CN115323613A - Antistatic oyster-based fiber flocculus and preparation process thereof - Google Patents
Antistatic oyster-based fiber flocculus and preparation process thereof Download PDFInfo
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- CN115323613A CN115323613A CN202211089468.3A CN202211089468A CN115323613A CN 115323613 A CN115323613 A CN 115323613A CN 202211089468 A CN202211089468 A CN 202211089468A CN 115323613 A CN115323613 A CN 115323613A
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- Prior art keywords
- oyster
- oyster shell
- antistatic
- superfine
- essential oil
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- 239000000835 fiber Substances 0.000 title claims abstract description 103
- 241000237502 Ostreidae Species 0.000 title claims abstract description 93
- 235000020636 oyster Nutrition 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 193
- 239000000843 powder Substances 0.000 claims abstract description 124
- 239000000341 volatile oil Substances 0.000 claims abstract description 71
- 229920001690 polydopamine Polymers 0.000 claims abstract description 46
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002270 dispersing agent Substances 0.000 claims abstract description 26
- 235000000983 citronellal Nutrition 0.000 claims abstract description 15
- 229930003633 citronellal Natural products 0.000 claims abstract description 15
- 244000178870 Lavandula angustifolia Species 0.000 claims abstract description 14
- 235000010663 Lavandula angustifolia Nutrition 0.000 claims abstract description 14
- 239000001102 lavandula vera Substances 0.000 claims abstract description 14
- 235000018219 lavender Nutrition 0.000 claims abstract description 14
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000009987 spinning Methods 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000000839 emulsion Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 18
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 229940037312 stearamide Drugs 0.000 claims description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 229920000728 polyester Polymers 0.000 claims description 14
- 238000004659 sterilization and disinfection Methods 0.000 claims description 14
- GLISOBUNKGBQCL-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(C)CCCN GLISOBUNKGBQCL-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000578 dry spinning Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 9
- 238000009960 carding Methods 0.000 claims description 9
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 229960004889 salicylic acid Drugs 0.000 claims description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims 2
- 239000002028 Biomass Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 230000006870 function Effects 0.000 abstract description 6
- 230000003385 bacteriostatic effect Effects 0.000 abstract description 5
- 210000005036 nerve Anatomy 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 230000001965 increasing effect Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- -1 cationic quaternary ammonium salt Chemical class 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 241000218645 Cedrus Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000015170 shellfish Nutrition 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- LQIAZOCLNBBZQK-UHFFFAOYSA-N 1-(1,2-Diphosphanylethyl)pyrrolidin-2-one Chemical compound PCC(P)N1CCCC1=O LQIAZOCLNBBZQK-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010033557 Palpitations Diseases 0.000 description 1
- 102000019307 Sclerostin Human genes 0.000 description 1
- 108050006698 Sclerostin Proteins 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000001914 calming effect Effects 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PPVFOZYARYOARE-UHFFFAOYSA-N guaiapate Chemical compound COC1=CC=CC=C1OCCOCCOCCN1CCCCC1 PPVFOZYARYOARE-UHFFFAOYSA-N 0.000 description 1
- 229950010056 guaiapate Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 150000002773 monoterpene derivatives Chemical class 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4309—Polyvinyl alcohol
-
- 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
- D01D5/04—Dry spinning methods
-
- 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
- D01D5/12—Stretch-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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/02—Cotton wool; Wadding
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the field of oyster-based fibers, in particular to an antistatic oyster-based fiber flocculus and a preparation process thereof. According to the invention, the oyster shell is not calcined but directly ground, so that the loss of organic biomass in the oyster shell is reduced; the relatively large adsorption capacity brought by the microporous structure of the oyster shell is utilized, the citronellal essential oil and the lavender essential oil are adsorbed by the oyster shell, the bacteriostatic action of the oyster shell powder is improved, and the functions of helping sleep and soothing nerves are also increased; furthermore, the polydopamine coating is adopted, so that on one hand, the dispersibility of the polydopamine coating is improved, on the other hand, the loss of the organic biomass can be reduced, the volatilization of essential oil components can be inhibited, and the service lives of the organic biomass and the essential oil components can be greatly prolonged; and the benzyl bromide is adopted to carry out quaternary ammonium ionization on the polydopamine, so that the antistatic effect of the polydopamine is improved, and the polydopamine and the dispersing agent are applied to the preparation of oyster-based fibers, so that the antistatic oyster-based fiber flocculus which is excellent in antistatic and antibacterial effects, contains a large amount of organic biomass and can help sleep and calm nerves is obtained.
Description
Technical Field
The invention relates to the field of oyster-based fibers, in particular to an antistatic oyster-based fiber flocculus and a preparation process thereof.
Background
Oysters (Oysters) are famous and common shellfishes in the world, the oyster yield in China accounts for the top of the oyster cultivation yield in the world, 20 kinds of Oysters are arranged in provinces of the coastal region, the Oysters are commonly called as fresh Oysters or big Oysters in the south China and are the most important economic shellfishes in the south China coastal region, wherein the Guangxi Bay Qinzhou Bay and the Guangxi Town Bay are famous oyster cultivation and seedling bases in China. At present, oyster is mainly developed in China by processing edible parts of the oyster, a large number of shells are discarded as garbage while the edible parts are utilized, and organic matters remained in the discarded shells are decayed and smelly in the long-term stacking process, so that the life of residents is harmed, and the environment is seriously polluted.
In recent years, with the continuous expansion of oyster cultivation scale in coastal provinces of China, how to change waste into valuable is achieved, and a large amount of cheap oyster shell resources are developed and utilized, which is paid much attention by researchers.
The basic structure of the oyster shell is divided into three layers: the outer layer is sclerostin cuticle with extremely thin thickness; the middle part is a prismatic layer which is interwoven by calcareous fibers, has a leaf-shaped structure and has natural air holes; the inner layer is a pearl layer and mainly comprises mineral substances such as calcium carbonate and the like and a small amount of organic matters. The oyster shell comprises two parts of inorganic matter and organic matter. The inorganic part is mainly calcium carbonate which accounts for more than 90 percent of the weight of the oyster shell, wherein calcium element accounts for (39.78 +/-0.23), and the inorganic part also contains more than 20 trace elements such as copper, iron, zinc, manganese, strontium and the like; the organic components of the oyster shell account for about 3-5% of the weight of the oyster shell, and the oyster shell contains 17 amino acids such as glycine, cystine, methionine and the like.
Oyster shells serving as a resource which is abundant, cheap and renewable are bound to become a hotspot of people in the future research and development, and more research results are applied to production and life. Due to the continuous development of advanced technologies such as superfine grinding, modification and the like in recent years, oyster shells are more and more commonly developed and researched at home and abroad, and the oyster shells are mainly shown in the fields of medicines, foods, health-care products, additives and the like. However, in the textile field, the development and application of oyster shells are less.
In recent years, along with the improvement of living standard of people, people put forward higher requirements on thermal clothes, some functional thermal materials are introduced into the market, the novel active thermal materials not only can reduce the loss of human body heat, but also can spontaneously absorb heat or release heat according to the change of external temperature and the requirement of a human body, and the ambient temperature of the human body is adjusted to obtain thermal comfort. In addition, people put forward higher requirements on the antistatic, bacteriostatic and anti-mite functions, the comfort level and even the health care functions of clothes. Traditional passive warm-keeping materials, such as natural fibers like cotton, hemp and fur of certain animals, and glue-sprayed cotton, are widely used and spread throughout the life of people, but the requirements of people cannot be met gradually.
The current Chinese invention application CN202010765516.0 discloses a preparation method of oyster-based fibers, compared with traditional polyester fibers, the oyster fibers have high strength and toughness, have the functions of antibiosis, deodorization, heat preservation, static resistance, ultraviolet resistance and the like, can meet the requirements of different application scenes, and have great popularization and application potentials. However, only the oyster shell is used as a calcium source, and the adopted oyster shell powder is calcined, crushed, dissolved and recrystallized to obtain the nano calcium carbonate, so that the method is time-consuming and labor-consuming, cannot effectively utilize the organic biomass in the oyster shell, causes great waste, and greatly increases the utilization cost of the oyster shell.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an antistatic oyster-based fiber flocculus and a preparation process thereof.
A preparation process of the antistatic oyster-based fiber flocculus comprises the following steps:
(1) Cleaning the surface of the oyster shell with water, placing the oyster shell into an aqueous solution containing 5-7wt% of an oxidant for disinfection, assisting ultrasonic oscillation for 20-30min, taking out the oyster shell, cleaning the oyster shell with water again, and finally drying to obtain a pretreated oyster shell;
(2) Crushing the pretreated oyster shell powder obtained in the step (1) to a size of 300 meshes, washing with water, and filtering for three times to obtain oyster shell coarse powder;
(3) Transferring the crushed oyster shell coarse powder to a strong bead mill, adding vinyl bis stearamide, and grinding to obtain superfine oyster shell powder with the particle size of 0.5-1 mu m;
(4) Mixing 10-20 parts by mass of superfine oyster shell powder and 50-100 parts by mass of essential oil, stirring and adsorbing for 20-30min, and centrifuging to obtain precipitate to obtain superfine oyster shell powder adsorbed by the essential oil;
(5) Mixing 10-20 parts by mass of superfine oyster shell powder adsorbed by the essential oil prepared in the step (4), 2-4 parts by mass of dopamine hydrochloride and 300-500 parts by mass of water, ultrasonically stirring for 20-40min to obtain emulsion, adjusting the pH of the emulsion to 7-9 by using 6-8wt% of trihydroxymethyl aminomethane aqueous solution, stirring for 5-10min at 20-40 ℃, adding 0.5-1 part by mass of salicylic acid, adjusting the pH to 7-9 by using 6-8wt% of trihydroxymethyl aminomethane aqueous solution, continuously stirring for 5-10min at 20-40 ℃, filtering and drying to obtain polydopamine modified superfine oyster shell powder;
(6) Mixing 0.1-0.5 part of benzyl bromide, 5-10 parts of polydopamine modified superfine oyster shell powder and 90-100 parts of water by mass, stirring and reacting at 70-80 ℃ for 20-40min, filtering, washing and drying to obtain quaternized superfine oyster shell powder;
(7) Mixing 5-10 parts of quaternized oyster shell powder, 2-4 parts of dispersant and 50-60 parts of polyvinyl alcohol resin according to parts by mass, and stirring and reacting at 150-200 ℃ and under the control pressure of 0.25-0.4Mpa for 40-80min to obtain a fiber solution;
(8) Adding the fiber liquid obtained in the step (7) into a spinning machine for dry spinning; the temperature of the spinning fiber liquid is 90-105 ℃ during extrusion, the diameter of a spinning hole is 0.05-0.1mm, the nitrogen hot air is used for protecting the position near the spinning hole, the temperature of the hot air is 110-130 ℃, and the spinning speed is 2-3m/min; stretching by adopting a mechanical stretching system, wherein the stretching ratio is 4.5, and the stretching temperature is 170-200 ℃, so as to obtain oyster-based fibers; and finishing by a carding lapping machine to obtain the antistatic oyster-based fiber flocculus.
The oxidant in the step (1) is one of sodium hypochlorite and hydrogen peroxide; preferably, the oxidant is sodium hypochlorite.
The ultrasonic power in the step (1) and the ultrasonic power in the step (5) are 400-1000W, and the frequency is 90-120Hz.
The adding amount of the vinyl bis stearamide in the step (3) is 0.5-1wt% of the weight of the oyster shell coarse powder.
The essential oil in the step (4) is at least one of citronellal essential oil and lavender essential oil; preferably, the essential oil is citronellal essential oil and lavender essential oil according to the mass ratio (1-2): (2-4) mixing.
The dispersant in the step (7) is one or a mixture of (3-aminopropyl) dimethylethoxy silane and polyacid polyester hyper-dispersant; preferably, the dispersant in the step (7) is (3-aminopropyl) dimethylethoxysilane and a polyacid polyester hyper-dispersant in a mass ratio of (1-2): (1-2) mixing.
In the prior art, most oyster shells are used as a calcium source, and the adopted oyster shell powder is calcined, crushed, dissolved and recrystallized to obtain the nano calcium carbonate. The organic biomasses such as various proteins, glycoproteins, polysaccharides, amino acids and the like in the oyster shells are one of the great advantages, and the other great advantage is the unique micropore structure. In textile application, most oyster shells are calcined, so that organic biomass in the oyster shells disappears, and the unique microporous structure of the oyster shells collapses easily, thereby greatly reducing the use value of the oyster shells, causing great waste and greatly increasing the utilization cost of the oyster shells.
Aiming at the problem, the invention provides that the oyster shell is not calcined but directly ground, so that the loss of organic biomass in the oyster shell is reduced as much as possible. Furthermore, the invention utilizes the larger adsorption capacity brought by the microporous structure of oyster shells to adsorb citronellal essential oil and lavender essential oil, wherein citronellal is a monoterpene organic matter and is used as the most widely existing antibacterial substance in essential oil, and the citronellal also has the widest spectrum of sterilization effect and is safe and harmless to human bodies. The sterilization mechanism of the sterilization agent is the same as that of most terpenoid sterilization agents, and the sterilization agent mainly influences the exchange process inside and outside the mould cells by changing the fluidity and permeability of the mould cell membranes, thereby leading to the inactivation of the mould. The lavender essential oil also has a calming effect on heart, can reduce hypertension, soothe palpitation and can effectively help sleep. The combination of the oyster shell powder and the oyster shell powder not only improves the bacteriostatic action of the oyster shell powder, but also increases the functions of sleep aiding and nerve soothing.
Further, the superfine oyster shell powder treated by the essential oil is coated by the polydopamine to obtain the polydopamine modified superfine oyster shell powder. The particle size of the superfine oyster shell powder is less than 1 mu m, and the smaller particle size shows that the superfine oyster shell powder has larger specific surface area, so the superfine oyster shell powder is easy to agglomerate and has poor dispersibility. The polydopamine coating is beneficial to improving the dispersibility of the polydopamine coating, can reduce the loss of the organic biomass and inhibit the volatilization of essential oil components, and greatly prolongs the service life of the organic biomass and the essential oil components. In addition, the polydopamine fiber is further treated by benzyl bromide, and the polydopamine surface contains a large amount of amino groups, so that the benzyl bromide is used for quaternization to form a large amount of cationic quaternary ammonium salt, the conductivity of the polydopamine fiber is enhanced, and the antistatic capacity of the polydopamine fiber is greatly improved by adding the polydopamine fiber into the fiber.
Finally, the invention further adopts the mixture of (3-aminopropyl) dimethylethoxysilane and the polyacid polyester hyper-dispersant as the dispersant for improving the dispersibility of the polydopamine modified superfine oyster-based fiber in the polyvinyl alcohol resin. According to the invention, firstly, the polyatomic acid polyester hyperdispersant is adopted to improve the dispersibility of the superfine oyster shell powder, and the-C-NH-or-C-O-is taken as a bridging group, and carboxyl is reacted with or chelated with a group on the surface of polydopamine, so that the dispersibility of the oyster shell powder is improved. On the other hand, the (3-aminopropyl) dimethylethoxysilane is used as a dispersing agent, and the principle of the dispersing agent is that the (3-aminopropyl) dimethylethoxysilane can be hydrolyzed to react with hydroxyl on polyvinyl alcohol, and a 3-aminopropyl group can react with polydopamine, so that the dispersion and anchoring of the polydopamine modified superfine oyster-based fiber in the polyvinyl alcohol resin are realized. The mechanical properties of the oyster-based fibers are further improved by the synergistic effect of the (3-aminopropyl) dimethylethoxysilane and the polyacid polyester hyperdispersant.
The invention has the beneficial effects that
According to the invention, the oyster shells are not calcined but directly ground, so that the loss of organic biomass in the oyster shells is reduced; the relatively large adsorption capacity brought by the microporous structure of the oyster shell is utilized, the citronellal essential oil and the lavender essential oil are adsorbed by the oyster shell, the bacteriostatic action of the oyster shell powder is improved, and the functions of helping sleep and soothing nerves are also increased; furthermore, the polydopamine coating is adopted, so that on one hand, the dispersibility of the polydopamine coating is improved, on the other hand, the loss of the organic biomass can be reduced, the volatilization of essential oil components can be inhibited, and the service lives of the organic biomass and the essential oil components can be greatly prolonged; and the benzyl bromide is adopted to carry out quaternary ammonium ionization on the polydopamine, so that the antistatic effect of the polydopamine is improved, and the polydopamine and the dispersing agent are applied to the preparation of oyster-based fibers, so that the antistatic oyster-based fiber flocculus which is excellent in antistatic and antibacterial effects, contains a large amount of organic biomass and can help sleep and calm nerves is obtained.
Detailed Description
Dopamine hydrochloride, CAS number: 62-31-7
Tris, CAS No.: 77-86-1
Polyvinyl alcohol resin, type: 117, cas No.: 9002-89-5, purchased from Kuraray, japan.
Citronellal essential oil, cat No.: 0528, jiangxi Cedar natural medicinal oil Co.
Lavender essential oil, cat #: 120307, jiangxi Cedar natural medicinal oil Co.
The polyacid polyester hyperdispersant adopted in the examples is polyacid polyester hyperdispersant Klamar ® 19161, item number: 100834, kralmar.
Example 1
A preparation process of an antistatic oyster-based fiber flocculus comprises the following steps:
(1) Cleaning the surface of the oyster shell with water, placing the oyster shell in an aqueous solution containing 6wt% of oxidant for disinfection, assisting ultrasonic oscillation for 30min, taking out the oyster shell, cleaning with water again, and finally drying to obtain a pretreated oyster shell;
(2) Crushing the pretreated oyster shell powder obtained in the step (1) to a size of 300 meshes, washing with water, and filtering for three times to obtain oyster shell coarse powder;
(3) Transferring the crushed oyster shell coarse powder to a strong bead mill, adding vinyl bis-stearamide, and grinding to obtain superfine oyster shell powder with the particle size of less than 1 mu m;
(4) Mixing 15 parts by mass of superfine oyster shell powder and 50 parts by mass of essential oil, stirring and adsorbing for 30min, and centrifuging to obtain precipitate to obtain superfine oyster shell powder adsorbed by the essential oil;
(5) Mixing 8 parts by mass of superfine oyster shell powder adsorbed by essential oil and 60 parts by mass of polyvinyl alcohol resin, and stirring and reacting at 180 ℃ and under the control pressure of 0.3Mpa for 60min to obtain a fiber solution;
(6) Adding the fiber liquid obtained in the step (5) into a spinning machine for dry spinning; the temperature of the spinning fiber liquid is 100 ℃ during extrusion, the diameter of a spinning hole is 0.05mm, nitrogen hot air is used for protecting the position near the spinning hole, the temperature of the hot air is 120 ℃, and the spinning speed is 2m/min; stretching by adopting a mechanical stretching system, wherein the stretching ratio is 4.5, and the stretching temperature is 180 ℃, so as to obtain oyster-based fibers; and finishing by a carding lapping machine to obtain the antistatic oyster-based fiber flocculus.
The oxidant in the step (1) is sodium hypochlorite.
The ultrasonic power in the step (1) is 800W, and the frequency is 90Hz.
The adding amount of the vinyl bis stearamide in the step (3) is 0.7wt% of the weight of the oyster shell coarse powder.
The essential oil in the step (4) is prepared from citronellal essential oil and lavender essential oil in a mass ratio of 2:3, and mixing.
Example 2
A preparation process of the antistatic oyster-based fiber flocculus comprises the following steps:
(1) Cleaning the surface of the oyster shell with water, placing the oyster shell in an aqueous solution containing 6wt% of oxidant for disinfection, assisting ultrasonic oscillation for 30min, taking out the oyster shell, cleaning the oyster shell with water again, and finally drying to obtain a pretreated oyster shell;
(2) Crushing the pretreated oyster shell powder obtained in the step (1) to a size of 300 meshes, washing with water, and filtering for three times to obtain oyster shell coarse powder;
(3) Transferring the crushed oyster shell coarse powder to a strong bead mill, adding vinyl bis-stearamide, and grinding to obtain superfine oyster shell powder with the particle size of less than 1 mu m;
(4) Mixing 15 parts of superfine oyster shell powder and 50 parts of essential oil by mass, stirring and adsorbing for 30min, and centrifuging to obtain precipitate to obtain superfine oyster shell powder adsorbed by the essential oil;
(5) Mixing 15 parts by mass of superfine oyster shell powder adsorbed by the essential oil prepared in the step (4), 3 parts by mass of dopamine hydrochloride and 300 parts by mass of water, ultrasonically stirring for 30min to obtain an emulsion, adjusting the pH of the emulsion to 8 by using a 7wt% trihydroxymethyl aminomethane aqueous solution, stirring for 10min at 30 ℃, adding 0.6 part by mass of salicylic acid into the emulsion, adjusting the pH of the emulsion to 8 by using a 7wt% trihydroxymethyl aminomethane aqueous solution, continuously stirring for 10min at 30 ℃, and filtering and drying to obtain polydopamine modified superfine oyster shell powder;
(6) Mixing 8 parts by mass of poly-dopamine modified superfine oyster shell powder and 60 parts by mass of polyvinyl alcohol resin, and stirring and reacting at 180 ℃ and under the control pressure of 0.3Mpa for 60min to obtain a fiber solution;
(7) Adding the fiber liquid obtained in the step (6) into a spinning machine for dry spinning; during extrusion, the temperature of the spinning fiber liquid is 100 ℃, the diameter of a spinneret orifice is 0.05mm, nitrogen hot air is used for protecting the position close to the spinneret orifice, the temperature of the hot air is 120 ℃, and the spinning speed is 2m/min; stretching by adopting a mechanical stretching system, wherein the stretching ratio is 4.5, and the stretching temperature is 180 ℃, so as to obtain oyster-based fibers; and finishing by a carding lapping machine to obtain the antistatic oyster-based fiber flocculus.
The oxidant in the step (1) is sodium hypochlorite.
And (3) the ultrasonic power in the step (1) and the ultrasonic power in the step (5) are 800W, and the frequency is 90Hz.
The adding amount of the vinyl bis stearamide in the step (3) is 0.7wt% of the weight of the oyster shell coarse powder.
The essential oil in the step (4) is prepared from citronellal essential oil and lavender essential oil according to the mass ratio of 2:3, and mixing.
Example 3
A preparation process of an antistatic oyster-based fiber flocculus comprises the following steps:
(1) Cleaning the surface of the oyster shell with water, placing the oyster shell in an aqueous solution containing 6wt% of oxidant for disinfection, assisting ultrasonic oscillation for 30min, taking out the oyster shell, cleaning with water again, and finally drying to obtain a pretreated oyster shell;
(2) Crushing the pretreated oyster shell powder obtained in the step (1) to a size of 300 meshes, washing with water, and filtering for three times to obtain oyster shell coarse powder;
(3) Transferring the crushed oyster shell coarse powder to a strong bead mill, adding vinyl bis-stearamide, and grinding to obtain superfine oyster shell powder with the particle size of less than 1 mu m;
(4) Mixing 15 parts by mass of superfine oyster shell powder and 50 parts by mass of essential oil, stirring and adsorbing for 30min, and centrifuging to obtain precipitate to obtain superfine oyster shell powder adsorbed by the essential oil;
(5) Mixing 15 parts by mass of superfine oyster shell powder adsorbed by the essential oil prepared in the step (4), 3 parts by mass of dopamine hydrochloride and 300 parts by mass of water, ultrasonically stirring for 30min to obtain an emulsion, adjusting the pH of the emulsion to 8 by using a 7wt% trihydroxymethyl aminomethane aqueous solution, stirring for 10min at 30 ℃, adding 0.6 part by mass of salicylic acid into the emulsion, adjusting the pH of the emulsion to 8 by using a 7wt% trihydroxymethyl aminomethane aqueous solution, continuously stirring for 10min at 30 ℃, and filtering and drying to obtain polydopamine modified superfine oyster shell powder;
(6) Mixing 0.3 part of benzyl bromide, 10 parts of polydopamine modified superfine oyster shell powder and 90 parts of water in parts by mass, stirring and reacting at 75 ℃ for 30min, and filtering, washing and drying to obtain quaternized superfine oyster shell powder;
(7) Mixing 8 parts of quaternized superfine oyster shell powder and 60 parts of polyvinyl alcohol resin according to parts by mass, and stirring and reacting at 180 ℃ and under the control pressure of 0.3Mpa for 60min to obtain a fiber solution;
(8) Adding the fiber liquid obtained in the step (7) into a spinning machine for dry spinning; the temperature of the spinning fiber liquid is 100 ℃ during extrusion, the diameter of a spinning hole is 0.05mm, nitrogen hot air is used for protecting the position near the spinning hole, the temperature of the hot air is 120 ℃, and the spinning speed is 2m/min; stretching by adopting a mechanical stretching system, wherein the stretching ratio is 4.5, and the stretching temperature is 180 ℃, so as to obtain oyster-based fibers; and finishing by a carding lapping machine to obtain the antistatic oyster-based fiber flocculus.
The oxidant in the step (1) is sodium hypochlorite.
And (3) the ultrasonic power in the step (1) and the ultrasonic power in the step (5) are 800W, and the frequency is 90Hz.
The adding amount of the vinyl bis stearamide in the step (3) is 0.7wt% of the weight of the oyster shell coarse powder.
The essential oil in the step (4) is prepared from citronellal essential oil and lavender essential oil according to the mass ratio of 2:3, and mixing.
Example 4
A preparation process of an antistatic oyster-based fiber flocculus comprises the following steps:
(1) Cleaning the surface of the oyster shell with water, placing the oyster shell in an aqueous solution containing 6wt% of oxidant for disinfection, assisting ultrasonic oscillation for 30min, taking out the oyster shell, cleaning the oyster shell with water again, and finally drying to obtain a pretreated oyster shell;
(2) Crushing the pretreated oyster shell powder obtained in the step (1) to a size of 300 meshes, washing with water, and filtering for three times to obtain oyster shell coarse powder;
(3) Transferring the crushed oyster shell coarse powder to a strong bead mill, adding vinyl bis-stearamide, and grinding to superfine oyster shell powder with the particle size of less than 1 mu m;
(4) Mixing 15 parts of superfine oyster shell powder and 50 parts of essential oil by mass, stirring and adsorbing for 30min, and centrifuging to obtain precipitate to obtain superfine oyster shell powder adsorbed by the essential oil;
(5) Mixing 15 parts by mass of ultrafine oyster shell powder adsorbed by the essential oil prepared in the step (4), 3 parts by mass of dopamine hydrochloride and 300 parts by mass of water, ultrasonically stirring for 30min to obtain an emulsion, adjusting the pH of the emulsion to 8 by using a 7wt% trihydroxymethyl aminomethane aqueous solution, stirring at 30 ℃ for 10min, adding 0.6 part by mass of salicylic acid, adjusting the pH to 8 by using a 7wt% trihydroxymethyl aminomethane aqueous solution, continuously stirring at 30 ℃ for 10min, filtering, and drying to obtain polydopamine-modified ultrafine oyster shell powder;
(6) Mixing 0.3 part of benzyl bromide, 10 parts of polydopamine modified superfine oyster shell powder and 90 parts of water in parts by mass, stirring and reacting at 75 ℃ for 30min, and filtering, washing and drying to obtain quaternized superfine oyster shell powder;
(7) Mixing 8 parts of quaternized superfine oyster shell powder, 3 parts of dispersing agent and 60 parts of polyvinyl alcohol resin according to parts by mass, and stirring and reacting at 180 ℃ and under the control pressure of 0.3Mpa for 60min to obtain a fiber solution;
(8) Adding the fiber liquid obtained in the step (7) into a spinning machine for dry spinning; the temperature of the spinning fiber liquid is 100 ℃ during extrusion, the diameter of a spinning hole is 0.05mm, nitrogen hot air is used for protecting the position near the spinning hole, the temperature of the hot air is 120 ℃, and the spinning speed is 2m/min; stretching by adopting a mechanical stretching system, wherein the stretching ratio is 4.5, and the stretching temperature is 180 ℃, so as to obtain oyster-based fibers; and finishing by a carding lapping machine to obtain the antistatic oyster-based fiber flocculus.
The oxidant in the step (1) is sodium hypochlorite.
And (3) the ultrasonic power in the step (1) and the ultrasonic power in the step (5) are 800W, and the frequency is 90Hz.
The adding amount of the vinyl bis stearamide in the step (3) is 0.7wt% of the weight of the oyster shell coarse powder.
The essential oil in the step (4) is prepared from citronellal essential oil and lavender essential oil according to the mass ratio of 2:3, and mixing.
The dispersing agent in the step (7) is prepared from (3-aminopropyl) dimethylethoxysilane and a polyacid polyester hyper-dispersing agent according to the mass ratio of 1:1 are mixed.
Example 5
A preparation process of the antistatic oyster-based fiber flocculus comprises the following steps:
(1) Cleaning the surface of the oyster shell with water, placing the oyster shell in an aqueous solution containing 6wt% of oxidant for disinfection, assisting ultrasonic oscillation for 30min, taking out the oyster shell, cleaning the oyster shell with water again, and finally drying to obtain a pretreated oyster shell;
(2) Crushing the pretreated oyster shell powder obtained in the step (1) to a size of 300 meshes, washing with water, and filtering for three times to obtain oyster shell coarse powder;
(3) Transferring the crushed oyster shell coarse powder to a strong bead mill, adding vinyl bis-stearamide, and grinding to obtain superfine oyster shell powder with the particle size of less than 1 mu m;
(4) Mixing 15 parts by mass of superfine oyster shell powder and 50 parts by mass of essential oil, stirring and adsorbing for 30min, and centrifuging to obtain precipitate to obtain superfine oyster shell powder adsorbed by the essential oil;
(5) Mixing 15 parts by mass of superfine oyster shell powder adsorbed by the essential oil prepared in the step (4), 3 parts by mass of dopamine hydrochloride and 300 parts by mass of water, ultrasonically stirring for 30min to obtain an emulsion, adjusting the pH of the emulsion to 8 by using a 7wt% trihydroxymethyl aminomethane aqueous solution, stirring for 10min at 30 ℃, adding 0.6 part by mass of salicylic acid into the emulsion, adjusting the pH of the emulsion to 8 by using a 7wt% trihydroxymethyl aminomethane aqueous solution, continuously stirring for 10min at 30 ℃, and filtering and drying to obtain polydopamine modified superfine oyster shell powder;
(6) Mixing 0.3 part of benzyl bromide, 10 parts of polydopamine-modified ultrafine oyster shell powder and 90 parts of water in parts by mass, stirring and reacting at 75 ℃ for 30min, and filtering, washing and drying to obtain quaternized ultrafine oyster shell powder;
(7) Mixing 8 parts of quaternized superfine oyster shell powder, 3 parts of dispersing agent and 60 parts of polyvinyl alcohol resin according to parts by mass, and stirring and reacting at 180 ℃ and under the control pressure of 0.3Mpa for 60min to obtain a fiber solution;
(8) Adding the fiber liquid obtained in the step (7) into a spinning machine for dry spinning; the temperature of the spinning fiber liquid is 100 ℃ during extrusion, the diameter of a spinning hole is 0.05mm, nitrogen hot air is used for protecting the position near the spinning hole, the temperature of the hot air is 120 ℃, and the spinning speed is 2m/min; stretching by adopting a mechanical stretching system, wherein the stretching ratio is 4.5, and the stretching temperature is 180 ℃, so as to obtain oyster-based fibers; and finishing by a carding lapping machine to obtain the antistatic oyster-based fiber flocculus.
The oxidant in the step (1) is sodium hypochlorite.
And (5) the ultrasonic power is 800W, and the frequency is 90Hz.
The addition amount of the vinyl bis-stearamide in the step (3) is 0.7wt% of the mass of the oyster shell coarse powder.
The essential oil in the step (4) is prepared from citronellal essential oil and lavender essential oil according to the mass ratio of 2:3, and mixing.
And (7) the dispersing agent is (3-aminopropyl) dimethylethoxysilane.
Example 6
A preparation process of the antistatic oyster-based fiber flocculus comprises the following steps:
(1) Cleaning the surface of the oyster shell with water, placing the oyster shell in an aqueous solution containing 6wt% of oxidant for disinfection, assisting ultrasonic oscillation for 30min, taking out the oyster shell, cleaning the oyster shell with water again, and finally drying to obtain a pretreated oyster shell;
(2) Crushing the pretreated oyster shell powder obtained in the step (1) to a size of 300 meshes, washing with water, and filtering for three times to obtain oyster shell coarse powder;
(3) Transferring the crushed oyster shell coarse powder to a strong bead mill, adding vinyl bis-stearamide, and grinding to obtain superfine oyster shell powder with the particle size of less than 1 mu m;
(4) Mixing 15 parts of superfine oyster shell powder and 50 parts of essential oil by mass, stirring and adsorbing for 30min, and centrifuging to obtain precipitate to obtain superfine oyster shell powder adsorbed by the essential oil;
(5) Mixing 15 parts by mass of superfine oyster shell powder adsorbed by the essential oil prepared in the step (4), 3 parts by mass of dopamine hydrochloride and 300 parts by mass of water, ultrasonically stirring for 30min to obtain an emulsion, adjusting the pH of the emulsion to 8 by using a 7wt% trihydroxymethyl aminomethane aqueous solution, stirring for 10min at 30 ℃, adding 0.6 part by mass of salicylic acid into the emulsion, adjusting the pH of the emulsion to 8 by using a 7wt% trihydroxymethyl aminomethane aqueous solution, continuously stirring for 10min at 30 ℃, and filtering and drying to obtain polydopamine modified superfine oyster shell powder;
(6) Mixing 0.3 part of benzyl bromide, 10 parts of polydopamine modified superfine oyster shell powder and 90 parts of water in parts by mass, stirring and reacting at 75 ℃ for 30min, and filtering, washing and drying to obtain quaternized superfine oyster shell powder;
(7) Mixing 8 parts of quaternized superfine oyster shell powder, 3 parts of dispersing agent and 60 parts of polyvinyl alcohol resin in parts by mass, and stirring and reacting at 180 ℃ and under the control pressure of 0.3Mpa for 60min to obtain fiber liquid;
(8) Adding the fiber liquid obtained in the step (7) into a spinning machine for dry spinning; the temperature of the spinning fiber liquid is 100 ℃ during extrusion, the diameter of a spinning hole is 0.05mm, nitrogen hot air is used for protecting the position near the spinning hole, the temperature of the hot air is 120 ℃, and the spinning speed is 2m/min; stretching by adopting a mechanical stretching system, wherein the stretching ratio is 4.5, and the stretching temperature is 180 ℃, so as to obtain oyster-based fibers; and finishing by a carding lapping machine to obtain the antistatic oyster-based fiber flocculus.
The oxidant in the step (1) is sodium hypochlorite.
And (5) the ultrasonic power is 800W, and the frequency is 90Hz.
The adding amount of the vinyl bis stearamide in the step (3) is 0.7wt% of the weight of the oyster shell coarse powder.
The essential oil in the step (4) is prepared from citronellal essential oil and lavender essential oil according to the mass ratio of 2:3, mixing the components.
The dispersant in the step (7) is a polybasic acid polyester hyper-dispersant.
Test example 1
The antistatic oyster-based fiber flocculus prepared in the embodiments 1-4 of the invention is prepared according to the national standard GB/T12703.2-2021 part 2 of the textile static electricity testing method: the surface density of the charge was measured by the manual rubbing method, and the results are shown in Table 1.
Table 1: measurement of surface Density of Charge
| Surface density of electric charge (uC/m) 2 ) | |
| Example 1 | 2.92 |
| Example 2 | 2.41 |
| Example 3 | 0.59 |
| Example 4 | 0.51 |
As can be seen from table 1, the oyster-based fiber flocculus of example 1 has the highest charge surface density, while the oyster-based fiber flocculus of example 2 has a lower charge surface density than that of example 1, because the oyster shell powder added to the oyster-based fiber flocculus of example 2 is modified by polydopamine, which has no conductivity, but shows weak conductivity after salicylic acid treatment, but the conductivity effect is not obvious. Therefore, in example 3, benzyl bromide is used to treat the poly-dopamine-modified ultrafine oyster shell powder, so that the quaternary ammonium salt of the amino group on the surface of the poly-dopamine-modified ultrafine oyster shell powder is salinized, thereby greatly enhancing the conductivity and the bacteriostatic effect of the poly-dopamine-modified ultrafine oyster shell powder. Example 4 the quaternized ultrafine oyster shell powder, a dispersing agent and polyvinyl alcohol resin are further mixed to prepare a fiber solution, and the quaternized ultrafine oyster shell powder in the obtained oyster-based fiber has good dispersibility, so that a uniform conductive network is formed, and the antistatic performance of the fiber is further enhanced.
Test example 2
The oyster-based fibers prepared in examples 1 to 6 were subjected to a tensile test using a universal tester. And (3) testing conditions are as follows: room temperature 25 ℃ and relative humidity 65%. The tensile rate was 1mm/min, and the breaking strength was measured, and the average value was taken for 5 times of each sample test. The test results are shown in Table 2.
Table 2: test results of breaking Strength
| Breaking strength/(N) | |
| Example 1 | 524 |
| Example 2 | 562 |
| Example 3 | 569 |
| Example 4 | 645 |
| Example 5 | 632 |
| Example 6 | 634 |
As shown in Table 2, the oyster-based fibers prepared by the method have good mechanical properties. The breaking strength of the oyster-based fiber prepared in the example 1 is lower than that of the oyster-based fiber prepared in the example 2, because the oyster shell powder added in the oyster-based fiber flocculus in the example 2 is modified by the polydopamine, and the polydopamine has abundant amino, hydroxyl and carboxyl groups on the surface, the compatibility of the superfine oyster shell powder and the polyvinyl alcohol resin is improved, and the influence of the inorganic filler on the mechanical property of the resin fiber is reduced. However, because the ultra-fine oyster-based fiber modified by the polydopamine has poor dispersibility, the ultra-fine oyster-based fiber modified by the polydopamine is used for improving the dispersibility of the ultra-fine oyster-based fiber modified by the polydopamine in a polyvinyl alcohol resin by adopting a dispersant prepared by mixing (3-aminopropyl) dimethylethoxysilane and a polyacid polyester hyper-dispersant. According to the invention, firstly, the dispersibility of the superfine oyster shell powder is improved by adopting the polyacid polyester hyperdispersant, and the fracture strength is improved to 634N in example 6, wherein-C-NH-or-C-O-is taken as a bridge group, and carboxyl is reacted with or chelated with a group on the surface of polydopamine, so that the dispersibility of the oyster shell powder is improved. On the other hand, the (3-aminopropyl) dimethylethoxysilane is used as a dispersing agent, the principle is that the (3-aminopropyl) dimethylethoxysilane can be hydrolyzed to react with hydroxyl on polyvinyl alcohol, and a 3-aminopropyl group can react with polydopamine, so that the dispersion and anchoring of the polydopamine modified superfine oyster-based fiber in the polyvinyl alcohol resin are realized. In the embodiment 4 of the invention, the mechanical property of the oyster-based fiber is further improved by adopting the synergistic effect of the (3-aminopropyl) dimethylethoxysilane and the polyacid polyester hyperdispersant.
Claims (9)
1. The preparation process of the antistatic oyster-based fiber flocculus is characterized by comprising the following steps of:
(1) Cleaning the surface of the oyster shell with water, placing the oyster shell in an oxidant-containing aqueous solution for disinfection, taking out the oyster shell, cleaning the oyster shell with water again with the assistance of ultrasonic oscillation, and finally drying to obtain a pretreated oyster shell;
(2) Crushing the pretreated oyster shells obtained in the step (1), washing with water, and filtering for three times to obtain coarse oyster shell powder;
(3) Transferring the crushed oyster shell coarse powder to a strong bead mill, adding vinyl bis stearamide, and grinding to obtain superfine oyster shell powder with the particle size of 0.5-1 mu m;
(4) Mixing the superfine oyster shell powder and the essential oil, stirring and adsorbing, and centrifuging to obtain a precipitate to obtain the superfine oyster shell powder adsorbed by the essential oil;
(5) Mixing the superfine oyster shell powder adsorbed by the essential oil prepared in the step (4), dopamine hydrochloride and water, performing ultrasonic stirring to obtain an emulsion, adjusting the pH of the emulsion by using a trihydroxymethyl aminomethane aqueous solution, then stirring, adding salicylic acid into the emulsion, adjusting the pH by using the trihydroxymethyl aminomethane aqueous solution, continuing stirring, filtering, and drying to obtain the polydopamine modified superfine oyster shell powder;
(6) Mixing benzyl bromide, polydopamine modified superfine oyster shell powder and water for reaction, filtering, washing and drying to obtain quaternized superfine oyster shell powder;
(7) Mixing the quaternized superfine oyster shell powder, a dispersing agent and polyvinyl alcohol resin, and stirring for reaction to obtain a fiber solution;
(8) Adding the fiber liquid obtained in the step (7) into a spinning machine for dry spinning; obtaining oyster-based fibers; and finishing by a carding lapping machine to obtain the antistatic oyster-based fiber flocculus.
2. The preparation process of the antistatic oyster-based fiber flocculus of claim 1, comprising the following steps:
(1) Cleaning the surface of the oyster shell with water, placing the oyster shell into an aqueous solution containing 5-7wt% of an oxidant for disinfection, assisting ultrasonic oscillation for 20-30min, taking out the oyster shell, cleaning the oyster shell with water again, and finally drying to obtain a pretreated oyster shell;
(2) Crushing the pretreated oyster shell powder obtained in the step (1) to a size of 300 meshes, washing with water, and filtering for three times to obtain oyster shell coarse powder;
(3) Transferring the crushed oyster shell coarse powder to a strong bead mill, adding vinyl bis stearamide, and grinding to obtain superfine oyster shell powder with the particle size of 0.5-1 mu m;
(4) Mixing 10-20 parts by mass of superfine oyster shell powder and 50-100 parts by mass of essential oil, stirring and adsorbing for 20-30min, and centrifuging to obtain precipitate to obtain superfine oyster shell powder adsorbed by the essential oil;
(5) Mixing 10-20 parts by mass of ultrafine oyster shell powder adsorbed by the essential oil prepared in the step (4), 2-4 parts by mass of dopamine hydrochloride and 300-500 parts by mass of water, ultrasonically stirring for 20-40min to obtain an emulsion, adjusting the pH of the emulsion to 7-9 by using 6-8wt% of a trihydroxymethyl aminomethane aqueous solution, stirring for 5-10min at 20-40 ℃, adding 0.5-1 part by mass of salicylic acid, adjusting the pH to 7-9 by using 6-8wt% of a trihydroxymethyl aminomethane aqueous solution, continuously stirring for 5-10min at 20-40 ℃, filtering, and drying to obtain poly-dopamine modified ultrafine oyster shell powder;
(6) Mixing 0.1-0.5 part of benzyl bromide, 5-10 parts of polydopamine modified superfine oyster shell powder and 90-100 parts of water by mass, stirring and reacting at 70-80 ℃ for 20-40min, filtering, washing and drying to obtain quaternized superfine oyster shell powder;
(7) Mixing 5-10 parts of quaternized oyster shell powder, 2-4 parts of dispersant and 50-60 parts of polyvinyl alcohol resin according to parts by mass, and stirring and reacting at 150-200 ℃ and under the control pressure of 0.25-0.4Mpa for 40-80min to obtain a fiber solution;
(8) Adding the fiber solution obtained in the step (7) into a spinning machine for dry spinning to obtain oyster-based fibers; and finishing by a carding lapping machine to obtain the antistatic oyster-based fiber flocculus.
3. The process for preparing the antistatic oyster-based fiber flocculus according to claim 2, wherein the oxidant in the step (1) is one of sodium hypochlorite and hydrogen peroxide.
4. The preparation process of the antistatic oyster-based fiber flocculus of claim 2, wherein the ultrasonic power in the step (1) is 400-1000W, and the frequency is 90-120Hz.
5. The process for preparing antistatic oyster-based fiber flocculus of claim 2, wherein the amount of the vinyl bis-stearamide added in the step (3) is 0.5-1wt% of the weight of the oyster shell coarse powder.
6. The process for preparing the antistatic oyster-based fiber flocculus as claimed in claim 2, wherein the essential oil in the step (4) is at least one of citronellal essential oil and lavender essential oil.
7. The preparation process of the antistatic oyster-based fiber flocculus of claim 2, wherein the dry spinning conditions in the step (8) are as follows: the temperature of the spinning fiber liquid is 90-105 ℃ during extrusion, the diameter of a spinneret orifice is 0.05-0.1mm, the nitrogen hot air is used for protecting the vicinity of the spinneret orifice, the temperature of the hot air is 110-130 ℃, and the spinning speed is 2-3m/min; stretching with a mechanical stretching system, wherein the draw ratio is 4.5, and the stretching temperature is 170-200 ℃.
8. The process for preparing the antistatic oyster-based fiber flocculus according to claim 2, wherein the dispersant is one or a mixture of (3-aminopropyl) dimethylethoxysilane and a polyacid polyester hyperdispersant.
9. An antistatic oyster-based fiber flocculus is characterized by being prepared by the preparation process of the antistatic oyster-based fiber flocculus according to any one of claims 1-8.
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