CN113122951B - Fiber filament prepared from graft polymer of cellulose and PET - Google Patents
Fiber filament prepared from graft polymer of cellulose and PET Download PDFInfo
- Publication number
- CN113122951B CN113122951B CN201911405152.9A CN201911405152A CN113122951B CN 113122951 B CN113122951 B CN 113122951B CN 201911405152 A CN201911405152 A CN 201911405152A CN 113122951 B CN113122951 B CN 113122951B
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- Prior art keywords
- pet
- solution
- cellulose
- reaction
- spinning
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- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 46
- 239000000835 fiber Substances 0.000 title claims abstract description 42
- 229920002678 cellulose Polymers 0.000 title claims abstract description 33
- 239000001913 cellulose Substances 0.000 title claims abstract description 33
- 238000009987 spinning Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 239000003208 petroleum Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000002166 wet spinning Methods 0.000 claims abstract description 14
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002981 blocking agent Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 114
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 78
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 64
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 55
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 37
- 238000005886 esterification reaction Methods 0.000 claims description 21
- 229920001747 Cellulose diacetate Polymers 0.000 claims description 20
- 238000006068 polycondensation reaction Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- 239000012760 heat stabilizer Substances 0.000 claims description 10
- 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 claims description 10
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 9
- 239000002608 ionic liquid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 229920000875 Dissolving pulp Polymers 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 239000004753 textile Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
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- 229920008347 Cellulose acetate propionate Polymers 0.000 claims description 2
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 2
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 230000015271 coagulation Effects 0.000 claims 1
- 238000005345 coagulation Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 124
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 118
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 48
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 33
- 235000010980 cellulose Nutrition 0.000 description 22
- 239000012482 calibration solution Substances 0.000 description 21
- 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 18
- 238000004448 titration Methods 0.000 description 18
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
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- 238000002474 experimental method Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 description 3
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 3
- 239000012154 double-distilled water Substances 0.000 description 3
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
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- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 description 1
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- HHHBEVPEYINXHC-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;dibutyl phosphate Chemical compound CCCCN1C[NH+](C)C=C1.CCCCOP([O-])(=O)OCCCC HHHBEVPEYINXHC-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- CDQXDHLIOUNOCQ-UHFFFAOYSA-N COP(=O)(OC)O.C(CCC)N1CN(C=C1)C Chemical compound COP(=O)(OC)O.C(CCC)N1CN(C=C1)C CDQXDHLIOUNOCQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- UNLFUFQHYWLHRE-UHFFFAOYSA-N P(=O)(OCC)(OCC)O.C(CCC)N1CN(C=C1)C Chemical compound P(=O)(OCC)(OCC)O.C(CCC)N1CN(C=C1)C UNLFUFQHYWLHRE-UHFFFAOYSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/284—Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Artificial Filaments (AREA)
Abstract
The preparation method comprises the steps of firstly preparing single-end hydroxylated PET by using at least one of m-methylbenzoic acid or p-methylbenzoic acid as a terminal blocking agent, then preparing a graft copolymer with cellulose, dissolving the graft copolymer in a solvent to prepare a spinning solution, and obtaining the fiber filament by a dry-jet wet spinning method. The method adopts monoacid as the end-capping reagent when synthesizing the single-end hydroxyl PET, and the monoacid can completely participate in the reaction, thereby avoiding the occurrence of side reaction, being convenient for regulating and controlling the molecular weight of the product PET and obtaining the PET with uniform molecular weight, and providing a foundation for subsequent spinning; after synthesizing the graft copolymer of cellulose and PET, dichloromethane and petroleum ether are used for sedimentation to purify and then spinning is carried out, so that the solubility of the graft copolymer in the spinning solution is better, the subsequent dry-jet wet spinning process is facilitated, and long fibers are successfully spun.
Description
Technical Field
The invention relates to the technical field of fiber yarns, in particular to a fiber filament prepared from a graft polymer of cellulose and PET.
Background
Cellulose and its derivatives are commonly used raw materials in nature, and the application fields are very wide. For example, Cellulose Diacetate (CDA) is one of the earliest commercialized cellulose derivatives of cellulose, has the advantages of degradability, good toughness, rich sources and the like, is widely applied to the fields of filtration membranes, cigarette filters, textiles and the like, and the CDA fiber obtained by spinning has a series of advantages, such as soft hand feeling, convenient dyeing and the like, but also has the disadvantages, such as low strength and poor wear resistance, thereby limiting the development and application of the CDA fiber.
The polyethylene terephthalate (PET) molecular chain is highly symmetrical, has strong crystallization capacity, and PET has excellent electrical insulation and chemical corrosion resistance, and high fiber strength and good wear resistance. The good performances enable PET to be widely used in the fields of clothing textile, external packaging, preparation of special films and the like, but the PET has the defects of low crystallization rate, non-degradability and the like, and further development and application of the PET are limited.
Based on the two points, the PET grafted and modified cellulose can combine the advantages of two materials, improve the defects of low strength and poor wear resistance of the fiber, and simultaneously reduce the use amount of PET and reduce environmental pollution by utilizing the advantage that the fiber can be degraded.
The patent CN201711391761.4 discloses a CDA-gPET fibrous membranes and their preparation, but they use the electrospinning process, generally resulting in a membrane material consisting of filaments with a diameter on the order of nanometers/micrometer on a microscopic scale. In addition, when the CDA-g-PET graft copolymer is produced by melt spinning, oxidative decomposition is likely to occur during melt spinning, and melt spinning is difficult, and a CDA-g-PET long fiber having excellent properties is not easily obtained.
Therefore, it is a problem to be solved to obtain a composite long fiber having both excellent tensile strength at break and water absorption capacity.
Disclosure of Invention
In order to solve the problems of low yield of intermediate products, high difficulty in obtaining long fibers, low breaking strength of the fibers or low water absorption rate in the process of preparing long fibers by using a graft polymer of cellulose and PET in the prior art, the invention provides a fiber filament prepared by using the graft polymer of cellulose and PET and a preparation method thereof.
In order to realize the technical purpose, the invention adopts the following technical scheme:
the first aspect of the present invention provides a method for preparing a fiber filament prepared from a graft polymer of cellulose and PET, comprising the steps of:
(1) preparation of single-terminal hydroxyl PET: mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.2-1.6, adding at least one selected from m-methyl benzoic acid or p-methyl benzoic acid as a capping agent, an esterification catalyst and a heat stabilizer, and carrying out esterification reaction and polycondensation reaction on the terephthalic acid and the ethylene glycol to obtain single-end hydroxylated PET;
(2) preparation of graft polymers of cellulose and PET: dissolving the PET with the single end hydroxylated in the step (1) in tetrachloroethane, and adding an ionic liquid, diisocyanate and an organic tin compound catalyst to obtain a tetrachloroethane solution of an isocyanate-terminated prepolymer; dissolving cellulose and/or derivatives thereof in tetrachloroethane solution, adding the solution into tetrachloroethane solution of the isocyanate-terminated prepolymer, purifying the product after the reaction of the two, settling the product by using dichloromethane and petroleum ether to obtain a solid product, and drying the solid product to obtain a purified graft copolymer of the cellulose and the PET;
(3) preparing a spinning solution: dissolving a graft copolymer of cellulose and PET in a solvent to obtain a bubble-free uniform spinning solution;
(4) spinning by dry-jet wet spinning: extruding the spinning solution through a spinneret plate with the aperture of 0.1-0.5mm, enabling the extrusion speed of a metering pump to be 6-9m/min, enabling the spinning solution to enter a coagulating bath after passing through an air section with the length of 3-10cm, and obtaining fiber filaments at the drafting rate of a first roller of 5-30 m/min.
Further, the molar ratio of the end-capping reagent to the terephthalic acid in step (1) is 0.025 to 0.5: 1. The capping agent is further preferably p-toluic acid.
Further, after adding the end-capping reagent, the esterification catalyst and the heat stabilizer in the step (1), firstly raising the temperature to 230-240 ℃, and carrying out esterification reaction on terephthalic acid and ethylene glycol; the polycondensation reaction is carried out in two steps, after the esterification reaction, the reaction temperature is firstly raised to 260-270 ℃, the vacuum degree is adjusted to 900-1100Pa, and the pre-polycondensation reaction is carried out for 50-70 min; then the reaction temperature is adjusted to 280-290 ℃ and the vacuum degree is 80-200Pa, and the secondary polycondensation reaction is carried out for 20-30 min.
Further, the heat stabilizer in step (1) is at least one selected from the group consisting of triphenyl phosphate, diphenyl phosphate, triphenyl phosphite and diphenyl phosphite, and is added in an amount of 0.5% to 3.0% by weight based on the terephthalic acid.
Further, the esterification catalyst in the step (1) is at least one of antimony trioxide, antimony acetate, ethylene glycol antimony, titanium dioxide or ethylene glycol titanium, and the addition amount of the esterification catalyst is 0.02 to 0.08 percent of the weight of the terephthalic acid.
Further, after the polycondensation reaction in the step (1) is finished, the method also comprises a step of purifying the synthetic product, wherein the purification is to dissolve the synthetic product in hexafluoroisopropanol and then use acetone for settling and drying to obtain the purified single-end hydroxylated PET.
Further, in the step (2), the mass concentration of the PET in tetrachloroethane is 2-15%. It reacts with ionic liquid, diisocyanate and organic tin compound catalyst at 60-80 deg.c for 2-6 hr.
Further, the temperature for reacting the cellulose and/or the derivative thereof with the isocyanate-terminated prepolymer in the step (2) is 65-75 ℃ and the time is 2-24 h.
Further, the mixing ratio of the PET, the cellulose and/or the derivative thereof in the step (2) is controlled so that the yield of the graft copolymer is 50% to 90%. The yield, defined as the ratio of the mass of the grafted product to the sum of the masses of the starting materials, is mainly influenced by the reaction time, the longer the reaction time, the higher the yield, but after a reaction time of more than 10 hours, the grafting is saturated and the yield no longer changes significantly. In the case of graft saturation, the maximum yield of the graft copolymer is controlled by adjusting the raw material addition ratio.
Further, the ionic liquid in the step (2) is at least one selected from phosphate ionic liquids, acetate ionic liquids and chloride ionic liquids, more specifically at least one selected from 1-butyl-3-methyl imidazole dibutyl phosphate, 1-butyl-3-methyl imidazole diethyl phosphate, 1-butyl-3-methyl imidazole dimethyl phosphate, 1-butyl-3-methyl imidazole acetate, 1-butyl-3-methyl imidazole chloride and 1-butyl-3-methyl pyridine chloride, preferably 1-butyl-3-methyl imidazole chloride, and the addition amount thereof is 0.1-10% by weight of the cellulose and/or the derivative thereof.
Further, the diisocyanate in the step (2) is selected from at least one of isophorone diisocyanate (IPDI), 2, 4-Toluene Diisocyanate (TDI), 4' -diphenylmethane diisocyanate (MDI), 1, 6-Hexamethylene Diisocyanate (HDI), 1, 5-Naphthalene Diisocyanate (NDI), and Xylylene Diisocyanate (XDI), preferably isophorone diisocyanate; the amount added is such that the molar ratio of PET terminal hydroxyl groups to diisocyanate is 1: 0.8-1.5.
The method for measuring the content of the PET terminal hydroxyl groups comprises the following steps: dissolving PET by using dehydrated tetrachloroethane as a solvent, adding excessive succinic anhydride to perform acylation reaction with a hydroxyl value in the PET, converting a tail end into a carboxyl group, ensuring that the reaction is performed in a forward reaction direction by using a proper amount of triethylamine, performing the reaction for a sufficient time (48 hours) at 25 ℃, performing the whole reaction under the conditions of no water and no oxygen, and settling and drying petroleum ether after the reaction is finished to obtain the PET with the modified terminal group.
The method comprises the following specific steps of preparing a standard potassium hydroxide-ethanol calibration solution, c (KOH) =0.6 mol/L, standing the solution for one week, taking supernatant for use, and calibrating by using an aqueous solution of potassium hydrogen phthalate during use, wherein the specific calibration process comprises the following specific steps:
weighing about 0.5 g of potassium hydrogen phthalate, dissolving the potassium hydrogen phthalate by using proper double distilled water, dropwise adding 10 drops of phenolphthalein reagent, and titrating the solution by using a potassium hydroxide ethanol standard titration solution until pink is kept for 30 seconds and the titration end point is obtained. And (3) solving the concentration of the standard potassium hydroxide ethanol calibration solution by utilizing an acid-base neutralization law, repeating the experiment for three times, and taking the average value as the concentration of the standard potassium hydroxide ethanol calibration solution.
Blank control group:
20mL of tetrachloroethane was charged into a single-neck flask, and the mixture was heated and stirred at 110 ℃. And (3) dropping 10 drops of phenolphthalein reagent after the temperature is reduced to room temperature, titrating the solution to pink by using a standard titration solution of potassium hydroxide ethanol, keeping the pink from changing color for 30s, namely a titration end point, and recording the volume of the consumed calibration solution of potassium hydroxide ethanol.
PET experimental group:
an appropriate amount of modified PET (accurate to 0.2 mg) was weighed into a single-neck bottle, tetrachloroethane equivalent to the blank was added, and the mixture was heated and stirred until completely dissolved. And (3) dropping 10 drops of phenolphthalein reagent after the temperature is reduced to room temperature, titrating the solution to pink by using a standard titration solution of potassium hydroxide ethanol, keeping the pink from changing color for 30s, namely a titration end point, and recording the volume of the consumed calibration solution of potassium hydroxide ethanol.
The hydroxyl number is calculated according to the following formula:
X 2 = ( V 1 -V 2 ) × c × 56.10/m –X 1 （1-2）
in the formula:
X 2 -hydroxyl number, mg KOH/g;
X 1 -acid number, mg KOH/g;
V 1 measuring the using amount, mL, of the potassium hydroxide ethanol calibration solution in the sample;
V 2 the amount of the potassium hydroxide ethanol used for calibrating the solution is mL in the blank experiment;
c, the concentration of the potassium hydroxide ethanol calibration solution, mol/L;
m is the weight of the sample, g;
56.10-molar mass of potassium hydroxide, g/mol.
The results of the measurements are expressed as the arithmetic mean of two parallel measurements, and two significant figures are retained, while the difference between the results of the two parallel measurements is not more than 0.5mg KOH/g.
Further, the organotin compound catalyst described in the step (2) is at least one selected from the group consisting of dibutyltin dilaurate, dibutyltin diacetate and stannous octoate, and the added amount thereof is 0.05 to 0.4% by weight of the terephthalic acid.
Further, the cellulose and/or the derivative thereof in the step (2) is microcrystalline cellulose or/and nano microcrystalline cellulose, and the number average molecular weight is 25000-60000; the cellulose derivative is at least one of cellulose acetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose or benzyl cellulose, and the number average molecular weight is 20000-100000.
Further, as a more specific embodiment, the purification in the step (2) is: and (2) dropwise adding dichloromethane with the volume of 0.5-2 times that of the reaction solution into the solution after the grafting reaction is finished to separate out floccules, dropwise adding petroleum ether with the volume of 0.3-1 time that of the reaction solution to further separate out floccules, pouring out the solution to leave precipitates, repeatedly washing the precipitates with dichloromethane and petroleum ether, and finally obtaining the purified graft polymer through vacuum drying.
Further, in the step (3), the mass ratio of the graft copolymer to the solvent is 1: 1.5-3, and obtaining the uniform spinning solution without bubbles by sealing and vacuum defoaming the spinning solution.
Further, the solvent used for preparing the spinning dope in the step (3) is at least one selected from the group consisting of 1,1,2, 2-tetrachloroethane, Hexafluoroisopropanol (HFIP) and dimethyl sulfoxide (DMSO), and is preferably dimethyl sulfoxide.
Further, the specific operation of dissolving the graft copolymer in the solvent to prepare the spinning solution in the step (3) is as follows: mixing the graft copolymer with the solvent, standing for 60-120min, fully swelling, heating to 75-95 ℃, and stirring at high speed for 24-36h to completely dissolve.
Further, the specific operating conditions for extruding the spinning solution through the spinneret in the step (4) are as follows: the pressure is controlled to be 0.2-0.5MPa, and the temperature is controlled to be 20-40 ℃. The coagulating bath is a DMSO aqueous solution with the mass concentration of 20% -35%.
It is a technical object of the second aspect of the invention to provide a fibre filament prepared by the above method.
The technical purpose of the third aspect of the invention is to provide the application of the fiber filament in clothing textile. The fiber yarn has high water absorption rate and high breaking strength, and has good application effect in clothing textile.
Compared with the prior art, the invention has the following advantages:
(1) the method adopts monoacid as the end-capping reagent when synthesizing the single-end hydroxyl PET, and the monoacid can completely participate in the reaction, thereby avoiding the occurrence of side reaction, being convenient for regulating and controlling the molecular weight of the product PET and obtaining the PET with uniform molecular weight, and providing a foundation for subsequent spinning;
(2) on the basis of reducing side reactions in the step (1), the graft copolymer of cellulose and PET is synthesized in the step (2), then dichloromethane and petroleum ether are used for settlement for purification, and then spinning operation is carried out, so that the graft copolymer has better solubility in the process of preparing the spinning solution, the subsequent dry-jet wet spinning process is facilitated, and the graft copolymer obtained by resynthesis of other end-capping agents such as monoacid and the like can generate a certain amount of insoluble substances in the process of preparing the spinning solution, and the spinning effect and the product performance are influenced.
(3) The long fiber is successfully spun by the graft polymer of the cellulose and the PET by adopting a dry-jet wet spinning method, the technical problem that the long fiber is difficult to spin by the graft polymer of the cellulose and the PET is solved, the fiber has excellent performance, higher water absorption rate and better fracture resistance, and the method is easy for large-scale production.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an infrared spectrum of the single-end hydroxylated PET prepared in the step (1) of example 1 before and after purification;
FIG. 2 nuclear magnetic spectrum of the single-end hydroxylated PET prepared in step (1) of example 1;
FIG. 3 is an IR spectrum of the graft copolymer CDA-g-PET prepared in example 1.
Fig. 4 and 5 are both apparent images of the fiber filaments prepared in example 1.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Graft polymers of cellulose CDA and PET were prepared in examples 1-4:
example 1
(1) Preparation of single-terminal hydroxyl PET: mixing terephthalic acid (PTA) and Ethylene Glycol (EG) in a molar ratio of 1:1.5, and simultaneously adding an end capping agent of p-toluic acid, an esterification catalyst of ethylene glycol antimony and a heat stabilizer of triphenyl phosphate, wherein the molar ratio of the p-toluic acid to the terephthalic acid is 0.025, and the ethylene glycol antimony and the triphenyl phosphate are respectively 0.05 percent and 3.0 percent of the terephthalic acid in weight; heating to 235 ℃ for esterification reaction, then heating to 265 ℃, keeping the vacuum degree at 1000Pa for pre-polycondensation reaction for 60min, heating to 285 ℃, adjusting the vacuum degree at 100Pa for polycondensation reaction for 25min, dissolving the synthetic product in hexafluoroisopropanol, and then using acetone for settling and drying to obtain the purified single-end hydroxylated polyethylene terephthalate (PET).
(2) Preparation of graft Polymer CDA-g-PET: dissolving the PET prepared in the step (1) in tetrachloroethane, wherein the mass concentration of the PET in the solution is 9%, adding 1-butyl-3-methylimidazolium chloride (the adding amount is 1% of the weight of CDA to be added), isophorone diisocyanate (the adding amount is 1:1.5 of the molar ratio of PET terminal hydroxyl groups to diisocyanate), and dibutyltin dilaurate (the adding amount is 0.4% of terephthalic acid), and obtaining a tetrachloroethane solution of an isocyanate-terminated prepolymer; dissolving Cellulose Diacetate (CDA) in tetrachloroethane solution, wherein the mass ratio of CDA to PET is 1:0.5, adding the solution into tetrachloroethane solution of the isocyanate-terminated prepolymer, reacting the solution and the tetrachloroethane solution, slowly dripping 1 time of dichloromethane of the volume of reaction liquid into the solution after the reaction is finished, separating out floccule, slowly dripping 0.5 time of petroleum ether of the volume of the reaction liquid, further separating out floccule, pouring out the solution, repeating the above purification process for 2 times, and finally obtaining the purified CDA-g-PET graft copolymer through vacuum drying.
The infrared spectrograms of the single-end hydroxylated PET prepared in the step (1) before and after purification are shown in figure 1; it can be seen that 1246cm -1 And 1105cm -1 The characteristic peak of (A) corresponds to the stretching vibration of CO on-COOC-, at 1722cm -1 The characteristic peak appears corresponding to the absorption peak of carbonyl stretching vibration at 873cm -1 The peak at (A) is the bending vibration of two adjacent CH's on the aromatic ring, which isThese standard peaks for PET indicate that the experiment succeeded in synthesizing PET. In addition, 3500cm -1 The left and right parts are stretching vibration peaks of unreacted O-H, the change of PET spectrogram before and after purification is compared, and 3500cm after purification is found -1 The stretching vibration peak of the unreacted hydroxyl at the left and right parts disappears, which shows that the ethylene glycol impurity is removed through purification, and the pure PET is obtained.
The nuclear magnetic spectrum of the single-end hydroxylated PET is shown in figure 2; it can be seen that the chemical shift is CF at A 3 COOD, wherein the peak 1 is a H displacement peak on a benzene ring of a main chain, the peak 2 is H on a hard segment methylene in the main chain, and the peak 3 is H of a methyl on chain-end p-methylbenzoic acid. The molecular weight of the resulting single-end hydroxylated PET can be calculated from the area ratio of the 3 peak to the 2 peak.
The infrared spectrogram of the graft copolymer CDA-g-PET prepared in the step (2) is shown in figure 3. The peak comparison table is shown in table 1. From the results of the IR spectrum analysis, it was found that after repeated purification to remove unreacted PET, the characteristic absorption peak of PET still appeared in the grafted product, and the peak was 1551cm -1 Has a characteristic peak of newly generated-NH-bending vibration, and proves the successful synthesis of the CDA-g-PET.
Table 1.
(3) Preparing a spinning solution: mixing the CDA-g-PET prepared in the step (2) with DMSO in a mass ratio of 1: 2.5, mixing, standing for 80min at normal temperature, fully swelling, heating to 90 ℃, mechanically stirring at a high speed of 300r/min for 36h, completely dissolving the solution, sealing the solution, and defoaming in vacuum to obtain the bubble-free uniform spinning solution.
(4) Spinning by a dry-jet wet spinning method: extruding the spinning solution under the pressure of 0.4MPa and at the temperature of 25 ℃, wherein the aperture of a spinneret plate is 0.5mm, a metering pump is 8m/min, 30% DMSO aqueous solution is taken as a coagulating bath, the air section is 5cm, and the drawing speed of one roll is set to be 10m/min to obtain the fiber filament. The appearance is shown in fig. 4 and 5.
Example 2
(1) Preparation of single-terminal hydroxyl PET: mixing terephthalic acid (PTA) and Ethylene Glycol (EG) in a molar ratio of 1:1.5, and simultaneously adding an end-capping reagent of m-methylbenzoic acid, an esterification catalyst of ethylene glycol antimony and a heat stabilizer of triphenyl phosphate, wherein the molar ratio of benzoic acid to terephthalic acid is 0.025:1, and the ethylene glycol antimony and the triphenyl phosphate are respectively 0.05 percent and 3.0 percent of the terephthalic acid in terms of weight; firstly heating to 230 ℃ for esterification reaction, then carrying out pre-polycondensation reaction for 60min at 265 ℃ and under the vacuum degree of 1000Pa, then heating to 285 ℃ and under the vacuum degree of 100Pa for polycondensation reaction for 25min, synthesizing the single-end hydroxylated polyethylene terephthalate (PET), dissolving the synthesized product in hexafluoroisopropanol, and then using acetone for settling and drying to obtain the purified PET.
(2) Preparation of graft Polymer CDA-g-PET: dissolving the PET prepared in the step (1) in tetrachloroethane, wherein the mass concentration of the PET in the solution is 9%, adding 1-butyl-3-methylimidazolium chloride (the adding amount is 1% of the weight of CDA to be added), isophorone diisocyanate (the adding amount is 1:1.5 of the molar ratio of PET terminal hydroxyl groups to diisocyanate), and dibutyltin dilaurate (the adding amount is 0.4% of terephthalic acid), and obtaining a tetrachloroethane solution of an isocyanate-terminated prepolymer; dissolving Cellulose Diacetate (CDA) in tetrachloroethane solution, wherein the mass ratio of CDA to PET is 1:0.5, adding the solution into tetrachloroethane solution of the isocyanate-terminated prepolymer, reacting the solution and the tetrachloroethane solution, slowly dripping 1 time of dichloromethane of the volume of reaction liquid into the solution after the reaction is finished, separating out floccule, slowly dripping 0.5 time of petroleum ether of the volume of the reaction liquid, further separating out floccule, pouring out the solution, repeating the above purification process for 2 times, and finally obtaining the purified CDA-g-PET graft copolymer through vacuum drying.
(3) Preparing a spinning solution: mixing the CDA-g-PET prepared in the step (2) with DMSO according to a mass ratio of 1: 2, mixing, standing for 120min at normal temperature, fully swelling, heating to 80 ℃, mechanically stirring at a high speed of 300r/min for 24h, sealing the solution after the solution is completely dissolved, and defoaming in vacuum to obtain the uniform spinning solution without bubbles.
(4) Spinning by a dry-jet wet spinning method: extruding the spinning solution under the pressure of 0.3MPa and at the temperature of 25 ℃, wherein the aperture of a spinneret plate is 0.2mm, a metering pump is 8m/min, 30% DMSO aqueous solution is taken as a coagulating bath, the air section is 7cm, and the drawing speed of one roll is set to be 10m/min to obtain the fiber filament.
Example 3
(1) Preparation of single-terminal hydroxyl PET: the molar ratio of terephthalic acid (PTA) to Ethylene Glycol (EG) is 1:1.2, meanwhile, an end capping agent of p-methyl benzoic acid, esterification catalysts of ethylene glycol antimony and a heat stabilizer of triphenyl phosphate are added, the molar ratio of the p-methyl benzoic acid to the terephthalic acid is 0.05:1, and the ethylene glycol antimony and the triphenyl phosphate are respectively 0.05 percent and 3.0 percent of the terephthalic acid by weight; heating to 240 ℃ for esterification, then heating to 270 ℃, keeping the vacuum degree at 1100Pa for pre-polycondensation reaction for 70min, heating to 290 ℃, adjusting the vacuum degree at 200Pa for polycondensation reaction for 20min, synthesizing the single-end hydroxylated polyethylene terephthalate (PET), dissolving the synthesized product in hexafluoroisopropanol, and then using acetone for sedimentation and drying to obtain the purified single-end hydroxylated polyethylene terephthalate (PET).
(2) Preparation of graft Polymer CDA-g-PET: dissolving the PET prepared in the step (1) in tetrachloroethane, wherein the mass concentration of the PET in the solution is 9%, adding 1-butyl-3-methylimidazole chloride salt (the adding amount is 1% of the weight of CDA to be added), isophorone diisocyanate (the adding amount is 1:1.5 of the molar ratio of terminal hydroxyl groups of the PET to the diisocyanate), and dibutyltin dilaurate (the adding amount is-0.4% of terephthalic acid), and obtaining a tetrachloroethane solution of an isocyanate-terminated prepolymer; dissolving Cellulose Diacetate (CDA) in tetrachloroethane solution, wherein the mass ratio of CDA to PET is 1:0.5, adding the solution into tetrachloroethane solution of the isocyanate-terminated prepolymer, reacting the solution and the tetrachloroethane solution, slowly dripping 1 time of dichloromethane of the volume of reaction liquid into the solution after the reaction is finished, separating out floccule, slowly dripping 0.5 time of petroleum ether of the volume of the reaction liquid, further separating out floccule, pouring out the solution, repeating the above purification process for 2 times, and finally obtaining the purified CDA-g-PET graft copolymer through vacuum drying.
(3) Preparing a spinning solution: mixing the CDA-g-PET prepared in the step (2) with DMSO according to a mass ratio of 1: 2, mixing, standing for 60min at normal temperature, fully swelling, heating to 95 ℃, mechanically stirring at a high speed of 300r/min for 30h, completely dissolving the solution, sealing the solution, and defoaming in vacuum to obtain the uniform spinning solution without bubbles.
(4) Spinning by a dry-jet wet spinning method: extruding the spinning solution under the pressure of 0.3MPa and at the temperature of 25 ℃, wherein the aperture of a spinneret plate is 0.3mm, a metering pump is 6m/min, a 20% DMSO aqueous solution is used as a coagulating bath, the air section is 3cm, and the drawing speed of one roll is set to be 20m/min to obtain the fiber filament.
Example 4
Steps (1), (2) and (3) were the same as in example 1;
(4) spinning by a dry-jet wet spinning method: extruding the spinning solution under the pressure of 0.2MPa and at the temperature of 40 ℃, wherein the aperture of a spinneret plate is 0.1mm, a metering pump is 7m/min, a 20% DMSO aqueous solution is used as a coagulating bath, the air section is 3cm, and the drawing speed of one roll is set to be 5m/min to obtain the fiber filament.
Example 5
Steps (1), (2) and (3) were the same as in example 1;
(4) spinning by a dry-jet wet spinning method: extruding the spinning solution under 0.2MPa and 40 ℃, wherein the aperture of a spinneret plate is 0.5mm, a metering pump is 9m/min, a 20% DMSO aqueous solution is used as a coagulating bath, an air section is 3cm, and the drawing speed of one roll is set to be 30m/min to obtain the fiber filament.
Example 6
(1) Preparation of single-terminal hydroxyl PET: mixing terephthalic acid (PTA) and Ethylene Glycol (EG) in a molar ratio of 1:1.2, and simultaneously adding an end-capping agent of m-methyl benzoic acid, an esterification catalyst of ethylene glycol antimony and a heat stabilizer of triphenyl phosphate, wherein the molar ratio of the m-methyl benzoic acid to the terephthalic acid is 0.05:1, and the ethylene glycol antimony and the triphenyl phosphate are respectively 0.05 percent and 3.0 percent of the terephthalic acid by weight; heating to 240 ℃ for esterification, then heating to 270 ℃, keeping the vacuum degree at 1100Pa for pre-polycondensation reaction for 70min, heating to 290 ℃, adjusting the vacuum degree at 200Pa for polycondensation reaction for 20min, dissolving the synthetic product in hexafluoroisopropanol, and then using acetone for sedimentation and drying to obtain the purified single-end hydroxylated polyethylene terephthalate (PET).
(2) Preparation of graft Polymer CDA-g-PET: putting the PET prepared in the step (1) into tetrachloroethane, wherein the mass concentration of the PET in the solution is 9%, adding 1-butyl-3-methylimidazolium chloride (the adding amount is 1% of the weight of CDA to be added), isophorone diisocyanate (the adding amount is 1:1.5 of the molar ratio of PET terminal hydroxyl groups to diisocyanate), and dibutyltin dilaurate (the adding amount is 0.4% of terephthalic acid), and obtaining a tetrachloroethane solution of an isocyanate-terminated prepolymer; dissolving Cellulose Diacetate (CDA) in tetrachloroethane solution, wherein the mass ratio of CDA to PET is 1:0.5, adding the solution into tetrachloroethane solution of the isocyanate-terminated prepolymer, reacting the solution and the tetrachloroethane solution, purifying, slowly dripping 1 time of dichloromethane in volume of reaction liquid into the solution after the reaction is finished to separate out floccule, slowly dripping 0.5 time of petroleum ether in volume of the reaction liquid, further separating out floccule, pouring out the solution, repeating the purification process for 2 times, and finally drying in vacuum to obtain the purified CDA-g-PET graft copolymer.
(3) Preparing a spinning solution: mixing the CDA-g-PET prepared in the step (2) with DMSO according to a mass ratio of 1: 2, mixing, standing for 60min at normal temperature, fully swelling, heating to 95 ℃, mechanically stirring at a high speed of 300r/min for 30h, completely dissolving the solution, sealing the solution, and defoaming in vacuum to obtain the uniform spinning solution without bubbles.
(4) Spinning by a dry-jet wet spinning method: extruding the spinning solution under the pressure of 0.3MPa and at the temperature of 25 ℃, wherein the aperture of a spinneret plate is 0.3mm, a metering pump is 6m/min, a 20% DMSO aqueous solution is used as a coagulating bath, the air section is 3cm, and the drawing speed of one roll is set to be 20m/min to obtain the fiber filament.
Example 7
Steps (1), (2) and (3) were the same as in example 2;
(4) spinning by a dry-jet wet spinning method: extruding the spinning solution under the pressure of 0.2MPa and at the temperature of 40 ℃, wherein the aperture of a spinneret plate is 0.1mm, a metering pump is 7m/min, a 20% DMSO aqueous solution is used as a coagulating bath, the air section is 3cm, and the drawing speed of one roll is set to be 5m/min to obtain the fiber filament.
Example 8
Steps (1), (2) and (3) were the same as in example 2;
(4) spinning by dry-jet wet spinning: extruding the spinning solution under the pressure of 0.2MPa and at the temperature of 40 ℃, wherein the aperture of a spinneret plate is 0.5mm, a metering pump is 9m/min, 20% DMSO aqueous solution is taken as a coagulating bath, the air section is 3cm, and the drawing speed of one roll is set to be 30m/min to obtain the fiber filament.
Examples 9 to 16
The operation conditions and the treatment process were the same as in examples 1 to 8, respectively, except that: the mass ratio of the CDA to the PET in the step (2) is 1:1, and the CDA-g-PET with different yields is obtained.
Comparative example 1
The operating conditions and the treatment process are the same as those of example 1, except that: and (5) directly entering a coagulating bath without passing through an air section in the step (4) to obtain the fiber filaments.
The results of measuring the acid value, hydroxyl value, proportion of single terminal hydroxyl group PET and molecular weight of PET prepared in step (1) of examples 1 to 3 and 6 are shown in Table 2.
The acid value determination method comprises the following steps: preparing a standard potassium hydroxide-ethanol calibration solution, wherein c (KOH) =0.1 mol/L, standing the solution for one week, taking supernatant for use, and calibrating by using an aqueous solution of potassium hydrogen phthalate when in use, wherein the specific calibration process is as follows:
weighing about 0.1 g of potassium hydrogen phthalate, dissolving the potassium hydrogen phthalate by using proper double distilled water, dropwise adding 10 drops of phenolphthalein reagent, and titrating the solution by using a potassium hydroxide ethanol standard titration solution until the pink color is kept for 30s without changing the color, namely the titration end point. And (3) solving the concentration of the standard potassium hydroxide ethanol calibration solution by utilizing an acid-base neutralization law, repeating the experiment for three times, and taking the average value as the concentration of the standard potassium hydroxide ethanol calibration solution.
Blank control group:
50 mL of tetrachloroethane was taken and put into a single-neck flask, and heated and stirred at 50 ℃. And (3) dropping 10 drops of phenolphthalein reagent after the temperature is reduced to room temperature, titrating the solution to pink by using a standard titration solution of potassium hydroxide ethanol, keeping the pink from changing color for 30s, namely a titration end point, and recording the volume of the consumed calibration solution of potassium hydroxide ethanol.
PET experimental group:
an appropriate amount of PET (accurate to 0.2 mg) was weighed into a single-neck flask, added with tetrachloroethane equivalent to the blank, and heated with stirring until completely dissolved. And (3) dropping 10 drops of phenolphthalein reagent after the temperature is reduced to room temperature, titrating the solution to pink by using a standard titration solution of potassium hydroxide ethanol, keeping the pink from changing color for 30s, namely a titration end point, and recording the volume of the consumed calibration solution of potassium hydroxide ethanol.
The acid number is calculated according to the following formula:
X= ( V 1 -V 2 ) × c × 56.10/m
in the formula:
x-acid number, mg KOH/g;
V 1 measuring the using amount, mL, of the potassium hydroxide ethanol calibration solution in the sample;
V 2 the amount of the potassium hydroxide ethanol used for calibrating the solution is mL in the blank experiment;
c, the concentration of the potassium hydroxide ethanol calibration solution, mol/L;
m-weight of sample, g;
56.10-molar mass of potassium hydroxide, g/mol.
The results of the two replicates are expressed as arithmetic means and two significant figures are retained, while the difference between the two replicates is no greater than 0.1 mg KOH/g.
The hydroxyl value measuring method comprises the following steps: dissolving PET by using dehydrated tetrachloroethane as a solvent, adding excessive succinic anhydride to perform acylation reaction with a hydroxyl value in the PET, converting a tail end into a carboxyl group, ensuring that the reaction is performed in a forward reaction direction by using a proper amount of triethylamine, performing the reaction for a sufficient time (48 hours) at 25 ℃, performing the whole reaction under the conditions of no water and no oxygen, and settling and drying petroleum ether after the reaction is finished to obtain the PET with the modified terminal group.
The method comprises the following specific steps of preparing a standard potassium hydroxide-ethanol calibration solution, c (KOH) =0.6 mol/L, standing the solution for one week, taking supernatant for use, and calibrating by using an aqueous solution of potassium hydrogen phthalate when in use, wherein the specific calibration process comprises the following steps:
weighing about 0.5 g of potassium hydrogen phthalate, dissolving the potassium hydrogen phthalate by using proper double distilled water, dropwise adding 10 drops of phenolphthalein reagent, and titrating the solution by using a potassium hydroxide ethanol standard titration solution until the pink color is kept for 30s without changing the color, namely the titration end point. And (3) solving the concentration of the standard potassium hydroxide ethanol calibration solution by utilizing an acid-base neutralization law, repeating the experiment for three times, and taking the average value as the concentration of the standard potassium hydroxide ethanol calibration solution.
Blank control group:
20mL of tetrachloroethane was charged into a single-neck flask, and the mixture was heated and stirred at 110 ℃. And (3) dropping 10 drops of phenolphthalein reagent after the temperature is reduced to room temperature, titrating the solution to pink by using a standard titration solution of potassium hydroxide ethanol, keeping the pink from changing color for 30s, namely a titration end point, and recording the volume of the consumed calibration solution of potassium hydroxide ethanol.
PET experimental group:
an appropriate amount of modified PET (accurate to 0.2 mg) was weighed into a single-neck bottle, tetrachloroethane equivalent to the blank was added, and the mixture was heated and stirred until completely dissolved. And (3) dropping 10 drops of phenolphthalein reagent after the temperature is reduced to room temperature, titrating the solution to pink by using a standard titration solution of potassium hydroxide ethanol, keeping the pink from changing color for 30s, namely a titration end point, and recording the volume of the consumed calibration solution of potassium hydroxide ethanol.
The hydroxyl number is calculated according to the following formula:
X 2 = ( V 1 -V 2 ) × c × 56.10/m –X 1
in the formula:
X 2 -hydroxyl number, mg KOH/g;
X 1 -acid number, mg KOH/g;
V 1 measuring the using amount, mL, of the potassium hydroxide ethanol calibration solution in the sample;
V 2 the amount of the potassium hydroxide ethanol used for calibrating the solution is mL in the blank experiment;
c, the concentration of the potassium hydroxide ethanol calibration solution, mol/L;
m is the weight of the sample, g;
56.10-molar mass of potassium hydroxide, g/mol.
The results of the measurements are expressed as the arithmetic mean of two parallel measurements, and two significant figures are retained, while the difference between the results of the two parallel measurements is not more than 0.5mg KOH/g.
The method for measuring the single-end hydroxyl PET ratio comprises the following steps: the proportion of the single-terminal hydroxyl PET in the synthetic PET is calculated by the following formula,
single terminal hydroxyl PET ratio = 2-Mn X 2 * 10 -3 / 56.1
Wherein Mn is the number average molecular weight (g/mol) of PET, X 2 Is the hydroxyl number (mg KOH/g) of PET and 56.10 is the molar mass (g/mol) of potassium hydroxide.
The method for measuring the molecular weight comprises the following steps: using Bruker AK600 NMR spectrometer with deuterated trifluoroacetic acid (CF) 3 COOD) as a solvent, Tetramethylsilane (TMS) as an internal standard, testing the nuclear magnetic spectrum of the single-ended hydroxyl PET at 25 ℃, and determining the structural composition and the molecular weight of the PET according to the chemical shift and the relative integral of related peaks in the figure.
Table 2.
As can be seen from Table 2, the acid value measurement of the resultant PET showed a very small acid value, indicating that the monoacid and terephthalic acid were almost completely reacted in the presence of an excess of ethylene glycol. The hydroxyl value of the synthesized PET is increased along with the increase of the adding amount of the end capping agent, because when other reaction conditions are the same, if the adding amount of the end capping agent is less, more ethylene glycol is removed from short chains of molecules in the polycondensation reaction stage, and the molecular weight of the final product is also higher. The molecular weight measurement result also shows that the more the addition amount of the end-capping reagent is, the smaller the molecular weight of the synthesized PET is, and the molecular weight of the synthesized PET can be accurately controlled by controlling the addition ratio of the end-capping reagent. By changing the type of the blocking agent, the p-methyl benzoic acid and the m-methyl benzoic acid have no significant difference.
The fiber filaments prepared in examples 1 to 16 and comparative example 1 were subjected to the water absorption and mechanical property measurement, and the results are shown in table 3. Table 3 shows that the breaking strength of the fiber filaments prepared by the method of the present invention is significantly improved on the premise of ensuring the water absorption of the fiber.
Table 3.
Claims (19)
1. A method of making a fiber filament made from a graft polymer of cellulose and PET comprising the steps of:
(1) preparation of single-terminal hydroxyl PET: mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.2-1.6, and adding at least one of m-methylbenzoic acid or p-methylbenzoic acid as a blocking agent, an esterification catalyst and a heat stabilizer, wherein the molar ratio of the blocking agent to the terephthalic acid is 0.025-0.5: 1; carrying out esterification reaction and polycondensation reaction on terephthalic acid and ethylene glycol to obtain single-end hydroxylated PET;
(2) preparation of graft polymers of cellulose and PET: dissolving the PET with the single end hydroxylated in the step (1) in tetrachloroethane, and adding an ionic liquid, diisocyanate and an organic tin compound catalyst to obtain a tetrachloroethane solution of an isocyanate-terminated prepolymer; dissolving cellulose and/or derivatives thereof in tetrachloroethane solution, adding the solution into tetrachloroethane solution of the isocyanate-terminated prepolymer, purifying the product after the reaction of the two, settling the product by using dichloromethane and petroleum ether to obtain a solid product, and drying the solid product to obtain a purified graft copolymer of the cellulose and the PET;
(3) preparing a spinning solution: dissolving a graft copolymer of cellulose and PET in a solvent to obtain a bubble-free uniform spinning solution;
(4) spinning by a dry-jet wet spinning method: extruding the spinning solution through a spinneret plate with the aperture of 0.1-0.5mm, enabling the extrusion speed of a metering pump to be 6-9m/min, enabling the spinning solution to enter a coagulating bath after passing through an air section with the length of 3-10cm, and obtaining fiber filaments at the drafting rate of a first roller of 5-30 m/min.
2. The preparation method according to claim 1, wherein after the end-capping reagent, the esterification catalyst and the heat stabilizer are added in the step (1), the temperature is increased to 240 ℃ at first, the terephthalic acid and the ethylene glycol are subjected to esterification reaction, after the esterification reaction, the polycondensation reaction is carried out in two steps, the reaction temperature is increased to 270 ℃ at first, the vacuum degree is adjusted to 900-1100Pa, and the pre-polycondensation reaction is carried out for 50-70 min; then the reaction temperature is adjusted to 280-290 ℃ and the vacuum degree is 80-200Pa, and the secondary polycondensation reaction is carried out for 20-30 min.
3. The method according to claim 1, wherein the heat stabilizer used in step (1) is at least one selected from the group consisting of triphenyl phosphate, diphenyl phosphate, triphenyl phosphite and diphenyl phosphite, and is added in an amount of 0.5 to 3.0% by weight based on the terephthalic acid.
4. The method according to claim 1, wherein the esterification catalyst in the step (1) is at least one selected from the group consisting of antimony trioxide, antimony acetate, antimony glycol, titanium dioxide and titanium glycol, and is added in an amount of 0.02 to 0.08% by weight based on the terephthalic acid.
5. The preparation method according to claim 1, wherein after the polycondensation reaction in step (1) is completed, the method further comprises a step of purifying the synthesis product, specifically, dissolving the synthesis product in hexafluoroisopropanol, and then precipitating and drying with acetone to obtain the purified single-end hydroxylated PET.
6. The method according to claim 1, wherein the mass concentration of the PET in tetrachloroethane in the step (2) is 2 to 15%.
7. The preparation method according to claim 1, wherein the PET in the step (2) is reacted with the ionic liquid, the diisocyanate and the organotin compound catalyst at 60-80 ℃ for 2-6 h.
8. The process according to claim 1, wherein the reaction of the cellulose and/or the derivative thereof with the isocyanate-terminated prepolymer in the step (2) is carried out at a temperature of 65 to 75 ℃ for a period of 2 to 24 hours.
9. The preparation method according to claim 1, wherein the mixing ratio of the PET, the cellulose and/or the derivative thereof in the step (2) is controlled to make the yield of the graft copolymer 50 to 90%.
10. The method according to claim 1, wherein the cellulose and/or the derivative thereof is at least one selected from the group consisting of cellulose acetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose and benzyl cellulose.
11. The method according to claim 1, wherein the purification in step (2) is specifically: and (2) dropwise adding dichloromethane with the volume of 0.5-2 times of the reaction liquid into the solution after the grafting reaction is finished to separate out floccules, dropwise adding petroleum ether with the volume of 0.3-1 time of the reaction liquid, further separating out the floccules, pouring out the solution to leave precipitates, repeatedly washing the precipitates with dichloromethane and petroleum ether, and finally drying in vacuum to obtain the purified graft polymer.
12. The method according to claim 1, wherein the graft copolymer and the solvent in the step (3) are mixed in a mass ratio of 1: 1.5-3 are mixed and dissolved.
13. The method of claim 1, wherein the uniform bubble-free spinning solution obtained in step (3) is obtained by hermetically vacuum-deaerating the spinning solution.
14. The production method according to claim 1, wherein the solvent used for producing the spinning dope in the step (3) is at least one selected from the group consisting of 1,1,2, 2-tetrachloroethane, hexafluoroisopropanol and dimethyl sulfoxide.
15. The method according to claim 1, wherein the step (3) of dissolving the graft copolymer in the solvent comprises the following steps: mixing the graft copolymer and the solvent, standing for 60-120min, fully swelling, heating to 75-95 ℃, and stirring at high speed for 24-36h to completely dissolve the graft copolymer.
16. The production method according to claim 1, wherein the specific operating conditions for extruding the spinning dope through the spinneret in the step (4) are: the pressure is controlled to be 0.2-0.5MPa, and the temperature is controlled to be 20-40 ℃.
17. The production method according to claim 1, wherein the coagulation bath in the step (4) is a DMSO aqueous solution having a mass concentration of 20% to 35%.
18. A fiber filament made by the process of any of claims 1-17.
19. Use of the fiber filament of claim 18 in apparel textile.
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Effective date of registration: 20231106 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |