CN103607913A - Cellulose esters having mixed-phase titanium dioxide particles for improved degradation - Google Patents
Cellulose esters having mixed-phase titanium dioxide particles for improved degradation Download PDFInfo
- Publication number
- CN103607913A CN103607913A CN201280030468.4A CN201280030468A CN103607913A CN 103607913 A CN103607913 A CN 103607913A CN 201280030468 A CN201280030468 A CN 201280030468A CN 103607913 A CN103607913 A CN 103607913A
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- Prior art keywords
- cellulose
- goods according
- goods
- mixing phase
- fiber
- Prior art date
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Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 239000002245 particle Substances 0.000 title claims abstract description 83
- 229920002678 cellulose Polymers 0.000 title claims abstract description 76
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 33
- 230000015556 catabolic process Effects 0.000 title description 12
- 238000006731 degradation reaction Methods 0.000 title description 12
- 239000000835 fiber Substances 0.000 claims abstract description 114
- 239000004014 plasticizer Substances 0.000 claims abstract description 35
- 150000002148 esters Chemical class 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims description 50
- 229920002301 cellulose acetate Polymers 0.000 claims description 42
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 235000019504 cigarettes Nutrition 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 11
- 239000001087 glyceryl triacetate Substances 0.000 claims description 9
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 9
- 229960002622 triacetin Drugs 0.000 claims description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 claims description 4
- 229920008347 Cellulose acetate propionate Polymers 0.000 claims description 4
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001727 cellulose butyrate Polymers 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000001069 triethyl citrate Substances 0.000 claims description 4
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000013769 triethyl citrate Nutrition 0.000 claims description 4
- YZWRNSARCRTXDS-UHFFFAOYSA-N tripropionin Chemical compound CCC(=O)OCC(OC(=O)CC)COC(=O)CC YZWRNSARCRTXDS-UHFFFAOYSA-N 0.000 claims description 4
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 claims description 3
- 229920006218 cellulose propionate Polymers 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 claims description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 38
- 229910010413 TiO 2 Inorganic materials 0.000 description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000013078 crystal Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 241000208125 Nicotiana Species 0.000 description 5
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000006065 biodegradation reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- -1 phosphorus compound Chemical class 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007596 consolidation process Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000002424 x-ray crystallography Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 2
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 2
- 238000001941 electron spectroscopy Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- OLGONLPBKFPQNS-UHFFFAOYSA-M sodium 2-(4-phenylphenyl)butanoate Chemical compound [Na+].CCC(C([O-])=O)c1ccc(cc1)-c1ccccc1 OLGONLPBKFPQNS-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- AVMNFQHJOOYCAP-UHFFFAOYSA-N acetic acid;propanoic acid Chemical compound CC(O)=O.CCC(O)=O AVMNFQHJOOYCAP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VLYWMPOKSSWJAL-UHFFFAOYSA-N sulfamethoxypyridazine Chemical compound N1=NC(OC)=CC=C1NS(=O)(=O)C1=CC=C(N)C=C1 VLYWMPOKSSWJAL-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 235000019505 tobacco product Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/067—Use of materials for tobacco smoke filters characterised by functional properties
- A24D3/068—Biodegradable or disintegrable
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
- A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
Abstract
Degradable cellulose esters are disclosed that have incorporated therein or thereon mixed-phase titanium dioxide particles. The esters may be in the form of filters prepared by applying a plasticizer, having the mixed-phase titanium dioxide particles dispersed therein, to cellulose ester fibers to obtain plasticized cellulose ester fibers; and thereafter forming the plasticized cellulose ester fibers into a filter. Alternatively, the particles may be added to the dope from which the fibers are spun, or blended with a cellulose ester intended for molded articles.
Description
Technical field
The present invention relates to cellulose ester, particularly, relate to the cellulose ester that shows improved degraded.
Background technology
Typical cigarette filter is made by the continuous filament yarn tow band of cellulose acetate base fiber, is called as cellulose acetate tow, or is called simply acetate tow.In various patents, described use acetate tow and manufactured filter tip, and tow can be plasticized.Referring to, for example, US Patent No. 2,794,239.
Except continuous fiber, can use short fiber, it is shorter, and it can promote filter-tip final degraded.Referring to, for example, US Patent No. 3,658,626, it discloses directly and has produced short fiber smoke filter element and its analog by continuous fiber tow.These short fibers also can be plasticized.
For the acetate tow of cigarette fiber, conventionally fiber Y-Shaped, little filament denier, consist of, it is by highly curling and tangle wittingly, as in US Patent No. 2,953, described in 838.Y type allows best cigarette filter, and it is compared and have minimum weight with other fiber shapes for given pressure drop.Referring to US Patent No. 2,829,027.The fiber of little filament denier, in the every filament denier of 1.6-8 (dpf) scope, is used to manufacture effective filter tip conventionally.In structure filter tip, the improved filter tip consolidation of curling permission of fiber and the tow weight reducing for given pressure drop.
Can acetate tow be changed into cigarette filter by tow regulating system and plugmaker (plugmaker), for example, in US Patent No. 3,017, described in 309.Tow regulating system is taken out tow from packing, sprawls and unties (de-registers) (" separately (bloom) ") fiber, and tow is sent to plugmaker.Plugmaker compression tow, wraps it with filter stick formation paper, and is cut to the rod that is applicable to length.In order further to increase filter-tip consolidation, nonvolatile solvent can be added in solvent (fiber is combined).These solvent bonding agent media are called as plasticizer in the industry; and always comprised glyceryl triacetate (triacetyl glycerine), two acetic acid binaryglycol esters, tfiethylene glycol diacetate, glyceryl tripropanoate, CitroflexA-2 and triethyl citrate.Wax has also been used to improve filter tip consolidation.Referring to, for example, US Patent No. 2,904,050.
Traditional plasticizer fiber-fiber binder is very effective for combination and selective filter.Yet plasticizer is not water miscible conventionally, and fiber will be
longin time, keep combination.In fact, due to the height entanglement character of filter fiber, solvent combination between fiber and the intrinsic slow degradation of cellulose acetate polymer, traditional cigarette filter tip may need degrade over several years and decompose after discarded.Therefore, attempt the cigarette filter that research and development have improved degradability.
US Patent No. 5,947,126 disclose a kind of cellulose acetate fibre bundle of being combined with water-soluble fibre-fiber bonding agent.Combining fiber wraps in the paper with the opposed end being fixed together with water-soluble filter stick formation adhesive for paper, and makes a plurality of short fibers (cuts) extend beyond half of fiber of this bundle bag.Thus, provide tobacco smoke filter, it decomposes and degrades within the relatively short time.
US Patent No. 5,947,127 disclose by the form with the aqueous solution or dispersion, or with particle form, water-soluble polymer are added in the tow of cellulose ester fiber and produce filter stick.It is said that tobacco filter tobacco is height hygroscopic water solution, and therefore, it contributes to alleviate environmental pollution.Can pass through in conjunction with biodegradation promotor, as citric acid, tartaric acid, malic acid etc., and/or light degradation promoter, as anatase titanium dioxide, improve the environment degradable of fiber, or titanium dioxide (preferably anatase titanium dioxide) can be used as brightening agent and provides.
Research Disclosure, 375-77 page disclosed the use of plasticizer in the filter tip processed by acetate tow and reduced the degraded of cigarette filter by fiber is combined in June, 1996, but due to fibre matting, only remove plasticiser and can not make filter tip decompose rapidly in environment.Therefore, author proposes to use the tow of rare type, namely, has when moist and will reduce significantly the fiber of the performance of tangling, and the environment of making can decompose filter tip.
US Patent No. 7,435,208 disclose cigarette filter, and it comprises the elongated filter assembly with the longitudinal axis.The slit at a plurality of intervals, is generally perpendicular to the longitudinal axis of filter assembly, and part extends in assembly.Slit can decompose filter tip and more easily degraded after being used and discarding.
US Patent No. 5,491,024 and 5,647,383 disclose staple fibre, and it comprises the titanium dioxide that having of cellulose esters and 0.05-5.0wt% is less than the average grain diameter of 100 nanometers.Before being extruded into tow, titanium dioxide is added in " spinning liquid (dope) " (that is, solvation cellulose esters).Any titanium dioxide that adds easily that can be before extruding.Titanium dioxide is preferably to have and is less than the average grain diameter of 10 nanometers and approximately 250 m
2the uncoated anatase material of the specific area of/g.
US Patent No. 5,512,230 disclose the method for spinning cellulose acetate fibre, and described cellulose acetate fibre has the cellulose esters of low every dehydrated glucose unit substitution value (DS/AGU).It is said the water of 5-40wt% is added in cellulose acetate (CA)/acetone spinning solution (spinning liquid) and produced and will allow to come with the CA with the DS/AGU of 1.9-2.2 the liquid that spins of solvent spinning fibre.
US Patent No. 5,970,988 disclose a kind of cellulose ester fiber with medium every dehydrated glucose unit substitution value (DS/AGU), and it comprises the pigment as photooxidation catalyst.Fiber can be used as the filter-tip material of tobacco product.Thus, the filter-tip material providing be all easy to dispersible and biodegradable, and can sustainable existence in environment.Described pigment can provide for titanium dioxide and in fiber, but the usual amounts comparing while being used as brightening agent in amount is large.
The open US2009/0151738 of United States Patent (USP) discloses a kind of degradable cigarette filter tip, it comprises plated film cellulose acetate tow, around the filter stick formation paper of filter element, and the filter element of the coating contacting with described tow or spherolite (pill).Described coating and/or spherolite can consist of the material that is suitable for the hydrolysis of catalysis cellulose acetate tow and water-soluble base material, make when water contacts described water-soluble base material, this material that is suitable for catalyzing hydrolysis is released, and the hydrolysis of catalysis cellulose acetate tow and degraded subsequently.
WO 2010/017989 discloses a kind of photodegradable plastics, and it comprises cellulose esters and additive (if suitable).The photocatalysis carbon modifying titanium dioxide that this photodegradable plastics comprises dispersion.It is said, when comparing with the product that wherein uses tradition or other modifying titanium dioxides, this photodegradable plastics shows the shockingly height of photocatalytic degradation to be increased.For example, first photodegradable plastics can be further processed to provide filter filament.
The open US2011/0023900 of WO 2009/093051 and United States Patent (USP) discloses tobacco smoke filter or filter element, it comprises the cylindrical filter stick of uniform filtering material substantially that girth is 14.0-23.2 millimeter, the short fiber that wherein filtering material comprises a plurality of random orientations uniformly substantially.
After deliberation mix the photocatalytic activity of phase titanic oxide.Referring to " Explaining the enhanced photocatalytic activity of Degussa P25 mixed-phase TiO2 using EPR ", J. Phys. Chem. B 107 (2003) 4545-4549.Separately refer to " Probing reaction mechanisms in mixed phase TiO2 by EPR ", Journal of Electron Spectroscopy and Related Phenomena, 150 (2006) 155-163.
Titanium Dioxide P25, Manufacture-Properties--Applications, Technical Bulletin Fine Particles, Number 80, Degussa Aerosil & Silanes Product Literature (not marking the date) has discussed the commercial use of mixing phase titanic oxide, comprises with photocatalyst with as photosemiconductor.
US Patent No. 5,720,803 disclose a kind of composition that comprises cellulose esters, described cellulose esters comprise having of 10wt% be at least no more than 2.15 average substitution degree low-substituted cellulose ester, and at least 4-week degradation rate of 60wt% is provided, the amount of carbon dioxide discharging as used according to ASTM 125209-91 is not determined as referring to.Said composition can comprise plasticizer, aliphatic polyester, photodissociation promoter (as anatase titanium dioxide), or biodegradation promotor, as organic acid and their ester.Described low substituted cellulose ester can be for having the average degree of polymerization of 50-250, the cellulose esters of however, residual base metal/alkaline-earth metal of the average substitution degree of 1.0-2.15 and 0.1-1.1 and the equivalent proportion of remaining sulfuric acid.It is said that this Biodegradable fibers cellulose ester compositions is applicable to manufacture various goods, comprise fibre, as tobacco filter.
US Patent No. 5,478,386 disclose a kind of composition that comprises cellulose esters, and described cellulose esters comprises at least low substituted cellulose ester with the average substitution degree that is no more than 2.15 of 10wt%.Said composition can comprise plasticizer, aliphatic polyester, photodissociation promoter (as anatase titanium dioxide), or biodegradation promotor, as organic acid and their ester.
US Patent No. 5,242,880 disclose a kind of Novel Titanium dioxide, comprise sodium, potassium, calcium, magnesium, barium, zinc or the magnesium salts of anatase titania and sulfuric acid or phosphoric acid.It is said that titanium dioxide can be used for the pigmentation of oxidizable polymer, simultaneously for this oxidizable polymer of photooxidation provides catalyst system.
US Patent No. 5,804,296 disclose and have comprised cellulose acetate or other cellulose esters, and the composition of anatase-type titanium oxide, and described anatase-type titanium oxide has the 30m of being not less than
2the specific area of/g, the primary particle size of 0.001-0.07 μ m, or be not less than 30m
2the primary particle size of the specific area of/g and 0.001-0.07 μ m.In order to improve photodegradation and dispersiveness, the surface that phosphoric acid salt or other phosphorus compound, polyalcohol, amino acid or other materials are processed titanium oxide.Said composition can also comprise plasticizer and/or aliphatic polyester, biodegradation promotor (as organic acid or its ester).
WO1995/29209 discloses and has mixed to produce painted cellulose acetate long filament by the dispersion in the carboxylate of polyalcohol and cellulose acetate and cellulose acetate by titanium dioxide.The dispersion that dry-spinning generates is to produce painted cellulose acetate long filament.
Bal á zs, the people such as N á ndor; " The effect of particle shape on the activity of nanocrystalline TiO2 photocatalysts in phenol decomposition "; Applied Catalysis B:Environmental, 84 (2008), 356-362 page, has studied form, namely spherically compares the impact on the photocatalytic activity of nanocrystal titanium dioxide optical catalyst with polyhedron.
Byrne, the people such as H.E.; " Characterization of HF-catalyzed silica gels doped with Degussa P25 titanium dioxide "; Journal of Non-Crystalline Solids, 355 (2009), 525-530 page, by by Degussa P25 Τ iO
2add in lyosol, use HNO
3synthesized SiO with this lyosol of HF acid catalysis
2/ TiO
2composite.Then by several different analytical technologies, characterized described composite.
Hurum, the people such as D. C.; At " Probing reaction mechanisms in mixed phase TiO2 by EPR "; Journal of Electron Spectroscopy and Related Phenomena, 150 (2006), in 155-163 page, by electron paramagnetic resonance spectroscopy, studied mixing phase TiO
2process of Charge Separation in photochemical catalyst.
Janus, the people such as M., at " Carbon-modified TiO2 photocatalyst by ethanol carbonisation "; Applied Catalysis B:Environmental; 63 (2006), in 272-276, studied by carbon and made the impact of titania powder modification on photocatalytic activity by ethanol carbonization.
Janus, the people such as M., at " Carbon Modified TiO2 Photocatalyst with Enhanced Adsorptivity for Dyes from Water "; Catal. Lett.; 131 (2009), in 506-511 page, by making the modification of business anatase titanium dioxide obtain new photochemical catalyst in alcohol atmosphere in pressure reactor.In the decomposable process of trisazo dyes, tested the photocatalytic activity of described material.
Lu, the people such as Xujie, at " Intelligent Hydrated-Sulfate Template Assisted Preparation of Nanoporous TiO2 Spheres and Their Visible-Light Application "; ACS Applied Materials & Interfaces; In 2010 12 months, study nano porous titanium dioxide ball and their application, comprised their photocatalytic activity.
The people such as Juergen Puls, at " Degradation of Cellulose Acetate-Based Materials:A Review "; Journal of Polymers and the Enviro nanometer ent: the 19th volume, the 1st phase; 2011; In 152-165 page, look back the cellulosic biological degradability of Dichlorodiphenyl Acetate, comprised the research that light degradation is carried out.
Yet, still need biodegradable fiber element ester, as for the preparation of those of cigarette filter, what especially show increase is using those of the ability of degrading in can being applied in every way the environment of filter-tip material.
Summary of the invention
On the one hand, the present invention relates to the goods that comprise cellulose esters, among described cellulose esters or on be incorporated to mixing phase titanic oxide particle.These goods can be the form of moulding article (molded article), or the form of cellulose ester fiber, for example, and the form of yarn or fabric.
Or described cellulose ester fiber can be filter-tip form, described filter tip is by a kind of comprising the plasticizer with the mixing phase titanic oxide particle being dispersed in being wherein applied to cellulose ester fiber to obtain plasticized fibre element; Prepared by the method that makes afterwards described plasticized fibre element ester fiber form filter-tip step.Aspect this; described plasticizer can comprise following one or more: glyceryl triacetate (triacetyl glycerine), two acetic acid binaryglycol esters, tfiethylene glycol diacetate, methyl phthalyl ethyl hexanol acid esters (methyl phthalyl ethyl glycollate), dibutyl phthalate, glyceryl tripropanoate, the mixture of CitroflexA-2, triethyl citrate and glyceryl triacetate and one or more polyethylene glycol.When goods of the present invention are filter-tip form, this filter tip can have one or more slits (slit), and can, for example, for cigarette.
Available mixing phase titanic oxide particle according to the present invention can comprise, for example, and the Anatase existing with the amount of 50%-98%, and with the Rutile Type that the amount of 2%-50% exists, in each situation, all by x-radiocrystallography, measure.Described particle can have, for example the about 300m of about 10-
2the surface area of/g, and can there is independently approximately 1 nanometer-Yue 100 nanometer, or the average grain diameter of 5 nanometer-50 nanometers.
The amount of the mixing phase titanic oxide particle providing to article according to the invention can change on a large scale, for example, from approximately 0.01 to about 20wt%, the weight based on these goods.
For example, when goods of the present invention are the form of fiber, they can, for example, by being dispersed in the solvent of this fiber of spinning therefrom, be dispersed in cellulose ester fiber.
Available cellulose esters according to the present invention can comprise one or more in cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate or acetylbutyrylcellulose, for example, there is about 1.8-approximately 2.7, or the cellulose acetate of the DS/AGU of about 1.9-approximately 2.5.
Other side of the present invention is as disclosed herein with claimed.
describe in detail
Although can be by the rutile of about 200 nanometers of size
typetitanium dioxide granule offers cellulose esters so that good light scattering and minimum photolytic activity to be provided, with by anatase titanium dioxide particle for strengthening the degraded of cigarette filter, but the present invention but relates to the titanium dioxide granule that mixes phase, below be described as mixing phase titanic oxide particle, its with by anatase form or rutile form, is formed separately those compare, the degraded under ultraviolet (UV) radiation strengthening is provided.Mixing phase titanic oxide particle of the present invention is for especially uncoated and have those of ultra-fine grain diameter (<100 nanometer), to realize optimal light activity.
We determine, when with rutile fully or when the Particle Phase of the crystal structure of anatase compares fully, the titanium dioxide granule with the mixture of anatase and rutile crystal structure, mixes phase particle, and the most degradation amount under the existence of ultraviolet ray (UV) radiation is provided.Thus, the present invention relates to wherein be incorporated to the cellulose esters of the titanium dioxide granule of the mixing phase with anatase and rutile crystal, especially there are those of uncoated surface and ultra-fine (<100 nanometer) particle diameter.Can in every way described mixing phase titanic oxide particle be offered to this cellulose esters.
When we say " Rutile Type " or " rutile-type crystal structure ", we refer to the structure by the modal native form of the definite titanium dioxide of its unique x-ray diffraction pattern.This mutually or crystal structure can, for example, by X-ray crystallography, differentiate.When we say " Anatase " or " Detitanium-ore-type crystal structure ", we refer to the known structure of being determined by its x-ray diffraction pattern.This mutually or crystal structure equally can, for example, by X-ray crystallography, differentiate.The structure of these phases or crystal is well-known in titanium dioxide field, easily in mode described herein, identifies to those skilled in the art thus.
Thus, mixing phase titanic oxide particle used according to the invention, is characterized by and in same particle, have rutile-type and Detitanium-ore-type crystal structure simultaneously.By term " mixing phase ", we are not intended to comprise one or another kind of particle in described two kinds of structures only with trace.Thus, the amount that is present in the Anatase in mixing phase particle is passable, for example, and from approximately 50% to approximately 99%, or from 60% to 98%, or from 75% to 95% variation, in each situation, all by X-ray crystallography, measure.Being present in Rutile Type in this particle can be equally in a similar fashion, for example, and from approximately 1% to approximately 50%, or from 2% to 40%, or from 5% to 25% variation, in each situation, all by X-radiocrystallography, measure.We have found that these particles are particularly suitable for strengthening the filter-tip degraded of wherein having used them.Do not wish to be limited to any theory, we think, the adaptability of this mixing phase particle may be because Rutile Type provides better ultraviolet ray (UV) to absorb, and Anatase provides better photocatalysis performance.Thus, the present invention relates to use and mix phase titanic oxide particle at cellulose esters (as for those of cigarette filter), do not consider the method for combination,, no matter be to provide to plasticizer, in fiber, still otherwise provide.
Of course, for example, by as the method for flame hydrolysis of titanium tetrachloride and so on, prepare according to available mixing phase titanic oxide particle of the present invention.Can obtain relatively highly purified mixing phase titanic oxide particle by the method.Referring to, for example, the Titanium Compounds (Inorganic) entry of Kirk-Othmer, Encyclopedia of Chemical Technology, 225-274 page, the 24th volume, the 4th edition, John Wiley and Sons, 1997.Also can use the gaseous oxidation of titanium tetrachloride.Id. also can use other method, the particle that wherein obtained has the mixture of Anatase and Rutile Type in same particle, as described.
The surface area of mixing phase titanic oxide particle of the present invention is passable, for example, and from approximately 10 to about 300m
2/ g, or from 20 to 200m
2/ g, or from 40 to 100m
2/ g changes, as measured by GAS ABSORPTION in BET specific area method.
The amount that offers the mixing phase titanic oxide particle of cellulose esters can change in wide scope, for example, and from approximately 0.01 to about 20wt.%, or from 0.2 to 10 wt.%, or from 0.2 to 5 wt.%.The amount of the titanium dioxide granule providing in some respects, can depend on the solution viscosity in fiber manufacture process.According to the present invention, the various particle diameters of titanium dioxide are available, for example, from approximately 1 nanometer to approximately 10 microns, from or 1 nanometer to 1 micron, from or 1 nanometer to 500 nanometer, or from 1 nanometer to 250 nanometer, or from 3 nanometer to 100 nanometers, or from 5 nanometer to 50 nanometers.We have found that, nano-scale particle is particularly useful for of the present invention.Do not wish to be limited to any theory, this may be because the use of less particle diameter provides higher surface area.Second possible reason is that little particle diameter is further penetrated in cellulose esters ultraviolet ray (UV) radiation, and degraded is advanced from surface, causes thus the more degraded of depths in cellulose esters.
Although given particle diameter refers to primary particle size, this optical active matter can not only exist with discrete particle, also with agglomerated thing, exists.We have found that, the particle existing as agglomerated thing compatibly strengthens generated filter-tip degraded, but can mill particle, for example, if necessary, to obtain more uniformly and primary particle size.
The titanium particle with uncoated applying is all applicable to the present invention.The coating agent that can be applied to titanium dioxide granule comprises, for example, and carbon coating.Can be combined on titanium dioxide surface or inner coating agent comprises, for example, carbon coating and hydrated metal sulfate (MSO
4* xH2O, M=Zn, Fe, Co, Mg etc.), do not wish to be limited to any theory, some coating (for example carbon coating) can, for example, by allowing visible absorption to promote the light degradation of filter-tip expectation.
Modification and unmodified titanium particle are all applicable to the present invention, for example carbon modified particles.Although mixing phase oxidation titanium particle according to the present invention is mainly Rutile Type and Anatase, described particle can therein or have carbon modification on it.Carbon modification or doping, can be for example, by ethanol carbonization or the absorption by dyestuff, realizes.Do not wish to be limited to any theory, some modification (for example carbon coating) can, for example, by allowing visible absorption, promote the light degradation of filter-tip expectation.Another kind of theory is that carbon modification (as carbon doping) can be suppressed at anatase in high-temperature process to the phase transformation of rutile and reduce crystalline size.
On the one hand, mixing phase titanic oxide particle of the present invention can be offered to this cellulose esters and " spin liquid ", that is, offer the cellulose esters being dissolved in acetone, therefrom spinning fibre element ester fiber.Can be in every way, for example, by being incorporated to cellulose acetate, glyceryl triacetate and Τ iO
2mixture, mixing phase titanic oxide particle is offered and spins liquid.Or described particle can pass through Τ iO
2be blended in hydrophilic solvent and provide, it will allow best particle to disperse.The further example that titanium dioxide granule is dispersed in cellulose ester fiber is included in US Patent No. 5,970, those that list in 988, and it is incorporated herein by reference, although being characterized as of titanium dioxide granule of the present invention mixes phase titanic oxide particle.
In moulding article, can, for example by with polymer concentrates high shear blend, mixing phase titanic oxide particle of the present invention is provided.
We have also determined, in the manufacture of cigarette filter, the use of the optical active matter in plasticizer also causes the decomposition rate of the increase of the filter structure that generates, as being exposed in environment out of doors, on the filter tip of ultraviolet ray (UV) radiation, measure.This is different from when forming fiber optical active matter is added in fiber, for example, spins in liquid, by optical active matter being added to cellulose esters as described in just now.Yet, the present invention relates to use and mix phase titanic oxide particle, no matter be to provide in cellulose ester fiber or in plasticizer or in both.In the common pending application with submitting to a little same dates, titanium dioxide granule is used in application protection in plasticizer separately, and no matter whether particle is to mix phase in itself.
Term used herein " plasticizer " is intended to describe a kind of solvent, and when being applied to cellulose ester fiber, it is by fiber solvent-combine.Available plasticizer according to the present invention comprise following one or more: the mixture of glyceryl triacetate (triacetyl glycerine), two acetic acid binaryglycol esters, tfiethylene glycol diacetate, glyceryl tripropanoate, CitroflexA-2, triethyl citrate and glyceryl triacetate and one or more polyethylene glycol.This blend or mixture can optionally comprise polymer, water-soluble polymer for example, as thering is a cellulose acetate of the DS/ADU of 0.6-0.9, polyester, as methylcellulose, hydroxyethylcellulose and hydroxypropyl cellulose, polyvinyl acetate (PVA) and polyvinyl alcohol (PVOH).
As used herein, mixing phase titanic oxide particle of the present invention is also referred to as " optical active matter ", and play this reagent, mean, in being added to the plasticizer that puts on cellulose ester fiber, or while being added to cellulose esters itself, improve when be exposed to UV radiation described in the ester speed of degrading.
When applying with plasticizer, any in can be is in many ways dispersed in mixing phase particle in plasticizer, for example, and by using high shear mixing equipment, as medium mill or ultrasonic probe.The stability of the mixing phase particle in plasticizer,, in filter tip manufacture process, particle keeps being suspended in the trend in plasticizer, can be by a certain amount of cellulose esters be added in plasticizer and is strengthened, for example, with about 0.1%-approximately 20%, or the amount of 0.2-10%, the viscosity of the plasticizer solution based on generated.Can be by providing a certain amount of polyethylene glycol further to strengthen stability to this plasticizer, described polyethylene glycol has, and for example, about 100-approximately 400, or the molecular weight of 200-1000, with about 0.1%-approximately 20%, or the amount of 0.2%-10%.
Those skilled in the art will easily recognize, at plasticizer but not provide optical active matter to allow to use traditional acetate tow in fiber, and without the formula of this ester or tow is done to any change.Yet the mixing phase particle in plasticizer may affect, for example, the viscosity of plasticizer, if especially combine stabilizing agent, as cellulose esters and/or polyethylene glycol.Thus, preferably select stabilizing agent in order to avoid affect viscosity, for example, by relatively low-molecular-weight cellulose esters or polyethylene glycol or both are provided.
Term used herein " cellulose esters " means can be by, and for example, melt-spun or solvent are spun into one or more cellulose esters of fiber, as cellulose acetate.Thus, available cellulose esters according to the present invention includes, but are not limited to, cellulose acetate, cellulose propionate and there is the cellulose butyrate of different degree of substitution, and these mixed ester, that is, and cellulose acetate propionate, acetylbutyrylcellulose and acetate propionate cellulose butyrate.Cellulose esters of the present invention can be two cellulose esters.The example of suitable ester comprises cellulose acetate, cellulose acetate propionate and acetylbutyrylcellulose thus, as in US Patent No. 1,698,049,1,683,347,1,880,808,1,880,560,1,984,147,2,129,052 and 3,617, described in 201, they are incorporated herein by reference.
Thus, although cigarette filter is made by cellulose acetate fibre traditionally, the present invention is not strictly limited to traditional ester.And; although the substitution value (DS/AGU) for typical every dehydrated glucose unit of the acetate of cigarette filter is approximately 2.45; but can easily use and there are a series of acetyl group levels; as 1.5-2.8 or 1.8-2.7 or 1.9-2.5; or for example, the ester of approximately 2.0 average DS/AGU also builds fiber.We notice that lower DS/AGU value can provide biodegradation faster.
Cellulose esters of the present invention can be spun into fiber, for example pass through melt-spun or by suitable solvent (for example pass through, acetone, acetone/water, oxolane, methylene chloride/methanol, chloroform, diox, DMF, methyl-sulfoxide, methyl acetate, ethyl acetate or pyridine) spinning.When by solvent spinning, type and the DS/AGU that ester replaces depended in the selection of solvent.For the suitable solvent of spinning fibre, be the acetone of the water that comprises 0-30%.For the cellulose acetate with the DS/AGU of 2.4-2.6, preferred spin solvent is the acetone that comprises the water that is less than 3%.For the cellulose acetate with the DS/AGU of 2.0-2.4, the aqueous acetone solution that preferred spin solvent is 5-15%.For the cellulose acetate with the DS/AGU of 1.7-2.0, the aqueous acetone solution that preferred solvent is 15-30%.
When melt spun fibre, cellulose esters or plasticized fibre element ester can have, the melt temperature of for example 120 ℃-250 ℃, or 180 ℃-220 ℃.The example that is used for the suitable plasticizer of melt spun fibre element ester comprises, but be not limited to diethyl phthalate, dipropyl phthalate, dibutyl phthalate, triacetyl glycerine, dioctyl adipate, polyethylene glycol-200 or polyethylene glycol-200 or PEG-4000.Preferred plasticizer for melt-spun comprises dibutyl phthalate, dioctyl adipate or PEG-4000.
The cellulose ester fiber using can be continuous fiber, can be maybe the short fiber with shorter length, and it makes fiber be easier to degraded.Thus, short fiber can have about 4-20 mm, or 5-18 mm, or the length of 7-16 mm.
Available cellulose ester fiber according to the present invention is normally curling, has, for example, the per inch crispation number of 4-20, or the per inch crispation number of 10-15.This fiber has 20-0.1 or the every filament denier of 5-1.5 (DPF) conventionally.In order to process, described fiber can optionally comprise lubricant or processing aid, and as mineral oil, with 0.1-3%, or the amount of 0.3%-0.8% is used.
Although particulate additives is generally added in fiber to strengthen filter-tip whiteness, these additives are generally the titanium dioxide granule of size approximately 200 nanometers, and this size provides good light scattering to have minimum photolytic activity.This titanium particle generally has inorganic coating from the teeth outwards to strengthen the dispersion of particle in spinning solution.Perhaps, titanium dioxide not being added in plasticizer traditionally, is not strengthen whiteness because it may limit filter-tip hardness.
Filter tip produced according to the invention may further include other characteristics that strengthens their degradeds, for example, by perpendicular to longitudinal axis slot, by being incorporated to short fiber, or in environment, tends to improve other shorter fibers of the speed of degraded.The further method that improves degradation rate can be included in plasticizer in conjunction with one or more polymer, water-soluble polymer for example, if yet this affect ability that plasticizer dissolves ester make optical active matter can be in plasticizing step process permeable fiber, this in fact may reduce degradation rate.However still available water-soluble polymer comprises a cellulose acetate of the DS/ADU with 0.6-0.9, and polyester, as methylcellulose, hydroxyethylcellulose and hydroxypropyl cellulose, polyvinyl acetate (PVA) and polyvinyl alcohol (PVOH).By following examples, further illustrate novel method provided by the invention and filter tip.
As mentioned above, the present invention is not limited to the cellulose esters that is fibers form for cigarette filter, but can also relate to other cellulose ester fiber, as being called as acetate yarn and for those of various textile applications (comprising clothing) in the industry.According to cellulose esters of the present invention, also can be the form of moulding article, or any other form known that is wherein desirably in the decomposition rate increasing in environment of cellulose esters.
Embodiment
embodiment:
In following examples, with traditional filter manufacturing machine, assembled filter tip sample, in filter tip manufacture process, 10% glyceryl triacetate is applied to fiber.
For the test of degrading, filter tip sample is placed in wire cylinder mould independently to the roof of building, so that enough UV radiation arrive described filter tip.This cage is placed in the overhead position of approximately 4 inches, so that it is minimized to be arranged in the sample in the puddle that is present in roof.Each roof research is comprised of the filter tip of ten 21 millimeters of each embodiment, is placed in wire cylinder mould, takes off paper and only leaves the filter-tip fiber of formation.Paper is removed, thereby the fiber in filter tip can directly be exposed to UV radiation, and determines thus the impact of optical active matter on degradability.Regularly collect the degraded that filter tip weighs to assess the fiber in filter tip.Result is that the weight of these ten filter tip samples is in the contrast of each test point.
In the different time, carry out twice independent outdoor weathering (weathering) test.Embodiment 1-4 represent first group test sample and embodiment 5-8B represents second group of sample of testing by roof outdoor weathering.Each group is all tested by above-mentioned degraded.
embodiment 1-is without TiO
2
Constructed to have and do not comprised TiO
2ten cigarette filters of cellulose acetate fibre.Be displayed in Table 1 outdoor weathering result for contrasting with embodiment 1-4.Result shows not have TiO
2the light degradation speed of cellulose acetate fibre limited.
the uncoated anatase TiO of embodiment 2-pigment size (210 nanometer)
2
With the uncoated anatase TiO that comprises 0.5% pigment size (210 nanometer)
2cellulose acetate fibre constructed ten traditional cigarette filters.In table 2, listed TiO
2the performance of (Tioxide A-HR), for contrasting with other laboratory samples.
the uncoated anatase TiO of embodiment 3-ultra-fine size (32 nanometer)
2
In order to illustrate, mix the amount of phase and the importance of crystalline size, with Nanotek (a kind of uncoated TiO of the ultra-fine size (32 nanometer) that can obtain from Nanophase that comprises 0.5%
2) cellulose acetate fibre prepared ten filter tips.This ultra-fine size TiO
2the percentage crystal phase structure anatase that is 94% and 6% rutile.Crystal structure is greater than 500, and this shows it is megacryst.In table 2, listed this ultra-fine size TiO
2all the other performances of (from the Nanotek of Nanophase).
the uncoated mixing phase TiO of embodiment 4-ultra-fine size (21 nanometer)
2
With the uncoated mixing phase TiO that comprises 0.5% ultra-fine size (21 nanometer)
2the cellulose acetate fibre of (P25 can obtain from Degussa) has been prepared ten filter tips.Note this TiO
2mixing phase in particle, 89% anatase and 11% rutile, and little crystalline size (301).In table 2, listed this TiO
2the performance of (from the P25 of Degussa).
As shown in Table 1, embodiment 4 provides the fastest degraded, wherein ultra-fine uncoated TiO
2particle consists of with the mixing of rutile (11%) mutually anatase (89%).Do not there is TiO
2filter tip after 10 months, there is 81% residuals weight; And the filter tip with uncoated anatase (94%) particle of pigment size (210 nanometer) has 38% residuals weight.The TiO of the ultra-fine size of the mixing phase in embodiment 4 (21 nanometer)
2there is 33% residuals weight.Notice that the another kind in embodiment 3 mixes phase TiO
2there is 72% residuals weight, shown higher rutile to anatase mixing ratio the importance together with less crystalline size.
The outdoor weathering result of table 1-
| Embodiment numbering | 1 | 2 | 3 | 4 |
| Tioxide A-HR TiO2, the % in fiber | - | 0.5 | - | - |
| Nanophase TiO 2, the % in fiber | - | - | 0.5 | - |
| Degussa P25 TiO 2, the % in fiber | - | - | - | 0.5 |
| Time, month | Wt % | Wt % | Wt % | Wt % |
| 0 | 100 | 100 | 100 | 100 |
| 2 | 93 | 89 | 91 | 84 |
| 4 | 93 | 85 | 87 | 76 |
| 6 | 91 | 73 | 88 | 62 |
| 7 | 89 | 64 | 86 | 53 |
| 8 | 85 | 52 | 81 | 42 |
| 9 | 82 | 44 | 76 | 34 |
| 10 | 81 | 38 | 72 | 33 |
Table 2-TiO
2additive Properties
| Embodiment numbering | 1 | 2 | 3 | 4 |
| TiO2 | - | Tioxide A-HR | Nanophase | Degussa P 25 |
| Particle diameter, nanometer | - | 210 | 32 | 21 |
| Anatase, % | - | 100 | 94 | 89 |
| Rutile, % | - | 0 | 6 | 11 |
| Anatase crystal size, | - | >1000 | 536 | 301 |
| Rutile crystal size, | - | - | 847 | 546 |
| BET surface area, m 2/g | - | 14 | 44 | 53 |
embodiment 5-without TiO
2
By not comprising TiO
2the cellulose acetate fibre of pigment has been constructed filter tip.In table 3, listed roof outdoor weathering result.
the anatase TiO of the coating of embodiment 6-pigment size (210 nanometer)
2
By the TiO that comprises 0.5wt%
2the cellulose acetate fibre of pigment has been prepared ten traditional cigarette filters.This TiO
2pigment has the average grain diameter of 210 nanometers and is comprised of the anatase particles with inorganic coating.Be displayed in Table 3 roof outdoor weathering result.In table 4, listed this TiO
2(Kronos1071) performance.
the mixing phase TiO that the ultra-fine size of embodiment 7A, 7B and 7C-is uncoated
2
(21 nano-scale)
With the AEROXIDE TiO that comprises the difference amount being present in fiber
2p 25 (the mixing phase TiO that a kind of ultra-fine size is uncoated
2) cellulose acetate fibre prepared ten filter tips.The filter tip of embodiment 7A has the described particle of 0.5 wt%.In embodiment 7B, cellulose acetate fibre has the described particle of 1.0 wt%.In embodiment 7C, cellulose acetate fibre has this identical particle of 2.0 wt%.In table 3, listed roof outdoor weathering result.In table 4, listed this TiO
2the performance of (being selected from the AEROXIDE P25 of Evonik).
the mixing phase TiO that the ultra-fine size of embodiment 8A and 8B-is uncoated
2
(14 nano-scale)
With the VP TiO that comprises different amounts
2p 90 (a kind of uncoated mixing phase TiO of ultra-fine size of the average grain diameter with approximately 14 nanometers
2) cellulose acetate fibre constructed ten filter tips.Embodiment 8A has the described particle of 0.5 wt%, and embodiment 8B has the described particle of 1.0 wt%.In table 3, listed roof outdoor weathering result.In table 4, listed this TiO
2the performance of (being selected from the VP P 90 of Evonik).
Table 3-roof outdoor weathering result
| Embodiment | 5 | 6 | 7A | 7B | 7C | 8A | 8B |
| Kronos 1071 TiO 2， % | - | 0.5 | - | - | - | - | - |
| P 25 TiO 2, the % in fiber | - | - | 0.5 | 1.0 | 2.0 | - | - |
| P 90 TiO 2, the % in fiber | - | - | - | - | - | 0.5 | 1.0 |
| Time, month | Wt. % | Wt. % | Wt. % | Wt. % | Wt. % | Wt. % | Wt. % |
| 0 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| 3 | 93 | 92 | 61 | 61 | 62 | 81 | 67 |
| 6 | 86 | 85 | 37 | 37 | 39 | 59 | 44 |
| 9 | 83 | 79 | 31 | 32 | 33 | 51 | 40 |
Table 4-TiO
2additive
| Embodiment numbering | 5 | 6 | 7A - 7C | 8A - 8B |
| TiO 2 | - | Kronos 1071 | AEROXIDE P25 | VP P90 |
| Particle size, nm | - | 210 | 21 | 14 |
| Anatase, % | - | 100 | 83 | 89 |
| Rutile, % | - | 0 | 17 | 11 |
| Anatase crystal size, | - | >1000 | 265 | 145 |
| Rutile crystal size, | - | - | 306 | 161 |
| BET surface area, m 2/g | - | 14 | 50 | 95 |
As shown in Table 3, there is the ultra-fine uncoated TiO by the mixing phase composition of anatase and rutile
2the embodiment 7 and 8 of particle provides the fastest degraded.Do not there is TiO
2filter tip after 9 months, there is 83% residuals weight; And the filter tip of anatase particles with the coating of pigment size has 79% residuals weight.Mix phase TiO
2embodiment #7A-7C has the residuals weight of 31-33%.Note other mixing phase TiO in embodiment 8A-8B
2there is 51% and 40% residuals weight.
Claims (20)
1. the goods that comprise cellulose esters, among described cellulose esters or on be incorporated to mixing phase titanic oxide particle.
2. goods according to claim 1, wherein said cellulose esters is the form of cellulose ester fiber.
3. goods according to claim 2, wherein said goods are filter-tip form, and described filter tip is by a kind of comprising the plasticizer with the mixing phase titanic oxide particle being dispersed in being wherein applied to described cellulose ester fiber to obtain the cellulose ester fiber of plasticising; With
Make afterwards the cellulose ester fiber of described plasticising form prepared by filter-tip method.
4. goods according to claim 3, wherein said plasticizer comprise following one or more: the mixture of glyceryl triacetate (triacetyl glycerine), two acetic acid binaryglycol esters, tfiethylene glycol diacetate, methyl phthalyl ethyl hexanol acid esters, dibutyl phthalate, glyceryl tripropanoate, CitroflexA-2, triethyl citrate and glyceryl triacetate and one or more polyethylene glycol.
5. goods according to claim 3, wherein said mixing phase titanic oxide particle comprises the Anatase that the amount with 50%-98% exists, and with the Rutile Type that the amount of 2%-50% exists, in each situation, all by x-radiocrystallography, measures.
6. goods according to claim 1, wherein said goods are the form of yarn.
7. goods according to claim 1, wherein said goods are the form of fabric.
8. goods according to claim 1, wherein said mixing phase titanic oxide particle has the about 300m of about 10-
2the surface area of/g.
9. goods according to claim 1, wherein said mixing phase titanic oxide particle has the average grain diameter of approximately 1 nanometer-Yue 100 nanometers.
10. goods according to claim 1, wherein said mixing phase titanic oxide particle has the average grain diameter of 5 nanometer-50 nanometers.
11. goods according to claim 1, the titanium dioxide granule that wherein said mixing phase titanic oxide particle is carbon-modification.
12. goods according to claim 2, are wherein dispersed in described mixing phase titanic oxide particle in described cellulose ester fiber.
13. goods according to claim 12, are wherein dispersed in described mixing phase titanic oxide particle in described cellulose ester fiber by being dispersed in the solvent of fiber described in therefrom spinning.
14. goods according to claim 1, wherein said cellulose esters comprises one or more in cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate or acetylbutyrylcellulose.
15. goods according to claim 1, the cellulose acetate that wherein said cellulose ester fiber comprises the DS/AGU with about 1.8-approximately 2.7.
16. goods according to claim 1, the cellulose acetate that wherein said cellulose esters comprises the DS/AGU with about 1.9-approximately 2.5.
17. goods according to claim 1, the amount that wherein offers the described mixing phase titanic oxide particle of described goods is the about 20wt% of about 0.01-, the weight based on described goods.
18. goods according to claim 3, wherein said filter tip further comprises one or more slits.
19. cigarette that comprise goods according to claim 2.
20. goods according to claim 1, wherein said goods are the form of moulding article.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/167239 | 2011-06-23 | ||
| US13/167,239 US20120325233A1 (en) | 2011-06-23 | 2011-06-23 | Cellulose esters having mixed-phase titanium dioxide particles for improved degradation |
| PCT/US2012/042451 WO2012177483A1 (en) | 2011-06-23 | 2012-06-14 | Cellulose esters having mixed-phase titanium dioxide particles for improved degradation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103607913A true CN103607913A (en) | 2014-02-26 |
Family
ID=46457029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280030468.4A Pending CN103607913A (en) | 2011-06-23 | 2012-06-14 | Cellulose esters having mixed-phase titanium dioxide particles for improved degradation |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20120325233A1 (en) |
| EP (1) | EP2723202A1 (en) |
| JP (1) | JP2014523241A (en) |
| KR (1) | KR20140047667A (en) |
| CN (1) | CN103607913A (en) |
| BR (1) | BR112013032688A2 (en) |
| CA (1) | CA2838082A1 (en) |
| MX (1) | MX2013014676A (en) |
| RU (1) | RU2014101981A (en) |
| WO (1) | WO2012177483A1 (en) |
Cited By (3)
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|---|---|---|---|---|
| CN108103604A (en) * | 2017-12-20 | 2018-06-01 | 南通大学 | Compound photo sensitive additive of degradation acetate fiber and its preparation method and application |
| CN114521673A (en) * | 2022-03-01 | 2022-05-24 | 湖北中烟工业有限责任公司 | Composite plasticizer and preparation method and application thereof |
| CN115005497A (en) * | 2022-07-20 | 2022-09-06 | 湖北中烟工业有限责任公司 | Degradable cigarette filter rod master batch and degradable cigarette filter rod |
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| US8720450B2 (en) * | 2010-07-30 | 2014-05-13 | R.J. Reynolds Tobacco Company | Filter element comprising multifunctional fibrous smoke-altering material |
| US9854833B2 (en) * | 2012-02-16 | 2018-01-02 | R. J. Reynolds Tobacco Company | Apparatus and associated method for forming a filter component of a smoking article |
| EP2837296A1 (en) * | 2013-08-12 | 2015-02-18 | Solvay Acetow GmbH | Catalytically degradable plastic and its use |
| KR102188528B1 (en) * | 2013-08-12 | 2020-12-08 | 솔베이 아세토우 게엠베하 | Process for manufacturing a product containing a catalytically active titanium compound |
| JP2015221955A (en) * | 2014-04-30 | 2015-12-10 | 三菱レイヨン・テキスタイル株式会社 | Fiber having deodorizing function and antibacterial function and manufacturing method therefor and knitted fabric |
| CN107278171A (en) * | 2014-07-10 | 2017-10-20 | 沙特基础全球技术有限公司 | Hydrogen is prepared by water photocatalysis on mixing phase titanium dioxide nanometer particle |
| EP3039970A1 (en) * | 2014-12-29 | 2016-07-06 | Philip Morris Products S.A. | Smoking article filters having oxo-additives |
| JP7217099B2 (en) * | 2018-07-12 | 2023-02-02 | 株式会社ダイセル | Cellulose acetate fiber, cellulose acetate tow band, and method for producing cellulose acetate tow band |
| WO2021014561A1 (en) * | 2019-07-23 | 2021-01-28 | 株式会社ダイセル | Cellulose acetate fiber production method and cellulose acetate fiber |
| KR20220069016A (en) * | 2019-08-27 | 2022-05-26 | 아쎄테이트 인터내셔널 엘엘씨 | Cellulose acetate tow with high DPF and low titanium dioxide content |
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Also Published As
| Publication number | Publication date |
|---|---|
| RU2014101981A (en) | 2015-07-27 |
| WO2012177483A1 (en) | 2012-12-27 |
| CA2838082A1 (en) | 2012-12-27 |
| MX2013014676A (en) | 2014-03-27 |
| US20120325233A1 (en) | 2012-12-27 |
| JP2014523241A (en) | 2014-09-11 |
| BR112013032688A2 (en) | 2017-01-24 |
| KR20140047667A (en) | 2014-04-22 |
| EP2723202A1 (en) | 2014-04-30 |
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