a, it is at least a making in 400～1000 gossypin, lignose, bamboo cellulose, flax fibre element and the sugarcane cellulose that cellulose spin dope then adopts the degree of polymerization.
Among the step b, being 3～250,000 alginate with molecular weight is dissolved in the deionized water in 1: 10～25 ratio, stirred 1～3 hour down at 20～45 ℃, dissolving back outgased 9～11 hours in temperature is 12～20 ℃ vacuum, maturation 12～20 hours under 20～30 ℃ temperature then, again after filtration, the degassing, make the alginate spinning solution.
Adopting molecular weight is that 3～250,000 the alginate and the degree of polymerization then are that 400～1000 cellulose is as raw material.
Among the step c, the weight ratio of alginate spinning solution and cellulose rayon spinning stoste is 1 in the co-blended spinning stoste: 0.51-5.11.
Among the step c, co-blended spinning stoste be alginate spinning solution and cellulose rayon spinning stoste in static mixer through being no less than 10
5Make after the inferior mixing.
Contain the coagulating agent that useful sulfuric acid, zinc sulfate and sodium sulphate or sulfuric acid, aluminum sulfate and sodium sulphate or sulfuric acid, denaturant and sodium sulphate are formed in the described coagulating bath.
The present invention adopts above technical scheme, compared with prior art, has the following advantages:
(1) the core-sheath compound fibre of forming by alginate and cellulose with cortex and core structure, the sandwich layer of composite fibre is made up of cellulose, cortex is made up of alginate or alginate and cellulose, can guarantee that alginate only is present in the cortex of human body contact, reduced the use amount of marine alga, reduced the production cost of fiber, improved the content of marine alga in the cortex, improved the quantity of the marine alga that contacts with human body, guaranteed that composite fibre has seaweed bio active function and health-care function preferably.
(2) in static mixer through being no less than 10
5Make co-blended spinning stoste after the inferior mixing, improved the mixed effect of alginate spinning solution and cellulose rayon spinning stoste in the co-blended spinning stoste.
(3) adopt molecular weight be 3～250,000 the alginate and the degree of polymerization be 400～1000 cellulose as raw material, can between the alginate cellulose, form firm ionic bond, thus the antibiotic persistence of raising composite fibre.
(4) owing to adopt viscose process and alginate and cellulose complex technique to prepare cellulose fibre, alginate only is present in the cortex of human body contact, has reduced production cost.
The present invention is described in detail below in conjunction with drawings and Examples.
Description of drawings
Accompanying drawing is the structural representation of marine alga and cellulose composite fiber in the embodiment of the invention.
Among the figure,
The 1-cortex, the 2-sandwich layer.
The specific embodiment
In addition with the cellulose cotton pulp of the degree of polymerization 400 through known alkali stain, squeezing, pulverizing, experienced, yellow, dissolving, mixing, filtration, maturation and deaeration operation, make cellulose rayon spinning stoste, control that chemical cellulose content is 8.8% in this rayon spinning stoste, alkalinity is 4.5%.
Placed static mixer through being no less than 10 by weight 1: 5.11 sodium alginate spinning solution and cellulose rayon spinning stoste then
5Inferior mixing, to mix, input cortex inlet measuring pump after pre-filtering, in addition cellulose rayon spinning stoste is delivered to sandwich layer inlet measuring pump, cortex inlet measuring pump and sandwich layer inlet measuring pump rotating ratio are 1: 2.18, behind the core-skin type composite spinning, enter temperature and be spinning moulding in 48 ℃ the coagulating bath, contain sulfuric acid 135g/l in the coagulating bath, the coagulating agent that zinc sulfate 13g/l and sodium sulphate 330g/l form, again through desulfurization, washing, oil, bleaching, baking operation, promptly obtain having the finished product core-sheath compound fibre of cortex 1 and sandwich layer 2 structures, as shown in the figure, sodium alginate content is 10% in the cortex 1, the content of sodium alginate is 3% in the fiber, and this composite fibre is applicable to the textile raw material and the fabric of medical treatment and health purpose.
Obtaining specification is the dried strong 1.95cN/dtex of the core-sheath compound fibre of 1.33dtex, and wet strong 1.05cN/dtex driedly stretches 18.5%.
In addition with the cellulose cotton pulp of the degree of polymerization 500 through known alkali stain, squeezing, pulverizing, experienced, yellow, dissolving, mixing, filtration, maturation and deaeration operation, make cellulose rayon spinning stoste, control that chemical cellulose content is 8.8% in this rayon spinning stoste, alkalinity is 4.5%.
Placed static mixer through being no less than 10 by weight 1: 4.2 sodium alginate spinning solution and cellulose rayon spinning stoste then
5Inferior mixing, to mix, input cortex inlet measuring pump after pre-filtering, in addition cellulose rayon spinning stoste is delivered to sandwich layer inlet measuring pump, cortex inlet measuring pump and sandwich layer inlet measuring pump rotating ratio are 1: 2.18, behind the core-skin type composite spinning, enter temperature and be spinning moulding in 48 ℃ the coagulating bath, contain sulfuric acid 130g/l in the coagulating bath, the coagulating agent that sodium sulphate 330g/l and 1.5% denaturant V315 form, again through desulfurization, washing, oil, bleaching, baking operation, promptly obtain having the finished product core-sheath compound fibre of cortex 1 and sandwich layer 2 structures, as shown in the figure, sodium alginate content is 18% in the cortex 1, the content of sodium alginate is 11% in the fiber, and this composite fibre is applicable to the textile raw material and the fabric of medical treatment and health purpose.
Obtain the core-sheath compound fibre that specification is 2.22dtex, the dried of core-sheath compound fibre is 2.05cN/dtex by force, and wet is 1.14cN/dtex by force, and dried stretching is 17.4%.
Embodiment 3, the manufacture method of marine alga and cellulose composite fiber, may further comprise the steps: being 100,000 sodium alginate with molecular weight is dissolved in the deionized water in 1: 16 ratio, under 28 ℃ temperature, stirred 2 hours, dissolving back is the degassing 10 hours in 14 ℃ the vacuum in temperature, maturation 14 hours under 22 ℃ temperature then more after filtration, the degassing, makes the sodium alginate spinning solution.
In addition with the cellulose cotton pulp of the degree of polymerization 600 through known alkali stain, squeezing, pulverizing, experienced, yellow, dissolving, mixing, filtration, maturation and deaeration operation, make cellulose rayon spinning stoste, control that chemical cellulose content is 8.8% in this rayon spinning stoste, alkalinity is 4.5%.
Placed static mixer through being no less than 10 by weight 1: 3.3 sodium alginate spinning solution and cellulose rayon spinning stoste then
5Inferior mixing, to mix, input cortex inlet measuring pump after pre-filtering, in addition cellulose rayon spinning stoste is delivered to sandwich layer inlet measuring pump, cortex inlet measuring pump and sandwich layer inlet measuring pump rotating ratio are 1: 2.18, behind the core-skin type composite spinning, enter temperature and be spinning moulding in 50 ℃ the coagulating bath, contain sulfuric acid 130g/l in the coagulating bath, the coagulating agent that sodium sulphate 330g/l and aluminum sulfate 10g/l form, again through desulfurization, washing, oil, bleaching, baking operation, promptly obtain having the finished product core-sheath compound fibre of cortex 1 and sandwich layer 2 structures, as shown in the figure, sodium alginate content is 27% in the cortex 1, the content of sodium alginate is 15% in the fiber, and this composite fibre is applicable to the textile raw material and the fabric of medical treatment and health purpose.
Obtain the core-sheath compound fibre that specification is 3.33dtex, the dried of core-sheath compound fibre is 1.90cN/dtex by force, and wet is 1.00cN/dtex by force, and dried stretching is 16.5%.
Embodiment 4, the manufacture method of marine alga and cellulose composite fiber, may further comprise the steps: being 140,000 sodium alginate with molecular weight is dissolved in the deionized water in 1: 19 ratio, under 32 ℃ temperature, stirred 2.5 hours, dissolving back is the degassing 10.5 hours in 15 ℃ the vacuum in temperature, maturation 16 hours under 23 ℃ temperature then more after filtration, the degassing, makes the sodium alginate spinning solution.
In addition with the cellulose cotton pulp of the degree of polymerization 700 through known alkali stain, squeezing, pulverizing, experienced, yellow, dissolving, mixing, filtration, maturation and deaeration operation, make cellulose rayon spinning stoste, control that chemical cellulose content is 8.8% in this rayon spinning stoste, alkalinity is 4.5%.
Placed static mixer through being no less than 10 by weight 1: 2.4 sodium alginate spinning solution and cellulose rayon spinning stoste then
5Inferior mixing, to mix, input cortex inlet measuring pump after pre-filtering, in addition cellulose rayon spinning stoste is delivered to sandwich layer inlet measuring pump, cortex inlet measuring pump and sandwich layer inlet measuring pump rotating ratio are 1: 0.68, behind the core-skin type composite spinning, enter temperature and be spinning moulding in 50 ℃ the coagulating bath, contain sulfuric acid 132g/l in the coagulating bath, the coagulating agent that zinc sulfate 11g/l and sodium sulphate 325g/l form, again through desulfurization, washing, oil, bleaching, baking operation, promptly obtain having the finished product core-sheath compound fibre of cortex 1 and sandwich layer 2 structures, as shown in the figure, sodium alginate content is 50% in the cortex 1, and the content of sodium alginate is 25% composite fibre in the fiber.
Obtain the core-sheath compound fibre that specification is 1.33dtex, the dried of core-sheath compound fibre is 2.35cN/dtex by force, and wet is 1.25cN/dtex by force, and dried stretching is 19.2%.
Embodiment 5, the manufacture method of marine alga and cellulose composite fiber, may further comprise the steps: being 180,000 sodium alginate with molecular weight is dissolved in the deionized water in 1: 22 ratio, under 36 ℃ temperature, stirred 3 hours, dissolving back is the degassing 11 hours in 16 ℃ the vacuum in temperature, maturation 17 hours under 24 ℃ temperature then more after filtration, the degassing, makes the sodium alginate spinning solution.
In addition with the cellulose cotton pulp of the degree of polymerization 800 through known alkali stain, squeezing, pulverizing, experienced, yellow, dissolving, mixing, filtration, maturation and deaeration operation, make cellulose rayon spinning stoste, control that chemical cellulose content is 8.8% in this rayon spinning stoste, alkalinity is 4.5%.
Then the sodium alginate spinning solution is imported cortex inlet measuring pump after pre-filtering, in addition cellulose rayon spinning stoste is delivered to sandwich layer inlet measuring pump, cortex inlet measuring pump and sandwich layer inlet measuring pump rotating ratio are 1: 0.14, behind the core-skin type composite spinning, enter temperature and be spinning moulding in 50 ℃ the coagulating bath, contain sulfuric acid 132g/l in the coagulating bath, the coagulating agent that zinc sulfate 11g/l and sodium sulphate 325g/l form, again through desulfurization, washing, oil, bleaching, baking operation, promptly obtain having the finished product core-sheath compound fibre of cortex 1 and sandwich layer 2 structures, as shown in the figure, sodium alginate content is 100% in the cortex 1, and the content of sodium alginate is 80% composite fibre in the fiber.
Obtain the core-sheath compound fibre that specification is 2.78dtex, doing of core-sheath compound fibre is by force 2.09
CN/dtex, wet is 1.15cN/dtex by force, dried stretching is 19.5%.
Embodiment 6, the manufacture method of marine alga and cellulose composite fiber, may further comprise the steps: being 220,000 sodium alginate with molecular weight is dissolved in the deionized water in 1: 23 ratio, under 38 ℃ temperature, stirred 2.5 hours, dissolving back is the degassing 11 hours in 18 ℃ the vacuum in temperature, maturation 18 hours under 26 ℃ temperature then more after filtration, the degassing, makes the sodium alginate spinning solution.
In addition with the cellulose cotton pulp of the degree of polymerization 900 through known alkali stain, squeezing, pulverizing, experienced, yellow, dissolving, mixing, filtration, maturation and deaeration operation, make cellulose rayon spinning stoste, control that chemical cellulose content is 8.8% in this rayon spinning stoste, alkalinity is 4.5%.
Placed static mixer through being no less than 10 by weight 1: 1.3 sodium alginate spinning solution and cellulose rayon spinning stoste then
5Inferior mixing, to mix, input cortex inlet measuring pump after pre-filtering, in addition cellulose rayon spinning stoste is delivered to sandwich layer inlet measuring pump, cortex inlet measuring pump and sandwich layer inlet measuring pump rotating ratio are 1: 0.68, behind the core-skin type composite spinning, enter temperature and be spinning moulding in 50 ℃ the coagulating bath, contain sulfuric acid 132g/l in the coagulating bath, the coagulating agent that zinc sulfate 11g/l and sodium sulphate 325g/l form, again through desulfurization, washing, oil, bleaching, baking operation, promptly obtain having the finished product core-sheath compound fibre of cortex 1 and sandwich layer 2 structures, as shown in the figure, sodium alginate content is 60% in the cortex 1, and the content of sodium alginate is 41% composite fibre in the fiber.
Obtain the core-sheath compound fibre that specification is 2.22dtex, the dried of core-sheath compound fibre is 2.55cN/dtex by force, and wet is 1.45cN/dtex by force, and dried stretching is 21.5%.
Embodiment 7, the manufacture method of marine alga and cellulose composite fiber, may further comprise the steps: being 250,000 sodium alginate with molecular weight is dissolved in the deionized water in 1: 25 ratio, under 45 ℃ temperature, stirred 3 hours, dissolving back is the degassing 11 hours in 20 ℃ the vacuum in temperature, maturation 20 hours under 30 ℃ temperature then more after filtration, the degassing, makes the sodium alginate spinning solution.
In addition with the cellulose cotton pulp of the degree of polymerization 1000 through known alkali stain, squeezing, pulverizing, experienced, yellow, dissolving, mixing, filtration, maturation and deaeration operation, make cellulose rayon spinning stoste, control that chemical cellulose content is 8.8% in this rayon spinning stoste, alkalinity is 4.5%.
Placed static mixer through being no less than 10 by weight 1: 0.51 sodium alginate spinning solution and cellulose rayon spinning stoste then
5Inferior mixing, to mix, input cortex inlet measuring pump after pre-filtering, in addition cellulose rayon spinning stoste is delivered to sandwich layer inlet measuring pump, cortex inlet measuring pump and sandwich layer inlet measuring pump rotating ratio are 1: 0.68, behind the core-skin type composite spinning, enter temperature and be spinning moulding in 50 ℃ the coagulating bath, contain sulfuric acid 132g/l in the coagulating bath, the coagulating agent that zinc sulfate 11g/l and sodium sulphate 325g/l form, again through desulfurization, washing, oil, bleaching, baking operation, promptly obtain having the finished product core-sheath compound fibre of cortex 1 and sandwich layer 2 structures, as shown in the figure, sodium alginate content is 80% in the cortex 1, and the content of sodium alginate is 62% composite fibre in the fiber.
Obtain the core-sheath compound fibre that specification is 3.33dtex, the dried of core-sheath compound fibre is 2.45cN/dtex by force, and wet is 1.35cN/dtex by force, and dried stretching is 20.5%.
Among the above embodiment, the sodium alginate spinning solution also can be according to present known method preparation, and embodiment 6 is a preferred version.
Claims (10)
1. marine alga and cellulose composite fiber, it is characterized in that: the core-sheath compound fibre with cortex and core structure that described composite fibre is made up of alginate and cellulose, the sandwich layer of composite fibre is made up of cellulose.
2. marine alga as claimed in claim 1 and cellulose composite fiber is characterized in that: the cortex of described composite fibre is made up of alginate or alginate and cellulose.
3. marine alga as claimed in claim 1 or 2 and cellulose composite fiber is characterized in that: described alginate accounts for 3～80% of composite fibre weight.
4. the preparation method of marine alga as claimed in claim 1 and cellulose composite fiber is characterized in that: described preparation method may further comprise the steps:
A, make cellulose rayon spinning stoste with cellulose;
B, make the alginate spinning solution with alginate;
C, being the sandwich layer spinning solution with cellulose rayon spinning stoste, is the cortex spinning solution with the alginate spinning solution;
Or alginate spinning solution and the mixed co-blended spinning stoste of cellulose rayon spinning stoste is the cortex spinning solution, adopts the core-skin composite spinning silk through the coagulating bath spinning moulding, obtains the skin-core structure composite fibre of moulding.
5. the preparation method of marine alga as claimed in claim 4 and cellulose composite fiber is characterized in that: described preparation method may further comprise the steps:
Skin-core structure composite fibre after the moulding obtains finished product marine alga and cellulose composite fiber through refining, baking operation.
6. the manufacture method of marine alga as claimed in claim 4 and cellulose composite fiber, it is characterized in that: among the step a, it is at least a making in 400～1000 gossypin, lignose, bamboo cellulose, flax fibre element and the sugarcane cellulose that cellulose spin dope adopts the degree of polymerization.
7. the manufacture method of marine alga as claimed in claim 4 and cellulose composite fiber, it is characterized in that: among the step b, being 3～250,000 alginate with molecular weight is dissolved in the deionized water in 1: 10～25 ratio, stirred 1～3 hour down at 20～45 ℃, dissolving back outgased 9～11 hours in temperature is 12～20 ℃ vacuum, maturation 12～20 hours under 20～30 ℃ temperature then more after filtration, the degassing, makes the alginate spinning solution.
8. the manufacture method of marine alga as claimed in claim 4 and cellulose composite fiber is characterized in that: among the step c, the weight ratio of alginate spinning solution and cellulose rayon spinning stoste is 1 in the co-blended spinning stoste: 0.51-5.11.
9. the manufacture method of marine alga as claimed in claim 4 and cellulose composite fiber is characterized in that: among the step c, co-blended spinning stoste be alginate spinning solution and cellulose rayon spinning stoste in static mixer through being no less than 10
5Make after the inferior mixing.
10. as the manufacture method of one of them described marine alga of claim 4-9 and cellulose composite fiber, it is characterized in that: contain the coagulating agent that useful sulfuric acid, zinc sulfate and sodium sulphate or sulfuric acid, aluminum sulfate and sodium sulphate or sulfuric acid, denaturant and sodium sulphate are formed in the described coagulating bath.
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| CN108842224A (en) * | 2018-06-13 | 2018-11-20 | 东华大学 | A kind of core-skin type graphene/alginic acid electrically conductive composite fibre and preparation method thereof |
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| CN110541209A (en) * | 2019-09-19 | 2019-12-06 | 东华大学 | Continuous preparation method of hydrogel optical fiber based on reactive spinning |
| CN110541209B (en) * | 2019-09-19 | 2021-08-10 | 东华大学 | Continuous preparation method of hydrogel optical fiber based on reactive spinning |
| CN112127009A (en) * | 2020-09-11 | 2020-12-25 | 嘉兴学院 | Cellulose/calcium alginate blend fiber with skin-core structure and preparation method thereof |
| CN112127009B (en) * | 2020-09-11 | 2022-10-14 | 嘉兴学院 | Cellulose/calcium alginate blend fiber with skin-core structure and preparation method thereof |
| CN114182379A (en) * | 2020-12-18 | 2022-03-15 | 青岛起初智能科技有限公司 | Antibacterial, deodorant, skin-care and health-care cellulose fiber and preparation method thereof |
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