TWI827733B - Method for preparing a functional fiber - Google Patents
Method for preparing a functional fiber Download PDFInfo
- Publication number
- TWI827733B TWI827733B TW108141686A TW108141686A TWI827733B TW I827733 B TWI827733 B TW I827733B TW 108141686 A TW108141686 A TW 108141686A TW 108141686 A TW108141686 A TW 108141686A TW I827733 B TWI827733 B TW I827733B
- Authority
- TW
- Taiwan
- Prior art keywords
- alkylene oxide
- polymer
- functional
- alkoxylated polyethyleneimine
- oxide segment
- Prior art date
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- 239000000835 fiber Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 113
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 93
- 239000013538 functional additive Substances 0.000 claims abstract description 74
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 125000002947 alkylene group Chemical group 0.000 claims description 62
- 238000009987 spinning Methods 0.000 claims description 41
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 30
- 239000012634 fragment Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- 229920002678 cellulose Polymers 0.000 claims description 13
- 239000001913 cellulose Substances 0.000 claims description 13
- 239000003094 microcapsule Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000004753 textile Substances 0.000 claims description 10
- 238000002166 wet spinning Methods 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 6
- 239000012876 carrier material Substances 0.000 claims description 5
- 238000002074 melt spinning Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 238000000578 dry spinning Methods 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003082 abrasive agent Substances 0.000 claims description 2
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229920005615 natural polymer Polymers 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 claims description 2
- 239000012782 phase change material Substances 0.000 claims description 2
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims 1
- 239000004566 building material Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- -1 ethylene oxide alkane Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004814 polyurethane Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 5
- 239000012991 xanthate Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 1
- CQXZMKRIHHGTKE-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione;ethene Chemical compound C=C.O=C1OCCOC(=O)C2=CC=C1C=C2 CQXZMKRIHHGTKE-UHFFFAOYSA-N 0.000 description 1
- WAZPLXZGZWWXDQ-UHFFFAOYSA-N 4-methyl-4-oxidomorpholin-4-ium;hydrate Chemical compound O.C[N+]1([O-])CCOCC1 WAZPLXZGZWWXDQ-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000012358 sourcing Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/22—Cellulose xanthate
- C08L1/24—Viscose
-
- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
Abstract
Description
本發明係關於一種功能性纖維之製備方法，其包含形成包含至少一種功能性添加劑、聚合物及烷氧基化聚伸乙亞胺之聚合物組合物的步驟。聚合物組合物經歷紡絲製程以生產功能性纖維。特定而言，本發明係關於一種製備功能性纖維中所使用之烷氧基化聚伸乙亞胺(polyethylenimine)，其中該功能性纖維包含聚合物基質及至少一種功能性添加劑。The present invention relates to a method for preparing functional fibers, which includes the steps of forming a polymer composition including at least one functional additive, a polymer and an alkoxylated polyethyleneimine. The polymer composition undergoes a spinning process to produce functional fibers. In particular, the present invention relates to an alkoxylated polyethylenimine used in the preparation of functional fibers, wherein the functional fibers comprise a polymer matrix and at least one functional additive.
紡織行業之各個領域對針對消費者具有額外功能益處之聚合物纖維材料之需求較高。此等纖維材料之應用領域包括：例如作為服裝行業之襯布材料、工業紡織物，例如衛生品應用(傷口敷料)；作為載體材料；作為建築及運輸材料；作為裝飾材料；或作為濾材，例如用於過濾廢水或濾出空氣及空氣與水成分之結合。There is a high demand in various areas of the textile industry for polymer fiber materials with additional functional benefits for consumers. The application fields of these fiber materials include: for example, as lining materials in the clothing industry, industrial textiles, such as hygiene applications (wound dressings); as carrier materials; as construction and transportation materials; as decorative materials; or as filter materials, such as In filtering waste water or filtering out air and the combination of air and water components.
包含功能性添加劑之織品原則上可藉由沿著紡織物附加值鏈的織品生產或纖維非編織網形成來獲得，在每種情況下根據功能性添加(additized)纖維，用添加劑分散液塗佈片狀紡織物結構或在已生產之纖維非編織網結構中併入固態或液態功能性添加劑。Fabrics containing functional additives can in principle be obtained by fabric production or nonwoven web formation of fibers along the textile value-added chain, in each case adding (additized) fibers according to the functionality, coating them with an additive dispersion Solid or liquid functional additives are incorporated into sheet-like textile structures or into non-woven web structures of already produced fibers.
在先前技術中，存在一些與功能性織品或纖維有關之技術。舉例而言，美國專利第6,540,807號係關於一種抗菌纖維技術，其中織品經編織以形成濾材且織品包括熱塑樹脂及抗細菌劑。舉例而言，美國專利第5,180,585號揭示一種可併入至聚合物熔融物中以製造纖維或其他製品之微生物抑制粒子。另一美國專利第5,897,673號教示與聚合纖維交聯之含有纖維之細金屬粒子。In the prior art, there are some technologies related to functional fabrics or fibers. For example, US Patent No. 6,540,807 relates to an antibacterial fiber technology in which a fabric is woven to form a filter material and the fabric includes a thermoplastic resin and an antibacterial agent. For example, US Patent No. 5,180,585 discloses a microbial inhibitory particle that can be incorporated into a polymer melt to make fibers or other articles. Another US Patent No. 5,897,673 teaches fine fiber-containing metal particles cross-linked with polymeric fibers.
具有相對較高分率之功能性添加劑以呈現賦予功能特性之更多附加益處的功能性纖維之生產，產生一些關於聚合物基質與功能性試劑之間的不相容性及含有聚合物之紡絲溶液在大量添加功能性試劑下的穩定性方面的技術問題。歸因於此，以功能性紡織品形式生產之先前技術材料可以僅含有少量之功能性試劑。因此，所製備之功能性纖維就功能性而言可僅符合相對低品質之要求，且在功能性纖維之生產製程期間始終需要額外量之功能性試劑。The production of functional fibers with relatively high fractions of functional additives to present more additional benefits imparting functional properties has raised some concerns regarding incompatibilities between polymer matrices and functional agents and polymer-containing fibers. Technical issues regarding the stability of silk solutions with the addition of large amounts of functional reagents. Due to this, prior art materials produced in the form of functional textiles can contain only small amounts of functional agents. Therefore, the prepared functional fibers may only meet relatively low quality requirements in terms of functionality, and additional amounts of functional reagents are always required during the production process of the functional fibers.
此為針對製備功能性纖維之製程而不遇到不相容性及穩定性問題的主要挑戰中的原因之一。因此，本發明之目標係解決市場對功能性纖維不斷增長之需求，該等功能性纖維應該便宜生產且亦具有令人滿意之功能。This is one of the reasons why it is one of the major challenges to manufacture functional fibers without encountering incompatibility and stability issues. Therefore, the aim of the present invention is to address the growing market demand for functional fibers that should be cheap to produce and also have satisfactory functionality.
在一個態樣中，本發明係關於一種功能性纖維之製備方法，其包含形成包含至少一種功能性添加劑、聚合物及烷氧基化聚伸乙亞胺之聚合物組合物的步驟，其中該烷氧基化聚伸乙亞胺具有連接至該聚伸乙亞胺之氮原子的環氧烷片段； 其中該等環氧烷片段選自由以下組成之群：環氧乙烷片段及C3- C6 -環氧烷片段；較佳地，該等環氧烷片段包含環氧乙烷片段及C3 -C6 -環氧烷片段；更佳地，該等環氧烷片段包含環氧乙烷片段及C3 -C4 -環氧烷片段；最佳地，該等環氧烷片段包含環氧乙烷及C3 -環氧烷； 其中環氧烷片段之量係平均在1至120個環氧烷片段/氮原子之範圍內，例如在1至100個環氧烷片段/氮原子、較佳地1至80個環氧烷片段/氮原子、更佳地1至70個環氧烷片段/氮原子、最佳地1至60個環氧烷片段/氮原子(諸如1至55個環氧烷片段/氮原子)之範圍內，且其中該烷氧基化聚伸乙亞胺之重量平均分子量(Mw)為1,000至1,000,000 g/mol，較佳地在5,000至500,000範圍內，更佳地在10,000至50,000範圍內，最佳地在30,000至50,000 g/mol範圍內。In one aspect, the present invention relates to a method for preparing functional fibers, which includes the step of forming a polymer composition comprising at least one functional additive, a polymer, and an alkoxylated polyethyleneimine, wherein the The alkoxylated polyethyleneimine has an alkylene oxide segment connected to a nitrogen atom of the polyethyleneimine; wherein the alkylene oxide segments are selected from the group consisting of: an ethylene oxide segment and C 3- C 6 -alkylene oxide segments; preferably, the alkylene oxide segments include ethylene oxide segments and C 3 -C 6 -alkylene oxide segments; more preferably, the alkylene oxide segments include ethylene oxide alkane segments and C 3 -C 4 -alkylene oxide segments; optimally, the alkylene oxide segments include ethylene oxide and C 3 -alkylene oxide; wherein the amount of the alkylene oxide segments is on average between 1 and 120 In the range of alkylene oxide fragments/nitrogen atom, for example, between 1 and 100 alkylene oxide fragments/nitrogen atom, preferably between 1 and 80 alkylene oxide fragments/nitrogen atom, and more preferably between 1 and 70 epoxy atoms. alkane segments/nitrogen atom, preferably 1 to 60 alkylene oxide segments/nitrogen atom, such as 1 to 55 alkylene oxide segments/nitrogen atom, and wherein the alkoxylated polyethyleneimine The weight average molecular weight (Mw) is 1,000 to 1,000,000 g/mol, preferably in the range of 5,000 to 500,000, more preferably in the range of 10,000 to 50,000, most preferably in the range of 30,000 to 50,000 g/mol.
在另一態樣中，本發明係關於一種功能性纖維之製備方法，其包含形成包含至少一種功能性添加劑、聚合物及烷氧基化聚伸乙亞胺之聚合物組合物的步驟，其中該烷氧基化聚伸乙亞胺具有本發明之烷氧基化聚伸乙亞胺中的環氧烷片段，該等環氧烷片段包含環氧乙烷片段及C3 -環氧烷片段，其中環氧烷片段之量係平均在35至70個環氧烷片段/氮原子之範圍內；較佳地，環氧烷片段之量係平均在35至60個環氧烷片段/氮原子之範圍內；更佳地，環氧烷片段之量係平均在35至55個環氧烷片段/氮原子之範圍內，且環氧乙烷片段與其餘環氧烷片段之莫耳比係在1:10至6:1 (例如1:10至5:1)之範圍內，較佳地在1:2至3:1之範圍內，更佳地在1:1至2:1 (諸如3:2)之範圍內，且本發明之烷氧基化聚伸乙亞胺的重量平均分子量係在20,000至50,000 g/mol、較佳地25,000至45,000 g/mol、更佳地35,000至40,000 g/mol範圍內。In another aspect, the invention is directed to a method of making functional fibers comprising the step of forming a polymer composition comprising at least one functional additive, a polymer and an alkoxylated polyethyleneimine, wherein The alkoxylated polyethyleneimine has alkylene oxide segments in the alkoxylated polyethyleneimine of the present invention, and the alkylene oxide segments include ethylene oxide segments and C 3 -alkylene oxide segments. , wherein the average amount of alkylene oxide fragments is in the range of 35 to 70 alkylene oxide fragments/nitrogen atom; preferably, the average amount of alkylene oxide fragments is in the range of 35 to 60 alkylene oxide fragments/nitrogen atom within the range of In the range of 1:10 to 6:1 (such as 1:10 to 5:1), preferably in the range of 1:2 to 3:1, more preferably in the range of 1:1 to 2:1 (such as 3 :2) within the range, and the weight average molecular weight of the alkoxylated polyethyleneimine of the present invention is 20,000 to 50,000 g/mol, preferably 25,000 to 45,000 g/mol, more preferably 35,000 to 40,000 g /mol range.
較佳地，至少一種功能性添加劑及烷氧基化聚伸乙亞胺在添加至聚合物中之前經摻合。較佳地，聚合物可溶解於溶劑中或可處於熔融狀態。Preferably, at least one functional additive and the alkoxylated polyethyleneimine are blended before being added to the polymer. Preferably, the polymer is soluble in the solvent or can be in a molten state.
在另一態樣中，本發明係關於一種烷氧基化聚伸乙亞胺在製備功能性纖維之製程中之用途，其中該功能性纖維包含聚合物基質及至少一種功能性添加劑。In another aspect, the present invention relates to the use of an alkoxylated polyethyleneimine in a process for preparing functional fibers, wherein the functional fibers comprise a polymer matrix and at least one functional additive.
本申請案現意外地發現功能性添加劑在纖維上及/或其內之滯留已得以改良。換言之，將烷氧基化聚伸乙亞胺添加於紡絲溶液中可改良聚合物纖維與功能性添加劑之相容性。The present application has unexpectedly discovered that retention of functional additives on and/or within fibers has been improved. In other words, adding alkoxylated polyethyleneimine to the spinning solution can improve the compatibility of polymer fibers and functional additives.
除非另外定義，否則本文中所使用之所有技術及科學術語具有與本發明所屬領域之一般熟悉此項技術者通常所理解相同之含義。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
表述「一(a/an)」、「該(the)」當用於定義術語時，包括術語之複數及單數形式二者。The expressions "a/an" and "the" when used to define a term include both the plural and the singular forms of the term.
如本文中所使用，表述「至少一個(種)」」意謂一或多個(種)且因此包括個別組分以及混合物/組合。As used herein, the expression "at least one" means one or more and thus includes individual components as well as mixtures/combinations.
如本文中所使用，詞語「包含(comprising)」(及包含之任何形式，諸如「包含(comprise/comprises)」)、「具有(having)」(及具有之任何形式，諸如「具有(have/has)」、包括(及包括之任何形式，諸如「包括(include/includes)」或「含有」(及含有之任何形式，諸如「含有(contain/contains)」為包含性或開端式的。其不排除額外、未列出之元素或方法步驟。As used herein, the words "comprising" (and any form of including, such as "comprise/comprises"), "having" (and any form of having, such as "have/ has), includes (and any form of including, such as "include/includes" or "contains" (and any form of contains, such as "contain/contains") is inclusive or open-ended. It Additional, non-listed elements or method steps are not excluded.
如本文中所使用之術語「聚合物」包括均聚物(亦即，由單一反應性化合物製備之聚合物)及共聚物(亦即，藉由使形成反應性單體化合物之至少兩種聚合物反應來製備之聚合物)二者。The term "polymer" as used herein includes homopolymers (i.e., polymers prepared from a single reactive compound) and copolymers (i.e., polymers prepared by polymerizing at least two reactive monomeric compounds that form the polymers prepared by reaction).
如本文中所使用之術語「聚合物組合物」係指包含至少一種聚合物組分之組合物。The term "polymer composition" as used herein refers to a composition comprising at least one polymer component.
如本文中所使用之術語「功能性添加劑」係指可添加至聚合纖維以執行所需功能之添加劑。The term "functional additive" as used herein refers to additives that can be added to polymeric fibers to perform a desired function.
如本文中所使用之術語「功能性纖維」意謂具有所需功能之纖維。The term "functional fibers" as used herein means fibers that have a desired function.
本發明之第一態樣係關於一種功能性纖維之製備方法，其包含形成包含至少一種功能性添加劑、聚合物及烷氧基化聚伸乙亞胺之聚合物組合物的步驟，其中該烷氧基化聚伸乙亞胺具有連接至該聚伸乙亞胺之氮原子的環氧烷片段； 其中該等環氧烷片段選自由以下組成之群：環氧乙烷片段及C3- C6 -環氧烷片段；較佳地，該等環氧烷片段包含環氧乙烷片段及C3 -C6 -環氧烷片段；更佳地，該等環氧烷片段包含環氧乙烷片段及C3 -C4 -環氧烷片段；最佳地，該等環氧烷片段包含環氧乙烷及C3 -環氧烷； 其中環氧烷片段之量係平均在1至120個環氧烷片段/氮原子範圍內，例如在1至100個環氧烷片段/氮原子、較佳地1至80個環氧烷片段/氮原子、更佳地1至70個環氧烷片段/氮原子、最佳地1至60個環氧烷片段/氮原子，諸如1至55個環氧烷片段/氮原子之範圍內，及 其中該烷氧基化聚伸乙亞胺之重量平均分子量(Mw)為1,000至1,000,000 g/mol，較佳地在5,000至500,000範圍內，更佳地在10,000至50,000範圍內，最佳地在30,000至50,000 g/mol範圍內。A first aspect of the present invention relates to a method for preparing functional fibers, which includes the step of forming a polymer composition comprising at least one functional additive, a polymer and an alkoxylated polyethyleneimine, wherein the alkoxylated polyethyleneimine Oxylated polyethyleneimine has an alkylene oxide segment connected to a nitrogen atom of the polyethyleneimine; wherein the alkylene oxide segments are selected from the group consisting of: an ethylene oxide segment and C 3- C 6 -alkylene oxide segments; preferably, the alkylene oxide segments include ethylene oxide segments and C 3 -C 6 -alkylene oxide segments; more preferably, the alkylene oxide segments include ethylene oxide fragments and C 3 -C 4 -alkylene oxide fragments; optimally, these alkylene oxide fragments include ethylene oxide and C 3 -alkylene oxide; wherein the amount of alkylene oxide fragments is on average between 1 and 120 In the range of alkylene oxide fragments/nitrogen atom, for example, 1 to 100 alkylene oxide fragments/nitrogen atom, preferably 1 to 80 alkylene oxide fragments/nitrogen atom, more preferably 1 to 70 alkylene oxide fragments/nitrogen atom /nitrogen atom, preferably 1 to 60 alkylene oxide fragments/nitrogen atom, such as a range of 1 to 55 alkylene oxide fragments/nitrogen atom, and wherein the weight average of the alkoxylated polyethyleneimine The molecular weight (Mw) is 1,000 to 1,000,000 g/mol, preferably in the range of 5,000 to 500,000, more preferably in the range of 10,000 to 50,000, most preferably in the range of 30,000 to 50,000 g/mol.
術語「聚伸乙亞胺」在本發明之上下文中不僅係指聚伸乙亞胺均聚物，且亦係指含有NH-CH2 -CH2 -NH結構元素連同其他伸烷基二胺結構元素(例如NH-CH2 -CH2 -CH2 -NH結構元素、NH-CH2 -CH(CH3 )-NH結構元素、NH-(CH2 )4 -NH結構元素、NH-(CH2 )6 -NH結構元素或(NH-(CH2 )8 -NH結構元素)，但該NH-CH2 -CH2 -NH結構元素就莫耳份額而言佔大部分。較佳聚伸乙亞胺含有就莫耳份額而言佔大部分之NH-CH2 -CH2 -NH結構元素，例如參考所有伸烷亞胺結構元素總計60 mol%或更多，更佳地總計至少70 mol%。在一特定實施例中，聚伸乙亞胺係指每分子帶有一個或零個伸烷亞胺結構元素之彼等聚伸烷基亞胺，該伸烷亞胺結構元素與NH-CH2 -CH2 -NH不同。The term "polyethyleneimine" in the context of the present invention refers not only to polyethyleneimine homopolymers, but also to polyethyleneimine containing the structural element NH- CH2- CH2 -NH together with other alkylenediamine structures. Elements (such as NH-CH 2 -CH 2 -CH 2 -NH structural element, NH-CH 2 -CH(CH 3 )-NH structural element, NH-(CH 2 ) 4 -NH structural element, NH-(CH 2 ) 6 -NH structural element or (NH-(CH 2 ) 8 -NH structural element), but the NH-CH 2 -CH 2 -NH structural element accounts for the majority in terms of molar fraction. Preferred polyethylene ethylene The amine contains a majority in molar fraction of the NH- CH2 - CH2 -NH structural elements, for example with reference to all alkylene imine structural elements totaling 60 mol% or more, preferably totaling at least 70 mol%. In a specific embodiment, polyethyleneimines refer to those polyalkyleneimines having one or zero alkyleneimine structural elements per molecule that are related to NH-CH 2 -CH 2 -NH is different.
本發明之上下文中之「聚伸乙亞胺」為分支鏈的，較佳為高度分支鏈的。分支程度可由熟習此項技術者根據實際應用來測定。"Polyethyleneimine" in the context of the present invention is a branched chain, preferably a highly branched chain. The degree of branching can be determined based on practical applications by those skilled in the art.
在一實施例中，其中環氧烷片段包含環氧乙烷片段及C3 -C6 -環氧烷片段；更佳地，環氧烷片段包含環氧乙烷片段及C3 -C4 -環氧烷片段；最佳地，環氧烷片段包含環氧乙烷片段及C3 -環氧烷片段。環氧乙烷片段與其餘環氧烷片段之莫耳比可在1:10至6:1 (例如1:10至5:1)之範圍內，較佳地在1:2至3:1之範圍內，更佳地在1:1至2:1之範圍內。在一最佳實施例中，環氧乙烷片段與其餘環氧烷片段之莫耳比為3:2。In one embodiment, the alkylene oxide segment includes an ethylene oxide segment and a C 3 -C 6 -alkylene oxide segment; more preferably, the alkylene oxide segment includes an ethylene oxide segment and a C 3 -C 4 - Alkylene oxide segments; optimally, the alkylene oxide segments include ethylene oxide segments and C 3 -alkylene oxide segments. The molar ratio of the ethylene oxide segments to the remaining alkylene oxide segments may range from 1:10 to 6:1 (for example, 1:10 to 5:1), preferably from 1:2 to 3:1 Within the range, preferably within the range of 1:1 to 2:1. In a preferred embodiment, the molar ratio of ethylene oxide segments to the remaining alkylene oxide segments is 3:2.
在本發明之一些較佳實施例中，本發明之烷氧基化聚伸乙亞胺中的環氧烷片段包含環氧乙烷片段及C3 -環氧烷片段，其中環氧烷片段之量係平均在35至70個環氧烷片段/氮原子之範圍內；較佳地，環氧烷片段之量係平均在35至60個環氧烷片段/氮原子之範圍內；更佳地，環氧烷片段之量平均在35至55個環氧烷片段/氮原子之範圍內，且環氧乙烷片段與其餘環氧烷片段之莫耳比係在1:10至6:1 (例如1:10至5:1)之範圍內，較佳地在1:2至3:1之範圍內，更佳地在1:1至2:1 (諸如3:2)之範圍內，且本發明之烷氧基化聚伸乙亞胺的重量平均分子量係在20,000至50,000 g/mol、較佳地25,000至45,000 g/mol、更佳地35,000至40,000 g/mol範圍內。In some preferred embodiments of the present invention, the alkylene oxide segments in the alkoxylated polyethyleneimine of the present invention include ethylene oxide segments and C 3 -alkylene oxide segments, wherein the alkylene oxide segments The amount is on average in the range of 35 to 70 alkylene oxide segments/nitrogen atom; preferably, the amount of alkylene oxide segments is on average in the range of 35 to 60 alkylene oxide segments/nitrogen atom; more preferably , the average amount of alkylene oxide fragments is in the range of 35 to 55 alkylene oxide fragments/nitrogen atom, and the molar ratio of ethylene oxide fragments to the remaining alkylene oxide fragments is between 1:10 and 6:1 ( For example, in the range of 1:10 to 5:1), preferably in the range of 1:2 to 3:1, more preferably in the range of 1:1 to 2:1 (such as 3:2), and The weight average molecular weight of the alkoxylated polyethyleneimine of the present invention is in the range of 20,000 to 50,000 g/mol, preferably 25,000 to 45,000 g/mol, and more preferably 35,000 to 40,000 g/mol.
在本發明之另一更佳實施例中，本發明之烷氧基化聚伸乙亞胺中之環氧烷片段包含環氧乙烷片段及C3 -環氧烷片段，環氧乙烷片段之量係在20至35個環氧乙烷片段/氮原子之範圍內，且C3 -環氧烷片段之量係在15至30個C3 -環氧烷片段/氮原子之範圍內；較佳地，環氧乙烷片段之量係在20至30個環氧乙烷片段/氮原子之範圍內，且C3 -環氧烷片段之量係在15至25個C3 -環氧烷片段/氮原子之範圍內。In another preferred embodiment of the present invention, the alkylene oxide segment in the alkoxylated polyethyleneimine of the present invention includes an ethylene oxide segment and a C 3 -alkylene oxide segment, and the ethylene oxide segment The amount is in the range of 20 to 35 ethylene oxide fragments/nitrogen atom, and the amount of C 3 -alkylene oxide fragments is in the range of 15 to 30 C 3 -alkylene oxide fragments/nitrogen atom; Preferably, the amount of ethylene oxide segments is in the range of 20 to 30 ethylene oxide segments/nitrogen atom, and the amount of C 3 -epoxy segments is in the range of 15 to 25 C 3 -epoxy segments. Within the range of alkane fragments/nitrogen atoms.
對用於獲得本發明之烷氧基化聚伸乙亞胺之方法不存在特定要求。本發明之烷氧基化聚伸乙亞胺可藉由經由此項技術中通常已知之方法，使聚伸乙亞胺烷氧基化來獲得。舉例而言，本發明之烷氧基化聚伸乙亞胺可藉由諸如US5445765中所描述之方法來獲得，其揭示內容以引用之方式併入。There are no specific requirements for the method used to obtain the alkoxylated polyethyleneimine of the invention. The alkoxylated polyethyleneimine of the present invention can be obtained by alkoxylating polyethyleneimine by a method generally known in the art. For example, the alkoxylated polyethyleneimine of the present invention can be obtained by methods such as those described in US Pat. No. 5,445,765, the disclosure of which is incorporated by reference.
上文所描述之本發明的烷氧基化聚伸乙亞胺(及其較佳實施例)經使用且應用於製備功能性纖維。上文所描述之本發明的烷氧基化聚伸乙亞胺(及其較佳實施例)可經使用且應用於功能性纖維之製備方法中，以便解決在將功能性添加劑併入至聚合物基質中時改良相容性及穩定性之需求。The alkoxylated polyethyleneimine of the present invention (and its preferred embodiments) described above is used and applied to prepare functional fibers. The alkoxylated polyethyleneimine of the present invention (and its preferred embodiments) described above can be used and applied in the preparation method of functional fibers to solve the problem of incorporating functional additives into the polymerization process. The need to improve compatibility and stability when in the physical matrix.
本發明之目的係提供一種具有較高功能益處之功能性纖維的製備方法，其視功能性添加劑之性質而用於各個使用領域。方法包含形成包含至少一種功能性添加劑、聚合物及烷氧基化聚伸乙亞胺之聚合物組合物的步驟。在一些實施例中，將至少一種功能性添加劑及烷氧基化聚伸乙亞胺添加至聚合物基質中以形成聚合物組合物。在一些實施例中，功能性添加劑及烷氧基化聚伸乙亞胺可分開地或同時添加至聚合物基質以形成聚合物組合物。在一些實施例中，功能性添加劑及烷氧基化聚伸乙亞胺在添加至聚合物基質中以形成聚合物組合物之前經摻合。在另一些實施例中，功能性添加劑及烷氧基化聚伸乙亞胺在併入至聚合物基質中以形成聚合物組合物之前經摻合且分散於溶劑中。任何習知攪拌技術可隨後用於均勻地形成聚合物組合物。The object of the present invention is to provide a method for preparing functional fibers with higher functional benefits, which can be used in various fields of use depending on the properties of the functional additives. The method includes the steps of forming a polymer composition comprising at least one functional additive, a polymer, and an alkoxylated polyethyleneimine. In some embodiments, at least one functional additive and alkoxylated polyethyleneimine are added to the polymer matrix to form a polymer composition. In some embodiments, functional additives and alkoxylated polyethyleneimine may be added to the polymer matrix separately or simultaneously to form the polymer composition. In some embodiments, the functional additive and the alkoxylated polyethyleneimine are blended before being added to the polymer matrix to form the polymer composition. In other embodiments, the functional additive and alkoxylated polyethyleneimine are blended and dispersed in a solvent prior to incorporation into the polymer matrix to form the polymer composition. Any conventional stirring technique can then be used to uniformly form the polymer composition.
根據本發明實施例中之任一者，烷氧基化聚伸乙亞胺以按聚合物之總量計0.01%至1.5重量%之量使用；功能性添加劑之分率係呈按聚合物之總量計1%至50重量%之量且功能性添加劑之平均直徑介於0.01至500微米。較佳地，烷氧基化聚伸乙亞胺以按聚合物之總量計0.01%至1%之量，更佳地0.05%至1重量%之量使用；功能性添加劑之分率係呈按聚合物之總量計5%至40重量%之量且功能性添加劑之平均直徑介於0.01至300微米。在一些較佳實施例中，烷氧基化聚伸乙亞胺與功能性添加劑之重量比係在1:100至1:10之範圍內，特定而言在1:70至1:30之範圍內，更特定而言在1:60至1:40之範圍內。According to any of the embodiments of the present invention, the alkoxylated polyethyleneimine is used in an amount of 0.01% to 1.5% by weight based on the total amount of the polymer; the proportion of the functional additive is based on the total amount of the polymer. The total amount is 1% to 50% by weight and the average diameter of the functional additives is between 0.01 and 500 microns. Preferably, the alkoxylated polyethyleneimine is used in an amount of 0.01% to 1%, more preferably 0.05% to 1% by weight based on the total amount of the polymer; the proportion of functional additives is The amount of the functional additive is 5% to 40% by weight based on the total amount of polymer and the average diameter of the functional additive is between 0.01 and 300 microns. In some preferred embodiments, the weight ratio of the alkoxylated polyethyleneimine to the functional additive is in the range of 1:100 to 1:10, specifically in the range of 1:70 to 1:30 Within, more specifically within the range of 1:60 to 1:40.
適合之功能性添加劑包括(但不限於)活性碳、碳黑、超級吸附劑、離子交換樹脂、相變材料、金屬氧化物、阻燃劑、研磨劑、沸石、片狀矽酸鹽(諸如膨潤土)或經修飾之片狀矽酸鹽、裝飾材料、石蠟、香料成品(fragrance finish)、蠟、油、奈米銀(nanosilver)、染料、多色劑及/或熱變色劑(thermos-chromic agent)、活性醫藥成分或抗菌劑、殺蟲劑或另外活性成分。Suitable functional additives include, but are not limited to, activated carbon, carbon black, super adsorbents, ion exchange resins, phase change materials, metal oxides, flame retardants, abrasives, zeolites, sheet silicates such as bentonite ) or modified flake silicate, decorative materials, paraffin, fragrance finish, wax, oil, nanosilver, dye, polychromic agent and/or thermos-chromic agent ), active pharmaceutical ingredients or antibacterial agents, pesticides or other active ingredients.
在一些實施例中，為展現其他功能性效果，在本發明之聚合物基質中混配且添加之功能性添加劑為微膠囊，且功能材料囊封於微膠囊中，其中微膠囊之材料可為甲殼素、聚胺甲酸酯彈性體或熱塑彈性體。微膠囊內部之材料稱為核心材料，而壁稱作殼層。用於生產功能性纖維之微膠囊具有幾微米與幾公釐之間的直徑。可藉由將核心材料微囊封而賦予纖維許多特定及功能特性，此核心材料可為對纖維執行特定功能之任何物質。In some embodiments, in order to exhibit other functional effects, the functional additives mixed and added in the polymer matrix of the present invention are microcapsules, and the functional materials are encapsulated in the microcapsules, where the material of the microcapsules can be Chitin, polyurethane elastomer or thermoplastic elastomer. The material inside the microcapsule is called the core material, and the wall is called the shell. Microcapsules used to produce functional fibers have diameters between a few microns and a few millimeters. Fibers can be given many specific and functional properties by microencapsulating a core material, which can be any substance that performs a specific function on the fiber.
出於本發明之目的，聚合物組合物可經歷用於製備包含聚合物基質及功能性添加劑之功能性纖維的紡絲製程。可經由熟習此項技術者已知之任何習知紡絲方法生產纖維。適合之紡絲製程包括諸如涉及紡絲溶液之彼等紡絲方法，諸如濕法紡絲及乾法紡絲、熔融紡絲及靜電紡絲製程。For the purposes of the present invention, the polymer composition may be subjected to a spinning process for producing functional fibers comprising a polymer matrix and functional additives. Fibers may be produced by any conventional spinning method known to those skilled in the art. Suitable spinning processes include such spinning methods as those involving spinning solutions, such as wet and dry spinning, melt spinning and electrospinning processes.
在典型濕法紡絲製程中，紡絲溶液或原液由聚合物或聚合物前驅體組合物形成。溶液含有溶劑中之溶解聚合物，該溶液可藉由將預成型聚合物與溶劑合併來製備或可藉由單體在溶液中之原位聚合反應來形成。濕法紡絲溶液與溶解聚合物經由紡絲頭泵送至此處被稱作纖維形成浴之凝固浴中，其中凝固纖維且移除濕法紡絲溶液溶劑，長絲或纖維在溶液離開紡絲頭且進入浴液時由溶解聚合物形成。在浴液之出口處，以所需特克斯(tex)或丹尼爾(denier)之集束形式收集纖維。所收集之纖維隨後加工、捲曲且乾燥，乾燥可包含使纖維結構收縮及鬆弛。最後，纖維經歷牽引(tow)及切斷操作。在乾法紡絲操作中，除了未形成纖維且溶劑未藉由凝固浴移除外，採取與濕法紡絲中相同之步驟，但形成纖維且溶劑藉由乾燥方式，諸如藉由在空氣流或惰性氣體中蒸發來移除。In a typical wet spinning process, a spinning solution or dope is formed from a polymer or polymer precursor composition. The solution contains dissolved polymer in a solvent and may be prepared by combining a preformed polymer with a solvent or may be formed by in situ polymerization of monomers in solution. The wet spinning solution and dissolved polymer are pumped through the spin head into a coagulation bath, referred to here as the fiber forming bath, where the fibers are coagulated and the wet spinning solution solvent is removed, and the filaments or fibers leave the spinning solution The head is formed from dissolved polymer when entering the bath. At the outlet of the bath, the fibers are collected in bundles of the required tex or denier. The collected fibers are then processed, crimped and dried, which may include shrinking and relaxing the fiber structure. Finally, the fiber undergoes towing and cutting operations. In a dry spinning operation, the same steps are taken as in wet spinning, except that fibers are not formed and the solvent is not removed by a coagulation bath, but the fibers are formed and the solvent is dried, such as by passing it through a stream of air. Or removed by evaporation in an inert gas.
根據本發明實施例中之任一者，功能性添加劑及烷氧基化聚伸乙亞胺可與聚合物基質混合以形成聚合物組合物。在一些實施例中，功能性添加劑及烷氧基化聚伸乙亞胺在將聚合物溶解於溶劑中之前與聚合物基質混合。在一些其他實施例中，可將功能性添加劑及烷氧基化聚伸乙亞胺添加至含有聚合物之紡絲溶液中以形成聚合物組合物。在一些其他實施例中，可將功能性添加劑及烷氧基化聚伸乙亞胺分開地或同時添加至含有聚合物之紡絲溶液中。在一些實施例中，功能性添加劑及烷氧基化聚伸乙亞胺在併入至含有聚合物之紡絲溶液中以形成聚合物組合物之前經摻合。在另外一些實施例中，功能性添加劑及烷氧基化聚伸乙亞胺在併入至含有聚合物之紡絲溶液中以形成聚合物組合物之前經摻合且分散於溶劑中。According to any of the embodiments of the present invention, functional additives and alkoxylated polyethyleneimine may be mixed with the polymer matrix to form a polymer composition. In some embodiments, functional additives and alkoxylated polyethyleneimine are mixed with the polymer matrix prior to dissolving the polymer in the solvent. In some other embodiments, functional additives and alkoxylated polyethyleneimine may be added to the polymer-containing spinning solution to form a polymer composition. In some other embodiments, the functional additive and the alkoxylated polyethyleneimine may be added to the polymer-containing spinning solution separately or simultaneously. In some embodiments, the functional additive and the alkoxylated polyethyleneimine are blended before being incorporated into the spinning solution containing the polymer to form the polymer composition. In other embodiments, the functional additive and the alkoxylated polyethyleneimine are blended and dispersed in the solvent prior to being incorporated into the spinning solution containing the polymer to form the polymer composition.
任何習知攪拌技術可隨後用於均勻地形成聚合物組合物。隨著烷氧基化聚伸乙亞胺之添加，功能性添加劑可良好地分散於用於形成纖維之整個含有聚合物之紡絲溶液中。成分分散意謂功能性添加劑實質上均勻地分佈於整個溶液中。較佳地，功能性添加劑並不自溶液之底部掉落或沈降於溶液之底部。Any conventional stirring technique can then be used to uniformly form the polymer composition. With the addition of alkoxylated polyethyleneimine, the functional additive is well dispersed throughout the polymer-containing spinning solution used to form the fibers. Ingredient dispersion means that the functional additive is distributed substantially uniformly throughout the solution. Preferably, the functional additive does not fall from the bottom of the solution or settle at the bottom of the solution.
關於將功能性添加劑及烷氧基化聚伸乙亞胺引入至含有聚合物之紡絲溶液，可使用任何方式之引入。功能性添加劑及烷氧基化聚伸乙亞胺以無水形式直接地添加至紡絲溶液中或作為分散液添加。另外，其可在添加至聚合物及紡絲溶液之溶劑中之前首先分散於溶劑中以形成分散液。若其以分散液形式供應，則分散液中所使用之溶劑較佳地能夠形成分散液且使功能性添加劑維持高度分散之狀態。分散液中所使用之溶劑與溶解聚合物之濕法紡絲溶液中所使用的溶劑為較佳相容且更佳可混溶的。含有功能性添加劑及烷氧基化聚伸乙亞胺之分散液可進一步包含分散劑及/或界面活性劑。Regarding the introduction of functional additives and alkoxylated polyethyleneimine into the polymer-containing spinning solution, any method of introduction may be used. Functional additives and alkoxylated polyethyleneimine are added directly to the spinning solution in anhydrous form or as a dispersion. Alternatively, it may be first dispersed in the solvent to form a dispersion before being added to the polymer and the solvent of the spinning solution. If it is supplied in the form of a dispersion, the solvent used in the dispersion is preferably capable of forming a dispersion and maintaining the functional additive in a highly dispersed state. The solvent used in the dispersion is preferably compatible and preferably miscible with the solvent used in the wet spinning solution in which the polymer is dissolved. The dispersion containing functional additives and alkoxylated polyethyleneimine may further contain a dispersant and/or surfactant.
當形成紡絲溶液時，可按任何次序添加各種組分。溶液應該使聚合物維持溶解狀態且可包括習知紡絲溶液溶劑。適合的溶劑包括水性溶劑、含水離子液體及有機溶劑，諸如二甲基甲醯胺、二甲基乙醯胺、二甲亞碸(DMSO)、碳酸伸乙酯、具有約45重量%至約55重量%之NaSCN濃度的硫代氰酸鈉(NaSCN)水溶液、具有約65%至約75重量%之較佳HNO3 濃度的硝酸(HNO3 )水溶液、具有約55重量%至約65重量%之ZnCl2 濃度的氯化鋅(ZnCl2 )水溶液、N-甲基嗎啉N-氧化物或N-甲基嗎啉N-氧化物單水合物；離子液體，諸如乙酸1-乙基-3-甲基咪唑鎓、氯化3-乙基-1-甲基咪唑鎓或氯化3-丁基-1-甲基咪唑鎓、二甲基甲醯胺、二甲基乙醯胺或與氯化鋰混合之二甲亞碸或NaOH-硫脲-水或視情況其混合物。當有機溶劑用於溶解聚合物時，相同溶劑較佳地用於形成含有功能性添加劑及烷氧基化聚伸乙亞胺之分散液。當水溶液用於溶解聚合物時，稀溶液或水較佳地用於形成含有功能性添加劑及烷氧基化聚伸乙亞胺之分散液。When forming the spinning solution, the various components can be added in any order. The solution should maintain the polymer in solution and may include conventional spinning solution solvents. Suitable solvents include aqueous solvents, aqueous ionic liquids, and organic solvents, such as dimethylformamide, dimethylacetamide, dimethylsulfoxide (DMSO), ethylene carbonate, having from about 45% to about 55% by weight An aqueous solution of sodium thiocyanate (NaSCN) with a NaSCN concentration of about 65% to about 75% by weight, an aqueous nitric acid (HNO 3 ) solution with a preferred HNO 3 concentration of about 65% to about 75% by weight, an aqueous solution of sodium thiocyanate (NaSCN) having a preferred HNO 3 concentration of about 55% to about 65% by weight. Aqueous zinc chloride (ZnCl 2 ) solution, N-methylmorpholine N-oxide or N-methylmorpholine N-oxide monohydrate at ZnCl 2 concentration; ionic liquids such as 1-ethyl-3-acetate Methylimidazolium, 3-ethyl-1-methylimidazolium chloride or 3-butyl-1-methylimidazolium chloride, dimethylformamide, dimethylacetamide or with chloride Lithium mixed with dimethyl sulfoxide or NaOH-thiourea-water or mixtures thereof as appropriate. When an organic solvent is used to dissolve the polymer, the same solvent is preferably used to form the dispersion containing the functional additive and the alkoxylated polyethyleneimine. When an aqueous solution is used to dissolve the polymer, a dilute solution or water is preferably used to form a dispersion containing the functional additive and the alkoxylated polyethyleneimine.
用於製備紡絲溶液之適合的聚合物之實例包括天然聚合物，例如多糖及多糖衍生物，尤其纖維素、醋酸纖維素、蛋白質及蛋白質衍生物；溶劑可成形之合成聚合物，諸如聚乳酸、聚丙烯腈、聚乙烯醇、聚氯乙烯、聚氧化乙烯、聚醯胺、聚醚碸、聚碸甲芳綸(polysulfone metha-aramid)或其共聚物。針對聚合物中之每一者，紡絲溶液中所存在之溶劑為習知的且為熟習此項技術者所已知。Examples of suitable polymers for preparing spinning solutions include natural polymers, such as polysaccharides and polysaccharide derivatives, especially cellulose, cellulose acetate, proteins and protein derivatives; solvent-formable synthetic polymers, such as polylactic acid. , polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyethylene oxide, polyamide, polyethersulfone, polysulfone metha-aramid or its copolymers. For each of the polymers, the solvents present in the spinning solution are conventional and known to those skilled in the art.
在本發明之一較佳實施例中，用於製備功能性纖維之方法包括以下步驟：使用纖維素漿作為原料；生產步驟包括浸漬、擠壓、壓碎、老化、硫化、過濾、熟化、紡絲、流出(sourcing)及乾燥；該方法亦包括功能性添加劑及烷氧基化聚伸乙亞胺之添加步驟，該添加步驟為將功能性添加劑及烷氧基化聚伸乙亞胺添加至硫化步驟中所獲得之黃原酸纖維素中，在攪拌之後，混合物完全溶解以形成聚合物組合物從而產生黏膠紡絲溶液。In a preferred embodiment of the present invention, the method for preparing functional fibers includes the following steps: using cellulose pulp as raw material; the production steps include impregnation, extrusion, crushing, aging, vulcanization, filtration, aging, spinning Silk, sourcing and drying; the method also includes the step of adding functional additives and alkoxylated polyethyleneimine to In the cellulose xanthate obtained in the vulcanization step, after stirring, the mixture is completely dissolved to form a polymer composition to produce a viscose spinning solution.
根據本發明實施例中之任一者，紡絲溶液中聚合物之濃度在按溶液之重量計約5重量%至約40重量%之範圍內，較佳在按溶液之重量計約5重量%至約20重量%之範圍內。According to any of the embodiments of the present invention, the concentration of the polymer in the spinning solution ranges from about 5% to about 40% by weight of the solution, preferably about 5% by weight of the solution. to about 20% by weight.
當所使用之紡絲方法為濕法紡絲時，纖維形成浴(亦可被稱作凝固浴)可包含任何習知之凝固浴介質。較佳地，纖維形成浴包含水-溶劑混合物或溶液，其在溶液經由紡絲頭泵送時有助於自紡絲溶液形成纖維長絲。熟習此項技術者將意識到待採納之適合技術及條件，諸如操作溫度、紡絲溶液之黏度視包括紡絲溶液之聚合組分及溶劑的許多因素而定。When the spinning method used is wet spinning, the fiber forming bath (which may also be called a coagulation bath) may contain any conventional coagulation bath medium. Preferably, the fiber forming bath contains a water-solvent mixture or solution which facilitates the formation of fiber filaments from the spinning solution as the solution is pumped through the spinning head. Those skilled in the art will appreciate that the appropriate technique and conditions to be employed, such as operating temperature, viscosity of the spinning solution, depend on many factors including the polymeric components of the spinning solution and the solvent.
根據本發明之一些實施例，功能性纖維可經由熔融紡絲製程來生產，該熔融紡絲製程藉由以下來進行：加熱及熔融聚合物，且將熔融聚合物自紡絲孔擠出至空氣中，同時在空氣中冷卻，以恆定速度捲繞並且在熔融材料薄化時固化，由此形成纖維，且接著執行熱拉伸以增強纖維之機械特性。在熔融紡絲製程中，在高於其熔點之溫度下自聚合製程獲得之可紡聚合物自紡絲板之孔擠出。According to some embodiments of the present invention, functional fibers can be produced through a melt spinning process by heating and melting a polymer, and extruding the molten polymer from the spinning hole into the air. , while cooling in air, winding at a constant speed and solidifying as the molten material thins, thereby forming fibers, and then performing thermal drawing to enhance the mechanical properties of the fibers. In the melt spinning process, the spinnable polymer obtained from the polymerization process at a temperature above its melting point is extruded from the holes of the spinning plate.
用於熔融紡絲製程之適合的聚合物為熟習此項技術者所已知。聚合物可選自此項技術中已知之能夠形成纖維之任何類型的聚合物，包括聚烯烴、聚乙烯、聚乙烯醇、聚酯、聚醯胺、含有作為共聚物嵌段之前述聚合物中之任一者的共聚物及其組合。此操作中之特定聚烯烴包括聚丙烯；聚乙烯；聚丁烯；及聚異丁烯；聚醯胺，諸如NYLON 6及NYLON 6.6；聚丙烯酸酯、聚苯乙烯、聚胺甲酸酯；縮醛樹脂；聚伸乙基乙烯醇(polyethylene vinyl alcohol)；聚酯包括聚對苯二甲酸伸乙酯、聚萘二甲酸伸乙酯、聚對苯二甲酸伸丙酯、聚(1,4-環己烯二亞甲基對苯二甲酸酯)、聚碳酸酯且脂族聚酯包括聚乳酸、聚苯硫醚、熱塑彈性體、聚丙烯腈、纖維素及纖維素衍生物、芳族聚醯胺、縮醛、氟聚合物、共聚物及其三聚物以及其混合物或摻合物。Suitable polymers for melt spinning processes are known to those skilled in the art. The polymer may be selected from any type of polymer known in the art capable of forming fibers, including polyolefins, polyethylene, polyvinyl alcohol, polyesters, polyamides, any of the foregoing polymers containing as copolymer blocks Copolymers of any of them and combinations thereof. Specific polyolefins in this operation include polypropylene; polyethylene; polybutylene; and polyisobutylene; polyamides such as NYLON 6 and NYLON 6.6; polyacrylates, polystyrenes, polyurethanes; acetal resins ; Polyethylene vinyl alcohol; Polyester includes polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, poly(1,4-cyclohexane) (ethylene dimethylene terephthalate), polycarbonate and aliphatic polyesters including polylactic acid, polyphenylene sulfide, thermoplastic elastomers, polyacrylonitrile, cellulose and cellulose derivatives, aromatic polyesters Amides, acetals, fluoropolymers, copolymers and terpolymers thereof and mixtures or blends thereof.
在本發明之一些實施例中，可將功能性添加劑及烷氧基化聚伸乙亞胺直接地添加至熔融聚合物。習知攪拌可隨後用於使功能性添加劑均勻地分散於整個聚合物熔融物中。在一些實施例中，功能性添加劑及烷氧基化聚伸乙亞胺可在引入至熔融聚合物中之前摻合。在另外一些實施例中，功能性添加劑及烷氧基化聚伸乙亞胺可在引入至熔融聚合物中以形成聚合物組合物之前經摻合且分散於溶劑中。In some embodiments of the present invention, functional additives and alkoxylated polyethyleneimine may be added directly to the molten polymer. Conventional stirring can then be used to evenly disperse the functional additive throughout the polymer melt. In some embodiments, the functional additive and the alkoxylated polyethyleneimine may be blended prior to introduction into the molten polymer. In other embodiments, the functional additive and the alkoxylated polyethyleneimine may be blended and dispersed in the solvent prior to introduction into the molten polymer to form the polymer composition.
烷氧基化聚伸乙亞胺之量介於按熔融聚合物之總重量計0.01%至1重量%，較佳地按熔融聚合物之總重量計0.01%至0.8重量%，功能性添加劑以範圍介於按熔融聚合物之總重量計1%至50重量%、較佳地按熔融聚合物之總量計5%至40重量%的量使用；且功能性添加劑之平均直徑介於0.01至500微米，較佳0.01至300微米。The amount of alkoxylated polyethyleneimine ranges from 0.01% to 1% by weight based on the total weight of the molten polymer, preferably 0.01% to 0.8% by weight based on the total weight of the molten polymer, and the functional additives are The range is 1% to 50% by weight based on the total weight of the molten polymer, preferably 5% to 40% by weight based on the total weight of the molten polymer; and the average diameter of the functional additive is between 0.01 and 0.01%. 500 microns, preferably 0.01 to 300 microns.
在一些實施例中，功能性添加劑及烷氧基化聚伸乙亞胺可在不存在溶劑之情況下摻合，特定而言，可在併入至聚合物熔融物中的步驟之前，在紡絲之前或在其他處理步驟期間在所需溫度下摻合以獲得均勻摻合物。將功能性添加劑混合至聚合物熔融物中且均勻地分散於整個聚合物熔融物中。在一些實施例中，功能性添加劑及烷氧基化聚伸乙亞胺在使用已知技術擠壓成可擠出顆粒之前與聚合物熔融物混合或摻合，其中功能性添加劑均勻地分散於整個聚合物基質中。在一個實施例中，生產功能性纖維之方法包含：製備作為基質之聚合物晶片(呈按纖維之總重量計10%至50重量%的量)以及功能性添加劑(呈按纖維之總重量計1%至50重量%的量)及烷氧基化聚伸乙亞胺(呈按纖維之總重量計0.01%至1重量%的量)之聚合物組合物，且由雙螺桿擠壓機混配以形成功能性母膠，接著將功能性母膠與額外聚合物基質組合，且將功能性母膠及額外聚合物熔融並且混合以形成複合材料，且接著使複合材料經歷紡絲、冷卻、熱拉伸及熱定型以形成功能性纖維。紡絲溫度、熱拉伸溫度及熱定型溫度為已知的或可由熟習此項技術者視聚合物類型及生產製程而進行調整。In some embodiments, the functional additives and the alkoxylated polyethyleneimine may be blended in the absence of a solvent, and specifically may be spun in the step prior to the step of incorporation into the polymer melt. The filaments are blended at the desired temperature before or during other processing steps to obtain a homogeneous blend. The functional additives are mixed into the polymer melt and evenly dispersed throughout the polymer melt. In some embodiments, the functional additives and the alkoxylated polyethyleneimine are mixed or blended with the polymer melt prior to extrusion into extrudable particles using known techniques, wherein the functional additives are uniformly dispersed in throughout the polymer matrix. In one embodiment, a method of producing functional fibers includes preparing polymer wafers as a matrix (in an amount of 10% to 50% by weight based on the total weight of the fibers) and functional additives (in an amount based on the total weight of the fibers) A polymer composition of 1% to 50% by weight) and alkoxylated polyethyleneimine (in an amount of 0.01% to 1% by weight based on the total weight of the fiber) and mixed by a twin-screw extruder Formulated to form a functional masterbatch, the functional masterbatch is then combined with an additional polymer matrix, and the functional masterbatch and the additional polymer are melted and mixed to form a composite material, and the composite material is then subjected to spinning, cooling, Heat stretching and heat setting to form functional fibers. The spinning temperature, heat drawing temperature and heat setting temperature are known or can be adjusted by those skilled in the art depending on the polymer type and production process.
在不受任何特定理論約束之情況下，咸信烷氧基化聚伸乙亞胺(對不同表面具有良好親和力)可用作極佳表面改質劑以改良在製備功能性纖維期間混合之聚合物基質與功能材料之間的界面相容性。Without being bound by any particular theory, it is believed that alkoxylated polyethyleneimine (which has good affinity for different surfaces) can be used as an excellent surface modifier to improve the polymerization mixed during the preparation of functional fibers. Interfacial compatibility between physical matrix and functional materials.
本發明之功能性纖維適用於多種物品，包括(但不限於)具有較高功能益處之服裝紡織物及工業紡織物，其視功能性添加劑之類型而用於各個應用領域，例如針對衛生品應用，作為傷口敷料、作為活性成分之載體材料或作為複合物中之載體材料、作為建築及運輸材料、作為裝飾材料或作為濾材，例如用於過濾及空氣與水成分(諸如磷酸鹽、硝酸鹽及銨-氮化合物)之結合。The functional fibers of the present invention are suitable for use in a variety of articles, including (but not limited to) clothing textiles and industrial textiles with higher functional benefits. They are used in various application fields depending on the type of functional additives, such as for sanitary products applications. , as wound dressing, as carrier material for active ingredients or as carrier material in composites, as construction and transport material, as decorative material or as filter material, e.g. for filtration and air and water components such as phosphates, nitrates and Ammonium-nitrogen compound) combination.
本發明進一步係關於一種如上述態樣中所描述之烷氧基化聚伸乙亞胺在製備功能性纖維之製程中的用途，其中該功能性纖維包含聚合物基質及至少一種功能性添加劑。The present invention further relates to the use of an alkoxylated polyethyleneimine as described in the above aspects in a process for preparing functional fibers, wherein the functional fibers comprise a polymer matrix and at least one functional additive.
本揭示內容進一步描述於以下實例中。實例僅為說明性的且不以任何方式限制如所描述及所主張之揭示內容之範疇。The present disclosure is further described in the following examples. The examples are illustrative only and do not limit in any way the scope of the disclosure as described and claimed.
實例Example 材料：Material:
烷氧基化聚伸乙亞胺(PEI)：烷氧基化PEI包含含有環氧乙烷片段及C3 -環氧烷片段之環氧烷片段，其中環氧烷片段之量係平均在35至55個環氧烷片段/氮原子之範圍內，且環氧乙烷片段與其餘環氧烷片段之莫耳比為3:2，且烷氧基化PEI之重量平均分子量係在35,000至40,000 g/mol範圍內。Alkoxylated polyethyleneimine (PEI): Alkoxylated PEI contains an alkylene oxide segment containing an ethylene oxide segment and a C 3 -alkylene oxide segment, where the amount of the alkylene oxide segment is on average 35 to 55 alkylene oxide fragments/nitrogen atom, and the molar ratio of ethylene oxide fragments to the remaining alkylene oxide fragments is 3:2, and the weight average molecular weight of the alkoxylated PEI is between 35,000 and 40,000 within the range of g/mol.
SiO2 ：由Sigma-Aldrich出售，平均直徑為100 nm。SiO 2 : Sold by Sigma-Aldrich, average diameter 100 nm.
PU微膠囊：聚胺甲酸酯芳香微膠囊，平均直徑為50 µm。PU microcapsules: polyurethane aromatic microcapsules with an average diameter of 50 µm.
界面活性劑：由Sigma-Aldrich出售之十二烷基硫酸鈉Surfactant: Sodium lauryl sulfate sold by Sigma-Aldrich
實例 1 纖維素漿(由棉絨製得)用作原料。黃原酸纖維素藉由使用任何習知生產製程獲得。將SiO2 粒子(1 kg)及烷氧基化PEI (20 g)添加至旋轉滾筒混合器且在80℃之溫度下攪拌1小時以獲得摻合物。將SiO2 粒子及烷氧基化聚伸乙亞胺之摻合物、黃原酸纖維素、氫氧化鈉及水均勻地混合以獲得經摻合之黏膠液體，隨後將該黏膠液體溶解於水中，過濾且去氣以獲得經摻合之紡絲原液。所獲得之紡絲原液含有5 wt%之α纖維素、2 wt%之SiO2 粒子、10 wt%之氫氧化鈉及水。 Example 1 Cellulose pulp (made from cotton linters) was used as raw material. Cellulose xanthate is obtained by using any conventional production process. SiO 2 particles (1 kg) and alkoxylated PEI (20 g) were added to a rotating drum mixer and stirred at a temperature of 80 °C for 1 hour to obtain a blend. Mix SiO 2 particles and a blend of alkoxylated polyethyleneimine, cellulose xanthate, sodium hydroxide and water uniformly to obtain a blended viscose liquid, and then dissolve the viscose liquid in water, filtered and degassed to obtain a blended spinning dope. The obtained spinning solution contained 5 wt% α-cellulose, 2 wt% SiO 2 particles, 10 wt% sodium hydroxide and water.
藉由在具有硫酸含量為120 g/L、硫酸鋅含量為11 g/L、硫酸鈉含量為330 g/L、溫度為58℃之凝固酸浴中紡絲且適當地拉伸來產生功能性纖維。所得功能性纖維在脫硫精製及乾燥之後獲得。Functionality is produced by spinning in a coagulated acid bath with a sulfuric acid content of 120 g/L, a zinc sulfate content of 11 g/L, a sodium sulfate content of 330 g/L, and a temperature of 58°C and stretching appropriately. fiber. The obtained functional fiber is obtained after desulfurization, refining and drying.
比較實例 A 功能性纖維藉由與實例1相同之程序來製備，不同之處在於不存在烷氧基化聚伸乙亞胺。 Comparative Example A functional fiber was prepared by the same procedure as Example 1 except that there was no alkoxylated polyethyleneimine.
比較實例 B 功能性纖維藉由與實例1相同之程序來製備，不同之處在於界面活性劑與SiO2 粒子而非本發明之烷氧基化聚伸乙亞胺一起用於製造摻合物。 Comparative Example B Functional fibers were prepared by the same procedure as Example 1, except that the surfactant was used with SiO2 particles instead of the alkoxylated polyethyleneimine of the present invention to make the blend.
實例 2 纖維素漿(由棉絨製得)用作原料。黃原酸纖維素藉由使用任何習知生產製程獲得。PU微膠囊(10kg，10 wt%)及烷氧基化PET (25 g)藉由在室溫下機械攪拌1小時而混合以獲得漿料。將包含PU微膠囊及烷氧基化聚伸乙亞胺之漿料、黃原酸纖維素、氫氧化鈉及水均勻地混合以獲得經摻合之黏膠液體，隨後將該黏膠液體溶解於水中，過濾且去氣以獲得經摻合之紡絲原液。所獲得之紡絲原液含有6 wt%之α纖維素、1 wt%之PU微膠囊、10 wt%之氫氧化鈉及水。 Example 2 Cellulose pulp (made from cotton linters) was used as raw material. Cellulose xanthate is obtained by using any conventional production process. PU microcapsules (10 kg, 10 wt%) and alkoxylated PET (25 g) were mixed by mechanical stirring at room temperature for 1 hour to obtain a slurry. The slurry containing PU microcapsules and alkoxylated polyethyleneimine, cellulose xanthate, sodium hydroxide and water are uniformly mixed to obtain a blended viscose liquid, and then the viscose liquid is dissolved in water, filtered and degassed to obtain a blended spinning dope. The obtained spinning solution contained 6 wt% α-cellulose, 1 wt% PU microcapsules, 10 wt% sodium hydroxide and water.
藉由在具有硫酸含量為120 g/L、硫酸鋅含量為11 g/L、硫酸鈉含量為330 g/L、溫度為58℃之凝固酸浴中紡絲且適當地拉伸來產生功能性纖維。所得功能性纖維在脫硫精製及乾燥之後獲得。Functionality is produced by spinning in a coagulated acid bath with a sulfuric acid content of 120 g/L, a zinc sulfate content of 11 g/L, a sodium sulfate content of 330 g/L, and a temperature of 58°C and stretching appropriately. fiber. The obtained functional fiber is obtained after desulfurization, refining and drying.
比較實例 C 功能性纖維藉由與實例2相同之程序來製備，不同之處在於不存在烷氧基化聚伸乙亞胺。 Comparative Example C functional fiber was prepared by the same procedure as Example 2 except that alkoxylated polyethyleneimine was not present.
比較實例 D 功能性纖維藉由與實例2相同之程序來製備，不同之處在於界面活性劑與PU微膠囊而非本發明之烷氧基化聚伸乙亞胺一起用於製造摻合物。 Comparative Example D functional fiber was prepared by the same procedure as Example 2, except that the surfactant was used with PU microcapsules instead of the alkoxylated polyethyleneimine of the present invention to make the blend.
量測纖維中功能性添加劑之含量
將所獲得之功能性纖維在100℃下溶解於含有50 wt%之N-甲基嗎啉-N-氧化物(NMMO)的水溶液中(水溶液與纖維之重量比為100:1)。將不可溶功能性材料過濾，用去離子水洗滌且在150℃下乾燥。稱取纖維中不可溶功能性添加劑之量。利用重複量測值計算平均值。纖維中功能性添加劑之含量結果展示於表1中。
表1
意外地發現，最終功能性纖維中功能性添加劑之濃度隨著烷氧基化聚伸乙亞胺之存在而增加，從而改良功能材料-聚合物基質之界面相容性。Unexpectedly, it was found that the concentration of functional additives in the final functional fiber increased with the presence of alkoxylated polyethyleneimine, thereby improving the interfacial compatibility of the functional material-polymer matrix.
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| JPS63303108A (en) * | 1987-06-03 | 1988-12-09 | Nippon Shokubai Kagaku Kogyo Co Ltd | Colorant for spun-dyed viscose rayon |
| CN107208361A (en) * | 2015-02-06 | 2017-09-26 | 巴斯夫欧洲公司 | Alkoxylate polyethyleneimine hydrophilic modifying fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113166406B (en) | 2023-11-07 |
| WO2020104303A1 (en) | 2020-05-28 |
| CN113166406A (en) | 2021-07-23 |
| TW202033613A (en) | 2020-09-16 |
| AU2019382753A1 (en) | 2021-05-27 |
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