CN1098275C - Cellulose triacetate and method for its production - Google Patents
Cellulose triacetate and method for its production Download PDFInfo
- Publication number
- CN1098275C CN1098275C CN98107303A CN98107303A CN1098275C CN 1098275 C CN1098275 C CN 1098275C CN 98107303 A CN98107303 A CN 98107303A CN 98107303 A CN98107303 A CN 98107303A CN 1098275 C CN1098275 C CN 1098275C
- Authority
- CN
- China
- Prior art keywords
- cellulose triacetate
- mannose
- xylose
- weight
- cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920002284 Cellulose triacetate Polymers 0.000 title claims abstract description 105
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims 3
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims abstract description 22
- 230000021736 acetylation Effects 0.000 claims abstract description 18
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005266 casting Methods 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract 28
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract 14
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract 14
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 7
- 238000004255 ion exchange chromatography Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 2
- 230000000397 acetylating effect Effects 0.000 claims 1
- 238000002834 transmittance Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 25
- 229920001131 Pulp (paper) Polymers 0.000 description 38
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 32
- 229960003487 xylose Drugs 0.000 description 32
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 description 26
- 239000010408 film Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000012528 membrane Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 235000011054 acetic acid Nutrition 0.000 description 9
- 150000004804 polysaccharides Polymers 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229920001282 polysaccharide Polymers 0.000 description 8
- 239000005017 polysaccharide Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 235000010980 cellulose Nutrition 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 6
- 150000001243 acetic acids Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011121 hardwood Substances 0.000 description 6
- 239000011122 softwood Substances 0.000 description 6
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 5
- 229920002301 cellulose acetate Polymers 0.000 description 5
- 238000007766 curtain coating Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 239000007799 cork Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- -1 Fatty acid ester Chemical class 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 241000586542 Aonidiella citrina Species 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- 241001343274 Dichrostachys spicata Species 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- XKGDWZQXVZSXAO-SFHVURJKSA-N Ricinolsaeure-methylester Natural products CCCCCC[C@H](O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-SFHVURJKSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000000937 inactivator Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- VCCPBPXMXHHRLN-UHFFFAOYSA-N methylsulfinylmethane;propan-2-one Chemical compound CC(C)=O.CS(C)=O VCCPBPXMXHHRLN-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
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- XKGDWZQXVZSXAO-UHFFFAOYSA-N ricinoleic acid methyl ester Natural products CCCCCCC(O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002002 slurry Substances 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical class CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
通过乙酰化具有甘露糖/木糖的摩尔比为0.35-3.0(以糖计)、α-纤维素含量为90-97%(重量)，甘露糖和木糖的总量为2-6摩尔%的低纯度纸浆，来制得平均乙酰化度58-62.5%的三乙酸纤维素。通过使用甘露糖/木糖之摩尔比为0.35-3.0的三乙酸纤维素可改善流延膜从载体上的可剥离性。通过在乙酰化步骤中使用每100重量份纸浆400-500重量份乙酸和/或用氧化剂处理三乙酸纤维素，可改进三乙酸纤维素的光学性能。通过本发明的方法，可通过从低纯度纸浆制备流延后具有高剥离性能和优良光学性能的三乙酸纤维素。By acetylation having a mannose/xylose molar ratio of 0.35-3.0 (as sugar), an alpha-cellulose content of 90-97% by weight, and a total of 2-6 mol% of mannose and xylose low-purity pulp to produce cellulose triacetate with an average degree of acetylation of 58-62.5%. The releasability of the cast film from the support can be improved by using cellulose triacetate in a mannose/xylose molar ratio of 0.35-3.0. The optical properties of cellulose triacetate can be improved by using 400-500 parts by weight of acetic acid per 100 parts by weight of pulp in the acetylation step and/or treating the cellulose triacetate with an oxidizing agent. By the method of the present invention, cellulose triacetate having high release performance and excellent optical properties after casting can be prepared from low-purity pulp.
Description
The present invention relates to the method that can be used for preparing the cellulose triacetate of protective membrane and prepare cellulose triacetate, this protective membrane can be used for the polarizer, colored filter, photosensitive photographic film etc.
Tri cellulose acetate membrane is tough and tensile and has good dimensional stability, thermotolerance and optical isotropy.Therefore, be widely used in various uses, as be used for optical thin film devices the base material base material of photochromics (as be used for), be used for the polarizer protective membrane (as the liquid crystal protective membrane) and the colored filter of liquid crystal (LC) device.Therefore, need tri cellulose acetate membrane to have satisfied optical property, as low yellowness index, haze, double refraction and high transparency.
In order to ensure satisfied optical property; tri cellulose acetate membrane is usually with following a kind of like this prepared; this technology comprises: the cotton linter pulp of the about 97-98% of acetylize alpha-cellulose content or highly purified hard wood pulp, carry out curtain coating (coating) containing the cellulose triacetate that obtains and the solution of solvent on carrier, and peel off the film that this obtains from carrier.
Yet when using the weak point linter pulp, the cost of cellulose triacetate is inevitable high.On the other hand, hard wood pulp is normally favourable aspect cost, but that casting films is peeled off from carrier is unsatisfactory, makes to be difficult to obtain satisfied surface smoothness and sufficiently high productivity.In addition, the paper pulp when using relative lower purity grade during as the about 90-97% of alpha-cellulose content, almost can not obtain the cellulose triacetate of high optical property, though may obtain some improvement at economic aspect.
Therefore, an object of the present invention is to provide a kind of cellulose triacetate of in the curtain coating process, guaranteeing to have good separability, and the method for preparing this cellulose triacetate.
Another object of the present invention provides a kind of preparation method, by this method even can prepare the cellulose triacetate with high stripping performance and satisfied optical property from lower purity grade paper pulp.
To achieve these goals, it is concurrent existing that the inventor has done big quantity research: being present in the rippability that the ratio convection current of seminose in the polysaccharide part (as the neutral polysaccharide part) in wood pulp or the cellulose triacetate and wood sugar delays has very big influence, and even when using when having the wood pulp of relative low levels alpha-cellulose, if the ratio of seminose and wood sugar and preparation condition are controlled as this paper defined, also can be made cellulose triacetate with good optical property.
Therefore, cellulose triacetate of the present invention contains seminose and wood sugar, and the ratio of the seminose/wood sugar of its ratio in the formation sugar of polysaccharide component (as the neutral polysaccharide component) is 0.35-3.0 (mole).In this cellulose triacetate, the total amount (combined amount) of seminose and wood sugar is about 1-5 mole %, the about 58-62.5% of average degree of acetylation of cellulose triacetate in constituting sugar (promptly constituting the monose of polysaccharide component).The cellulose triacetate that satisfies above-mentioned condition has good optical property, as the about 1-10 of yellowness index, the about 1-8 of haze value, the about 60-100% of transparency.Cellulose triacetate with these performances can be used for preparing film.
In preparation method of the present invention,, be the ratio with seminose/wood sugar in constituting sugar that the paper pulp acetylize of 0.35-3.0 (mole) becomes cellulose triacetate in monose.In the method, can use low-purity paper pulp, as alpha-cellulose content be the paper pulp of 90-97% (weight) or in constituting sugar the total amount of seminose and wood sugar be the paper pulp of 2-6 mole %.In order further to improve optical property, the amount and/or the product cellulose triacetate available oxidant that preferably increase acetate in the acetoxylation conversion zone are handled.
In this manual, term " rhodia " refers to " cellulose triacetate " sometimes.In addition, unless stated otherwise, " seminose " and " wood sugar " this paper refers to constitute the corresponding component of polysaccharide component (as the neutral polysaccharide component), and this will introduce in following analysis.That is, " seminose " and " wood sugar " refers to seminose and the wood sugar that exists in paper pulp or the cellulose triacetate, the amount of its indication in seminose and wood sugar as monose value, this will be measured in will analyzing below.
The invention is characterized in: to constitute the monose of polysaccharide component, this cellulose triacetate contains the seminose and the wood sugar of specified proportion, and can be used for preparing film.Therefore, in cellulose triacetate of the present invention, the ratio of seminose/wood sugar (mol ratio) is about 0.35/1 to 3.0/1, preferably is about 0.35/1 to 2.5/1, and more preferably from about 0.35/1 to 2/1.More specifically, the ratio (mol ratio) of seminose/wood sugar is about 0.5/1 to 1.5/1, and is about 0.7/1 to 1.3/1 especially.The ratio of the seminose/wood sugar in the cellulose triacetate can be substantially equal to the corresponding proportion in the former slip.Usually, the ratio that is difficult to obtain seminose/wood sugar is higher than the cellulose triacetate of 3/1 (mol ratio).On the other hand, if the relative quantity of seminose is too low, casting films tends to be adversely affected from the separability on the carrier.
In cellulose triacetate, constituting sugar, the total amount of seminose and polysaccharide (combined amount) can be for example be about 1-5 mole %, preferably about 1.6-4 mole %, 2-3.5 mole % (as 2.5-3.5 mole %) more preferably from about.
One say that by the way " seminose " and " wood sugar " is the main composition sugar of the hemicellulose (xylan, grape mannosans etc.) that contains in the paper pulp.
Can analyze the sugar composition of magma neutralized product cellulose triacetate by following manner.
Preparation sample (scheme)
The sample of the 200mg thorough drying of accurately weighing, add the sulfuric acid of 3ml 72% and under the ice bath cooling sonication be no more than 2 hours and dissolve this sample fully.In above-mentioned solution, add 39ml distilled water then, fully shake, in nitrogen gas stream, refluxed 3 hours under 110 ℃, and allow its cooling more than 30 minutes.Add the 14g barium carbonate then and under frozen water cooling by ultrasonic neutralization.After 30 minutes, add other 10g barium carbonate being neutralized into the about 5.5-6.5 of pH, and filter.Dilute 100 times of this filtrates (weight ratio) with ultra-pure water, to make test specimens.
Analyze
Under following condition by this sample of ion chromatography.
High performance liquid chromatography (HPLC, Dionex Co., DX-AQ) detector: pulse amperometer (Au electrode) post: Dionex Co., Carbo Pac PA-1 (250 * 4mm) eluents: 2mM NaOH. flow velocity: 1.0ml/ branch. post column: Dionex Co., AMMS-II.
From the calibration curve of drawing with seminose, wood sugar and glucose authentic sample, can record the mol ratio of seminose, wood sugar and glucose.Each is formed contents of monosaccharides and represents with mole %, and the total amount of above-mentioned 3 components counts 100%.Should understand that the combined amount of seminose and wood sugar refers to hemicellulose level sometimes in this manual.
In order to improve dimensional stability, wet fastness and thermotolerance, the average degree of acetylation of cellulose triacetate can be for example be about 58-62.5%, preferably about 58.5-62%, 59-62% (as 60-61%) more preferably from about.
Degree of acetylation is represented the amount of the acetate of bonding, and represents with the weight percentage of the Mierocrystalline cellulose bonding acetate of per unit weight.Can measure its degree of acetylation according to the method for the mensuration degree of acetylation described in the ASTM D-817-91 (testing method of rhodia etc.).Testing method is as follows.The pre-dry cellulose triacetate of 1.9g of accurately weighing, be dissolved in 150ml acetone-dimethyl sulfoxide (DMSO) mixture (4: 1, v/v) in, add the water-soluble 1N sodium hydroxide solution of 30ml, and 25 ℃ of saponification 2 hours.Add phenolphthalein as indicator, and with 1N sulfuric acid (concentration factor: the F) sodium hydroxide of overtitration.Use the same method and carry out a blank test, and calculate degree of acetylation according to following formula.Degree of acetylation (%)=[6.5 * (B-A) * F]/W wherein A represents to join 1N vitriolic amount (ml) in the sample, and B represents to be added to the 1N vitriolic amount (ml) in the blank sample, and F represents 1N vitriolic concentration factor, and W is the weight of sample.
The polymerization degree of rhodia is represented with viscometric degree of polymerization, is about 200-400, preferably about 250-400, more preferably from about 270-400 (as 290-400).Usually, the about 270-350 of viscometric degree of polymerization.
Mean polymerisation degree can be measured according to people's such as Uda limiting viscosity method.(Kazuo Uda ﹠amp; HideoSaito: fibre science and technological associations' magazine (Journal of the Society of Fiber Science andTechnology) Japan, the 18th volume, No.1,105-120,1962).Testing method is as follows.
By predetermined concentration C (2.00g/L) cellulose triacetate is dissolved in the mixture (9: 1, weight ratio) of methylene chloride-methanol.Then, this solution is injected Ostward viscometer and be determined at 25 ℃ of these solution stream and cross time t (second) between the viscometer scale.On the other hand, measure blank flushing time t with above-mentioned solvent mixture
0(second), and calculate viscometric degree of polymerization according to following formula:
η
Relatively=t/t
0
[η]=(ln η
Relatively)/C
DP=[η]/(6 * 10
-4) wherein t represent the flushing time (second) of this solution, t
0The flushing time (second) of expression solvent, C represents the concentration (g/L) of the cellulose triacetate of this solution, η
RelativelyThe expression relative viscosity, [η] is limiting viscosity, and DP is a viscometric degree of polymerization.
For example, when using methylene chloride-methanol=9/1 (weight ratio) as solvent mixture, the viscosity of 6% (weight) cellulose triacetate can for example be about 200-700mPa.s, preferably about 250-600mPa.s, and be in particular 250-500mPa.s.
The yellowness index (YI) of the yellow scale will of cellulose triacetate for example can be about 1-10 (preferred 1-7,2-8 usually), and the haze value is about 1-8 (preferred 1-5,2-7 usually).The transparency of cellulose triacetate for example can be about 60-100% (preferred 70-100%, more preferably 75-100%), and is generally about 70-85%.
Following mensuration YI, haze and transparency.[yellowness index (YI)]
The pre-dry cellulose triacetate of 12.0g (CTA) of accurately weighing adds 88.0g methylene chloride-methanol mixture (9: 1, w/w), and dissolving (concentration that contains CTA is the solution of 12% (weight)) fully.Use color difference meter (Nippon Denshoku Kogyo Co., Led., color difference meter ∑ 90) and glass cell (45mm is wide, 45mm height, optical path length 10mm), measure and by following formula calculating YI.
YI=YI
2-YI
1YI wherein
1The YI of expression methylene chloride-methanol mixture (9: 1, w/w), YI
2The YI of the solution of expression CTA12% (weight ratio).[haze]
The pre-dry 12.0g cellulose triacetate of accurately weighing, add 88.0g methylene chloride-methanol mixture (9: 1, w/w), dissolving (CTA 12% (weight ratio) solution) fully.
Use turbidometer (Nippon Denshoku Kogyo Co., Ltd.) and glass cell (45mm is wide, 45mm height, optical path length 10mm), following mensuration.
The methylene chloride-methanol mixture (9: 1, w/w) add in the glass cell, this glass cell is placed turbidometer, return to zero and proofread and correct.Then, CTA 12% (weight ratio) solution is placed glass cell, this glass cell is placed turbidometer, write down its reading.[transparency]
The pre-dry cellulose triacetate of 8.0g (CTA) of accurately weighing, add the 125.3g methylene chloride-methanol (9: 1, w/w) mixture, and dissolving (CTA6% (weight ratio) solution) fully.
The AKA photoelectricity chromascope of cesium phototube and strainer No.12 is equipped with in use, the methylene chloride-methanol mixture (9: 1, w/w) put into the glass cell that optical path length is 100mm, and measure blank transparence.Then, the solution of CTA6% (weight ratio) is placed in the glass cell that optical path length is 100mm, and measures its transparence.As 100%, the percentage ratio of transparency value that writes down this sample solution is as the transparence of this sample blank transparency value.
Cellulose triacetate of the present invention can contain one or more softening agent, comprising: for example, and phosphoric acid ester such as triphenylphosphate (TPP), Tritolyl Phosphate (TCP) etc.; Phthalic ester such as dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP) (DOP), di-2-ethylhexyl phthalate etc.; Fatty acid ester is as butyl oleate, acetyl methyl ricinoleate, Uniflex DBS etc.; Citrate is as citric acid acetyl triethyl (OACTE), acetyl tributyl citrate (OACTB) etc.; Triphen pregnancy acid esters etc.
Cellulose triacetate can contain antiaging agent, receives agent and other auxiliary agents as oxidation inhibitor, UV light absorber, peroxide decomposer, radical scavenger, metal inactivator or sequestrant, acid.If desired, this cellulose triacetate can contain these other auxiliary agents, as nucleator, inorganic powder (as diatomite, lime carbonate, titanium dioxide etc.), thermo-stabilizer, fire retardant and tinting material.
In the methods of the invention, the specific paper pulp of acetylize prepares cellulose triacetate.The ratio (mol ratio) of seminose/wood sugar therefore, in monose, it is about 0.35/1 to 3.0/1[preferred 0.5/1 to 3/1 that raw material paper pulp should have, more preferably 0.7/1 to 2/1] is as mentioning cellulose triacetate.These paper pulp comprise the paper pulp of at least mainly being made up of cork (needlebush) slurry, and this soft wood pulp can use with cotton linter pulp and/or hard wood pulp.With respect to 100 weight part soft wood pulps, the ratio of cotton linter pulp and/or hard wood pulp can be at 0-300 weight part (as the 0-200 weight part), preferably select in about 0-100 weight part.
Compare with hard wood pulp with cotton linter pulp, the alpha-cellulose content of soft wood pulp is few, and this alpha-cellulose content is the sign of purity, and therefore, the purity of soft wood pulp is relatively low.For this reason, consider the optical property of cellulose triacetate, use soft wood pulp normally disadvantageous.Yet, according to technology of the present invention, can improve the optical property of cellulose triacetate, keep casting films on carrier, to have good separability simultaneously, in addition when use about 90-97% (weight), preferably about 92-96% (weight), more preferably from about 93-95% (weight), particularly the low-purity paper pulp of about 90-95% (weight) alpha-cellulose content are also like this.
About the total amount of seminose in the paper pulp and wood sugar (half fibre weight), for example, for about 2-6 mole %, be in particular 2.5-5 mole % (as 3-5 mole %).From a kind of like this paper pulp,, can make cellulose triacetate with satisfied optical property according to the inventive method.
Cellulose triacetate can be prepared by conventional preparation technology, for example, uses method, acetate method and the methylene dichloride method of sulfuric acid as catalyzer.Cellulose triacetate is preparation by the following method usually: with acetate etc. handle former slip (Mierocrystalline cellulose) (activation step), this former slip of usefulness diacetyl oxide acetylize in the presence of sulfuric acid catalyst; to make cellulose triacetate (acetylize step); with this triacetate of hydrolysis, regulate its degree of acetylation (saponification step).
In the method, can spray acetate mist or acetic acid aqueous solution by going up, or, can carry out its activation step by paper pulp being immersed in the bath of acetate or acetic acid aqueous solution to paper pulp (Mierocrystalline cellulose).With respect to 100 weight part paper pulp (Mierocrystalline cellulose), the amount of acetate is about the 10-100 weight part, preferably about 20-80 weight part, more preferably from about 30-60 weight part.
The amount that is used for the diacetyl oxide of acetylize step can be selected in helping the scope of above-mentioned degree of acetylation.Therefore, based on 100 weight part paper pulp (Mierocrystalline cellulose), the amount of diacetyl oxide can for example be about 230-300 weight part, preferably about 240-290 weight part, more preferably from about 250-280 weight part.
In the acetylize step, acetate is usually as solvent.The acetate amount that is used for this purpose for example can be about 200-700 weight part, and preferably about 300-600 weight part, and 350-500 weight part more preferably from about are with respect to per 100 weight part paper pulp (Mierocrystalline cellulose).
The seminose that contains aforementioned proportion when use and wood sugar are when having the paper pulp (the particularly paper pulp of mainly being made up of soft wood pulp) of relative high hemicellulose level thus, and common optical property to cellulose triacetate has adverse influence.For the transparency of using this paper pulp and reducing its yellowness index and improve cellulose triacetate; suggestion increases the amount of acetate in the acetylize step; make it be not less than about 400 weight parts (as the 400-500 weight part); preferably be not less than 450 weight parts (as the 450-500 weight part), with respect to 100 weight part paper pulp.
The vitriolic amount is generally about 1-15 weight part in per 100 weight part Mierocrystalline celluloses, preferably about 5-15 weight part, and preferably about 5-10 weight part.
Can for example carry out saponification step under about 50-70 ℃ the temperature.
In order further to improve the optical property of cellulose triacetate, suggestion is at suitable preparatory phase oxidizer treatment cellulose triacetate, for example behind the acetylization reaction or after saponification (hydrolysis) reaction.No matter the consumption of acetate is how in the acetylize step, be effectively with this processing of oxygenant, but the cellulose triacetate that makes when the acetate acetylize of use increasing amount so when oxidized, the optical property of cellulose triacetate further improves.
Spendable oxygenant comprises but is not limited to: hydrogen peroxide; Peracid is as peroxyformic acid, peracetic acid, peroxybenzoic acid, lauroyl peroxide, benzoyl peroxide base etc.; And organo-peroxide, as diacetyl peroxide base etc.Each can be used singly or in combination these oxygenants.Preferred oxygenant is that those remove the oxygenant that does not stay any obvious resistates easily from cellulose triacetate, comprises hydrogen peroxide, peroxyformic acid and peracetic acid.Preferred especially hydrogen peroxide and peracetic acid.
The amount of oxygenant can be selected according to needed optical parameter value, according to 100 weight part cellulose triacetates, can for example about 0.01-5 weight part, and preferably about 0.1-2.5 weight part, and be about the 0.1-1 weight part especially.
Can be suitable under the temperature of oxygenant, for example about 20-100 ℃, preferably about 30-70 ℃, handle with oxygenant.
In order to improve the stability of cellulose triacetate, can in the product cellulose triacetate, add thermo-stabilizer, as an alkali metal salt (as sylvite, sodium salt etc.) or alkaline earth salt (calcium salt, magnesium salts, strontium salt, barium salt etc.).
The cellulose triacetate that makes is thus made dope (dope) and carry out curtain coating on appropriate carriers with organic solvent usually, in the dry back of part (leather hard), peels off this film from carrier.Dry then record from film with the preparation film.
The above-mentioned organic solvent of mentioning comprises: for example, halogenated hydrocarbon (as methylene dichloride, ethylene dichloride etc.), ketone (as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.), ester class (as manthanoate such as ethyl formate etc., acetic ester such as methyl acetate and ethyl acetate etc., ethyl lactate etc.), ethers (such as diox, glycol dimethyl ether etc.), the mixture of cellosolve class (as methylcyclohexane, ethyl cellosolve etc.), cellosolve acetate (as acetic acid methyl cellosolve, acetate ethyl cellosolve etc.) and these solvents.This solvent can contain nitro-compound (as Nitromethane 99Min., nitroethane, nitropropane etc.) and/or lower alcohol (as methyl alcohol, ethanol, Pyranton etc.).
The amount of solvent can not selected in convection current ductility and processibility have the scope of disadvantageous effect.Therefore, based on 100 weight part cellulose triacetates, the usage quantity of solvent can for example be about 150-1000 weight part (cellulose triacetate of about 10-40% (weight ratio) concentration), preferred about 200～900 weight parts (cellulose triacetate concentration is 10～30% weight ratios).The concentration of cellulose triacetate is about 10-25 (weight) % (for example, 10-20 (weight) %) usually in dope.
Carrier can be the carrier of any routine, for example can be mirror polish or speculum metal carrier (as stainless steel carrier).
Because cellulose triacetate of the present invention has good rippability, the film of leather hard can be peeled off from carrier easily, and the result can obtain the very high cellulose triacetate of surface flatness.In addition, tri cellulose acetate membrane of the present invention has good optical property (yellowness factor, haze and transparency).
Can select the thickness of tri cellulose acetate membrane according to desired purposes, for example about 5-500 μ m, preferably about 10-200 μ m, more preferably from about in 20-150 μ m (especially at the 50-150 μ m) scope.
Cellulose triacetate of the present invention not only can be used for photographic film, polarizer protective membrane or colored filter film by the curtain coating technology, and can utilize its good separability by as spin coating process it being used as the material of preparation Film Optics film and device.
Because cellulose triacetate of the present invention contains the seminose and the wood sugar of specified proportion, it is easy to peel off to obtain the film of high surface flatness from carrier in casting method.In addition, even make raw material, also can obtain the cellulose triacetate of good optical property with the paper pulp of low-purity.
Embodiment
The following examples are to be used for more illustrated in greater detail the present invention, must not think to limit scope of the present invention.
Embodiment 1
Spraying activates to 100 weight part cork sulfite pulps (alpha-cellulose content 94.5%, the about 2.0 moles of % of mannose content, the about 1.8 moles of % of wood sugar content) with 50 weight part glacial acetic acids.In activatory mixture, add 470 weight part glacial acetic acids, 265 weight part diacetyl oxides and 8.3 weight part vitriolic mixtures, and carry out esterification in a usual manner then.Afterwards, the reaction that is hydrolyzed, making degree of acetylation is 61.3%, viscometric degree of polymerization is 301 cellulose triacetate (CTA, 1.42 moles of % of mannose content, 1.51 moles of % of wood sugar content).The YI of this CTA is 6.6, haze value 5.2 and transparency are 82.2%.
Above-mentioned 100 weight part CTA are mixed with 320 weight part methylene dichloride, 40 weight part methyl alcohol, 25 weight part butanols and 15 weight part triphenylphosphates (TPP), make dope.At room temperature go up this dope of curtain coating at slick stainless steel plate (carrier), and at room temperature placed 3-4 minute with the thickness of about 1mm.Then, according to the separability of this film of following criterion evaluation from the carrier.The peelable grade of film is " zero ".Zero: just can peel off smoothly with minimum peeling force, and film surface is smooth.*: can not peel off smoothly when feeling sizable peeling force is arranged, film is peeled off off-chip still on stainless steel plate.
Embodiment 2
Spraying activates to 100 weight part cork sulfite pulps (alpha-cellulose content 94.5%, the about 2.0 moles of % of mannose content, the about 1.8 moles of % of wood sugar content) with 50 weight part glacial acetic acids.In activatory mixture, add 445 weight part glacial acetic acids, 265 weight part diacetyl oxides and 8.3 weight part vitriolic mixtures, and carry out esterification in a usual manner then.Afterwards; reaction is hydrolyzed; and based on 100 weight part CTA; the hydrogen peroxide of 0.2 weight part is mixed with this hydrolysising product solution equably as SYNTHETIC OPTICAL WHITNER; to make degree of acetylation is 60.9%; viscometric degree of polymerization is 313 cellulose triacetate (CTA, 1.23 moles of % of mannose content, 1.34 moles of % of wood sugar content).The YI of this CTA is 3.1, haze value 2.7 and transparency are 79.2%.
When the mode identical with embodiment 1 assessed the rippability of this film on carrier, the peelable grade of this film only was " zero ".
Embodiment 3
Except using cork sulfite pulp (alpha-cellulose content 96.1%, the about 1.4 moles of % of mannose content, the about 1.4 moles of % of wood sugar content) to replace the former slip of embodiment 1 usefulness, the method that repeats embodiment 1 in other respects prepares cellulose triacetate (CTA).The mannose content of this CTA is that 0.76 mole of %, wood sugar content 0.73 mole of %, YI are 6.8, haze value 6.0; Transparency is 84.0%.As the rippability of embodiment 1 assessment CTA on carrier, comment rank be " zero ".Comparative example
Spraying activates to 100 weight part hardwood kraft pulp (alpha-cellulose content 98.3%, the about 0.3 mole of % of mannose content, the about 1.1 moles of % of wood sugar content) with 50 weight part glacial acetic acids.In activatory mixture, add 445 weight part glacial acetic acids, 265 weight part diacetyl oxides and 8.3 weight part vitriolic mixtures, and carry out esterification in a usual manner then.Afterwards, the reaction that is hydrolyzed, making degree of acetylation is 61.0%, viscometric degree of polymerization is 286 cellulose triacetate (CTA, 0.28 mole of % of mannose content, 1.03 moles of % of wood sugar content).The YI of this CTA is 9.5, haze value 3.4 and transparency are 74.2%.
As embodiment 1, assess the rippability of this film, be chosen as " * ".
Claims (8)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870703A (en) * | 1973-06-21 | 1975-03-11 | Canadian Cellulose Company Lim | Production of cellulose esters |
| CN1087645A (en) * | 1992-09-24 | 1994-06-08 | 代科化学工业株式会社 | fatty acid ester of cellulose, cellulose diacetate and preparation method thereof |
| JPH08319301A (en) * | 1995-05-29 | 1996-12-03 | Daicel Chem Ind Ltd | Cellulose acetate and its production |
| JPH0977801A (en) * | 1995-09-14 | 1997-03-25 | Daicel Chem Ind Ltd | Homogenous cellulose-acetate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870703A (en) * | 1973-06-21 | 1975-03-11 | Canadian Cellulose Company Lim | Production of cellulose esters |
| CN1087645A (en) * | 1992-09-24 | 1994-06-08 | 代科化学工业株式会社 | fatty acid ester of cellulose, cellulose diacetate and preparation method thereof |
| JPH08319301A (en) * | 1995-05-29 | 1996-12-03 | Daicel Chem Ind Ltd | Cellulose acetate and its production |
| JPH0977801A (en) * | 1995-09-14 | 1997-03-25 | Daicel Chem Ind Ltd | Homogenous cellulose-acetate |
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