CN100338276C - Polyester fiber and false twisted yarn made thereof - Google Patents
Polyester fiber and false twisted yarn made thereof Download PDFInfo
- Publication number
- CN100338276C CN100338276C CNB2003801003524A CN200380100352A CN100338276C CN 100338276 C CN100338276 C CN 100338276C CN B2003801003524 A CNB2003801003524 A CN B2003801003524A CN 200380100352 A CN200380100352 A CN 200380100352A CN 100338276 C CN100338276 C CN 100338276C
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- China
- Prior art keywords
- general formula
- polyester
- acid
- yarn
- polyester fiber
- 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 - Fee Related
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- 229920000728 polyester Polymers 0.000 title claims abstract description 191
- 239000000835 fiber Substances 0.000 title claims abstract description 87
- -1 phosphorus compound Chemical class 0.000 claims abstract description 104
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 52
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 50
- 239000011574 phosphorus Substances 0.000 claims abstract description 50
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims description 130
- 229920000642 polymer Polymers 0.000 claims description 127
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 86
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000010936 titanium Substances 0.000 claims description 33
- 125000003118 aryl group Chemical group 0.000 claims description 32
- 150000002148 esters Chemical group 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 150000008065 acid anhydrides Chemical class 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 3
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- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical class OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 claims description 2
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- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 24
- 239000004753 textile Substances 0.000 description 22
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- 239000000243 solution Substances 0.000 description 16
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- 238000001816 cooling Methods 0.000 description 10
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- 238000004804 winding Methods 0.000 description 9
- 238000009825 accumulation Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000009987 spinning Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
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- 239000004408 titanium dioxide Substances 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000003203 everyday effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000009940 knitting Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 3
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
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- 239000002480 mineral oil Substances 0.000 description 3
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- 239000008188 pellet Substances 0.000 description 3
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MVXKNWUEHVHFBD-UHFFFAOYSA-N C(=O)CP(O)(=O)O.[O] Chemical compound C(=O)CP(O)(=O)O.[O] MVXKNWUEHVHFBD-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000004125 X-ray microanalysis Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
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- WSTSJXXSZFUDDG-UHFFFAOYSA-N (1-ethoxy-2-oxo-2-phenylethyl)phosphonic acid Chemical compound C(C)OC(P(O)(=O)O)C(C1=CC=CC=C1)=O WSTSJXXSZFUDDG-UHFFFAOYSA-N 0.000 description 1
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- LLJFNWVJKMVHIL-UHFFFAOYSA-N (2-methoxy-2-oxoethyl)phosphonic acid Chemical compound COC(=O)CP(O)(O)=O LLJFNWVJKMVHIL-UHFFFAOYSA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- CXYYVOJURSDSRL-UHFFFAOYSA-N (4-ethylphenyl) dihydrogen phosphate Chemical compound CCC1=CC=C(OP(O)(O)=O)C=C1 CXYYVOJURSDSRL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- YNXICDMQCQPQEW-UHFFFAOYSA-N 1-naphthyl dihydrogen phosphate Chemical compound C1=CC=C2C(OP(O)(=O)O)=CC=CC2=C1 YNXICDMQCQPQEW-UHFFFAOYSA-N 0.000 description 1
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- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
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- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
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- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- OTJLUSCKEQAWFT-UHFFFAOYSA-N phenacylphosphonic acid Chemical compound OP(O)(=O)CC(=O)C1=CC=CC=C1 OTJLUSCKEQAWFT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical class CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000009964 serging Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 238000009970 yarn dyeing Methods 0.000 description 1
Images
Abstract
The object of invention is to provide a polyester fiber having excellent color tone and enabling stable draw false-twisting treatment to form a false twist yarn free from fluff and having extremely high quality. The polyester fiber having a single fiber fineness of 0.1-1.0 dtex is produced by melt-spinning a polyester produced by the polycondensation in the presence of a catalyst composed of a reaction product of a specific titanium compound and a phosphorus compound.
Description
Technical field
The present invention relates to polyester fiber and the false twist textured yarn that comprises this fiber.Specifically, the present invention relates to have good color and be in harmonious proportion the polyester fiber of good false twist texturing performance and the false twist textured yarn that comprises this fiber.
Background technology
Recently, comprise the woven fabric or the knit goods of fiber number 1dtex or lower low-titer polyester fiber, and the various textiless of autopolyester fiber production, owing to its softness obtained extensive use with feel imitative chamois leather.In addition, be widely used as interior decoration materials and interior decoration lining and automobile cover for seat by the polyester false twist texturing filament yarn that above-mentioned low-titer polyester filament false twist texturing is produced, reason is not only soft but also high dim property, water imbibition and the hygroscopicity of protecting arranged from the textiles of false twist textured yarn manufacturing.The low-titer polyester fiber is difficult to make as mentioned above, thus various producd fibers improved technological process are provided, for example, Japan Patent No.3,043,414.
Yet, in the conventional melt spun technology of polyester polymers, a kind of phenomenon takes place, promptly, produce foreign matter, and adhere to and accumulate in around the melt extrusion cavities of melt-blowing plate, along with the passing of melt-spun time, the foreign matter that is accumulated hinders the melt extrusion proper flow, cause the bending of melt extrusion tow, swing or rotation (hereinafter can be called informal squeeze-out phenomenon), at last, the melt extrusion tow contacts with the foreign matter that is gathered, so fracture.Above-mentioned foreign matter can be called the spinnerets foreign matter.
Specifically, when the low polyester fiber of produce by the melt spinning method, reel then 1dtex or littler filament fiber number, the spinnerets foreign matter produces the polymer melt extrusion condition and has a strong impact on, and informal squeeze-out phenomenon just takes place at short notice, thereby on fiber, produce lousiness, impel fibrous fracture, thereby be difficult to carry out continuously melt spinning.In addition, above-mentioned informal phenomenon in cooling of polymer melt tow and curing schedule, makes the polymer melt tow form inhomogeneous fibre structure, and so the gained polyester fiber also has inhomogeneous internal structure.Therefore, when gained silvalin drawn and false twist texturing process, inhomogeneous internal structure causes the continuous generation of lousiness and yarn breakage takes place again and again.
Known, spinnerets production of foreign matters and accumulation are derived from the antimony that retains in polyester polymers.Antimony is derived from the polycondensation catalyst that is used for making polyester polymers.Antimony-containing catalyst has the performance of promotion polycondensation good for making polyester, particularly for polyethylene terephthalate polymer, and prepared polyester fiber has good color tone, so, recently be extensive use of antimony-containing catalyst in practice, therefore in the normal polyester fiber, extensively contain antimony.
Alternatively, as the polycondensation catalyst that is used for polyester polymers, except antimonial, go back known titanium compound, for example fourth alkoxytitanium.When using titanium compound, produce the problem that the gained polyester polymers has light-yellow tinge, so the gained polyester fiber is not suitable for fabric because of light-yellow tinge, although the foreign matter around spinnerets produces and accumulation descends.
Summary of the invention
The object of the present invention is to provide to have good color and be in harmonious proportion the polyester fiber of good false twist texturing performance, and do not have or do not have substantially lousiness, therefore have high-quality, as to comprise a polyester fiber false twist textured yarn.The invention solves normal polyester fiber and the problems referred to above that comprise the false twist textured yarn of this fiber.
Above-mentioned purpose can realize by polyester fiber of the present invention and false twist textured yarn.
Polyester fiber of the present invention comprises the polyester polymers as principal component, has 0.1～1.0dtex filament fiber number,
Wherein:
Polyester polymers is the polymer that aromatic dicarboxylic acid ester's polycondensation is made by in the presence of catalyst,
Described catalyst comprises and is selected from mixture (1) or the product of stipulating below (2),
Be used for mixture of catalysts (1) and comprise (A) and (B), and (A) mix with (B);
(A) a kind of titanium compound composition comprises and is selected from least a in (b):
(b) product of the aromatic polycarboxylic acid shown in the alkoxytitanium of general formula (I) and the general formula (II):
In described general formula (I), R
1, R
2, R
3And R
4Represent the alkyl or phenyl that contains 1～20 carbon atom independently of one another respectively, m represents integer 1～4, when m represents integer 2,3 or 4, and 2,3 or 4 R
2And R
3Can be respectively mutually the same or differ from one another,
In general formula (II), n represents integer 2～4; The perhaps product of the acid anhydride of the acid of the alkoxytitanium of general formula (I) and general formula (II);
(B) phosphorus compound composition comprises at least a phosphorus compound by general formula (III) expression:
In described general formula (III), R
5, R
6And R
7Represent the alkyl group that contains 1～4 carbon atom, X representative-CH independently of one another respectively
2-group or-CH (Y)-group, wherein Y represents phenyl,
The consumption that is used for the mixture (1) of polycondensation catalyst should satisfy following relationship formula (i) and (ii) represented requirement:
1≤M
P/M
Ti≤15 (i)
With
10≤M
P+M
Ti≤100 (ii)
Wherein, M
TiThe ratio of the mM value of the titanium elements that representative contains in titanium compound composition (A) and aromatic dicarboxylic acid ester's mole value is represented with percentage, and M
PThe ratio of the mM value of the P elements that representative contains in phosphorus compound composition (A) and aromatic dicarboxylic acid ester's mole value is represented with percentage; With
The product (2) that is used for catalyst comprises (C) and (D), and (C) and (D) reacts;
Wherein:
(C) titanium compound composition comprises and is selected from least a in following (c):
(c) alkoxytitanium of representing by general formula (I);
In described general formula (I), R
1, R
2, R
3And R
4Represent the alkyl or phenyl that contains 1～20 carbon atom independently of one another respectively, m represents integer 1～4, when m represents integer 2,3 or 4, and 2,3 or 4 R
2And R
3Can be respectively mutually the same or differ from one another
(D) phosphorus compound composition comprises at least a phosphorus compound by general formula (IV) expression,
In described general formula (IV), R
8Representative contains the alkyl of 1～20 carbon atom or contains the aryl of 6～20 carbon atoms, and p represents integer 1 or 2.
In polyester fiber of the present invention, at the composition that is used for mixture of catalysts (1) (A) be used in every kind of composition of composition (C) of product (2) of catalyst, alkoxytitanium (a) and (c) the reaction mol ratio of each and general formula (II) aromatic polycarboxylic acid or its acid anhydride be preferably 2: 1 to 2: 5.
In polyester fiber of the present invention, be used for the product of catalyst (2), the preferable range of the reacting dose ratio of composition (D) and composition (C), during with ratio (P/Ti) expression of the molar weight of the phosphorus atoms that contains in the composition (D) and the molar weight of the titanium atom that in composition (C), contains, it is 1: 1 to 3: 1.
In polyester fiber of the present invention, for product (2), the phosphorus compound of general formula (IV) is preferably from mono alkyl phosphate.
In polyester fiber of the present invention, the aromatic dicarboxylic acid dialkyl preferably carries out the prepared person of ester exchange reaction by the dialkyl and the aklylene glycol of aromatic dicarboxylic acid in the presence of titanium-containing catalyst.
In polyester fiber of the present invention, aromatic dicarboxylic acid is preferably from terephthalic acid (TPA), 1,2-naphthalenedicarboxylic acid, phthalic acid, M-phthalic acid, diphenyl dicarboxylic acid and biphenoxyl ethane dicarboxylic acids; Aklylene glycol is selected from ethylene glycol, 1,4-butanediol, 1, ammediol, propylene glycol, neopentyl glycol, 1,6-hexylene glycol and ten dimethylene glycol.
In polyester fiber of the present invention, polyester polymers is preferably from polyethylene terephthalate, poly terephthalic acid 1, ammediol ester and poly terephthalic acid 1,4-butanediol ester.
In polyester fiber of the present invention, the inherent viscosity of polyester polymers is preferably 0.45～0.70, and the solution in the comfortable o-chlorphenol is measured under 35 ℃.
False twist textured yarn of the present invention comprises the polyester fiber that limits in the present invention.
In false twist textured yarn of the present invention, the L of false twist texturing polyester fibers
*Value and b
*The difference of value is preferably 91.0～99.0.
Description of drawings
Fig. 1 is the illustrative figure of production method embodiment that expression the present invention contains the false twist textured yarn of polyester fiber.
The specific embodiment
Polyester fiber of the present invention comprises as the polyester polymers of principal component and has 0.1～1.0dtex filament fiber number.
Polyester polymers is by making the aromatic dicarboxylic acid ester carry out the producer of polycondensation institute in the presence of special catalyst.
The production method of polyester fiber of the present invention preferably includes: batch with the polyester polymers melt spinning with under coiling speed (spinning speed) 2500～4000m/min, more preferably batch under 2500～3500m/min.Optional, after the melt-spun step, carry out the stretching and the heat treatment of melt-spun fibre.The polyester mutifilament yarn of under aforesaid high coiling speed, producing can be directly through false twist texturing process (this process can contain stretch and/or heat treatment) so that false twist textured yarn is provided.
In the present invention, the catalyst that is used for producing above-mentioned polyester polymers comprises at least one and is selected from the part that is used for described mixture of catalysts (1) and product (2).These will be explained hereinafter.
Being used for described mixture of catalysts (1) is the mixture of titanium compound composition (A) and phosphorus compound composition (B).Titanium compound composition (A) comprises at least a being selected from (a) by the alkoxytitanium of general formula (I) expression and (b) compound of the product of the aromatic polycarboxylic acid represented of alkoxytitanium and the general formula (II) of general formula (I) or its acid anhydride.
In the present invention, be configured for the alkoxytitanium (a) and (b) of the titanium compound composition (A) of catalyst mixture (1), in polyester polymers, has highly dissoluble respectively by catalysis polycondensation reaction preparation, perhaps, described polyester polymers had high-affinity respectively, therefore, be contained in titanium compound (a) and (b) deposition, bonding and accumulation around the spinnerets in the polyester polymers, the gained polyester fiber presented low-qualityly also can not rupture.
In the alkoxytitanium represented by general formula (I), R
1, R
2, R
3And R
4Represent alkyl group or phenyl group respectively, the preferred alkyl group.Preferably, alkyl group has 1～20 carbon atom, more preferably 1～6 carbon atom.In addition, in general formula (I), m represents integer 1～4, and preferred 1～3. Represent integer 2,3 or, two, three or four R at 4 o'clock at m
2And R
3Can be respectively mutually the same or differ from one another.
In general formula (II), n represents integer 2～4, and preferred 3 or 4.
Be used for the mixture of polycondensation catalyst (1), phosphorus compound (B) composition comprises at least a compound by general formula (III) representative:
In described general formula (III), R
5, R
6And R
7Represent the alkyl group that contains 1～4 carbon atom, X representative-CH independently of one another respectively
2-group or-CH (Y)-group (wherein Y represents phenyl group).
The product (2) that is used for polycondensation catalyst is the product of titanium compound composition (C) and phosphorus compound composition (D).
Titanium compound composition (C) comprises at least a following (a) and the compound (b) of being selected from:
(a) alkoxytitanium of above-mentioned general formula (I) representative,
(b) aromatic polycarboxylic acid of general formula (I) alkoxytitanium and general formula (II) representative or the product of its acid anhydrides.
Phosphorus compound composition (D) comprises at least a phosphorus compound by general formula (IV) representative:
In described general formula (IV), R
8Representative contains the alkyl group of 1～20 carbon atom or contains the aromatic yl group of 6～20 carbon atoms, and p represents integer 1 or 2.
Can be used for the product (2) that catalyst of the present invention uses and present in fact enough dissolubilities or polyester polymers is shown in fact enough affinitys in polyester polymers, its reason is that the titanium compound composition that is contained in the product (2) has highly dissoluble in polyester polymers.The product (2) that is contained in the polyester polymers does not deposit, bonds in the melt-spun process and is accumulated in around the SPINNERETS FOR MELT SPINNING.So can access and have high-quality polyester fiber.
Can be used for titanium compound composition (A) that polycondensation catalyst of the present invention uses or general formula (C) (I) alkoxytitanium (a) preferably from tetraisopropoxy titanium, four titanium propanolates, four titanium n-butoxide, purity titanium tetraethoxide, four phenoxide titaniums, three metatitanic acids, eight Arrcostabs and two metatitanic acids, six Arrcostabs.
With alkoxytitanium (a) or (c) general formula (II) aromatic polycarboxylic acid of reaction and acid anhydride thereof preferably from the acid anhydride of phthalic acid, trimellitic acid, benzene-1, petroleum benzene pregnancy acid (pyrromellitic acid) and above-mentioned acid.Specifically, when using trimellitic anhydride, gained product (b) shows high affinity to polyester polymers, therefore becomes one of reason that prevents the foreign matter accumulation.
In order to carry out about titanium compound composition (A) or alkoxytitanium (C) (a) or (c) and the reaction of general formula (II) aromatic polycarboxylic acid or its acid anhydrides, preferably aromatic polycarboxylic acid or its acid anhydride are dissolved in the solvent, be added drop-wise in the gained solution with alkoxytitanium (a) or (c), heat gained reactant mixture 30min at least down at 0～200 ℃ then.Above-mentioned solvent is preferably from ethanol, ethylene glycol, 1, ammediol, 1,4-butanediol, benzene and dimethylbenzene.
For alkoxytitanium (a) or (c) and the reaction mol ratio of general formula (II) aromatic polycarboxylic acid or its acid anhydride without limits.Yet if the alkoxytitanium ratio is too high, the tone of gained polyester polymers can be demoted and/or softening point can reduce so.On the contrary, if the alkoxytitanium ratio is too low, so just be difficult to carry out polycondensation reaction.So, alkoxytitanium (a) or (c) and the reaction mol ratio of the aromatic polycarboxylic acid of general formula (II) or its acid anhydride preferably be controlled at 2: 1 to 2: 5 scope.
By above-mentioned reaction reaction products resulting (b) or (d), can be under without refining condition, perhaps by adopt acetone, methyl alcohol and/or ethyl acetate carry out re-crystallization step refining after use.
Can be used for the mixture (1) that polycondensation catalyst of the present invention uses phosphorus compound composition (B) general formula (III) phosphorus compound (phosphonate compound) preferably for example from phosphate derivatives, dimethyl ester, diethylester, dipropyl and the dibutyl ester of methoxycarbonyl methanephosphonic acid, ethoxycarbonyl methanephosphonic acid, the third oxygen formyl methanephosphonic acid, fourth oxygen formyl methanephosphonic acid, benzoyl methanephosphonic acid, ethoxy benzoyl methanephosphonic acid, the third oxygen phenylmethane methanephosphonic acid and fourth oxygen benzoyl methanephosphonic acid.
Be used for the use of aromatic dicarboxylic acid ester's phosphorus compound composition (B) polycondensation reaction, that comprise general formula (III) phosphorus compound (phosphonate compound), compare with conventional phosphorus compound as reaction stabilizer, the composition (B) and the reaction of titanium compound composition (A) are more gently carried out, the catalytic activity life-span of titanium compound composition (A) in polycondensation process prolonged, and the quantity that makes the titanium compound composition (A) that is contained in the polycondensation system and aromatic dicarboxylic acid ester is than descending.In addition, a large amount of reaction stabilizers are joined in the polycondensation reaction system that contains general formula (III) phosphorus compound composition (B), the heat endurance of gained polyester polymers is reduced.The tone of gained polyester polymers is descended.
Mixture (1) is being used as under the situation of polycondensation catalyst, and the consumption of mixture (1) should satisfy following relationship formula (i) and (ii) represented requirement:
1≤M
P/M
Ti≤15 (i)
With
10≤M
P+M
Ti≤100 (ii)
Wherein, M
TiThe ratio of the mM value of the titanium elements that representative contains in titanium compound composition (A) and aromatic dicarboxylic acid ester's mole value is represented with percentage, and M
PThe ratio of the mM value of the P elements that representative contains in phosphorus compound composition (A) and aromatic dicarboxylic acid ester's mole value is represented with percentage.
Ratio M
P/ M
TiBe 1 or higher, but be not more than 15, be preferably 2 or higher, but be not more than 10.If ratio M
P/ M
TiLess than 1, the gained polyester polymers can have light yellow tone.In addition, if described ratio greater than 15, the gained polycondensation catalyst shows the not enough catalytic activity for polycondensation reaction, the preparation of target polyesters polymer can be difficult to carry out like this.The M that can be used for catalyst of the present invention
P/ M
TiThe scope of ratio is compared with this scope of common Ti-P catalyst, is narrower.And, the ratio M of mixture of the present invention (1)
P/ M
TiLimited range, make the gained catalyst show the good catalytic action that conventional Ti-P catalyst can not obtain.
In addition, (M
Ti+ M
P) sum is 10 or higher, but be not more than 100, preferred 20 or higher, but be not more than 70.(M
Ti+ M
P) sum is less than 10, the gained polyester polymers can present not enough fibre forming property, and this can make effective production of carrying out in the melt-spun process of polyester polymers become can not to carry out smoothly, and makes the gained polyester fiber not have suitable performance.In addition, if (M
Ti+ M
P) sum is greater than 100, in gained polyester polymers melt-spun process, foreign matter can be deposited on around the SPINNERETS FOR MELT SPINNING, but sedimental amount is few.In general, M
TiValue is preferably 2～5, and more preferably 3～10.
Product (2) is being used as under the situation of polycondensation catalyst of the present invention, general formula (IV) phosphorus compound that is used for phosphorus compound composition (D) comprises, mono alkyl phosphate, for example, phosphoric acid-positive butyl ester, phosphoric acid-own ester, phosphoric acid-(dodecyl) ester and phosphoric acid-oil base ester; The mono phosphoric acid ester aryl ester, for example, phosphoric acid-phenyl ester, phosphoric acid-benzyl ester, phosphoric acid-(4-ethylphenyl) ester, phosphoric acid-biphenyl ester, phosphoric acid-naphthyl ester and phosphoric acid-anthryl ester; Phosphate dialkyl ester, for example diethyl phosphate, di(2-ethylhexyl)phosphate propyl ester, dibutylphosphoric acid ester, di(2-ethylhexyl)phosphate lauryl and di(2-ethylhexyl)phosphate oil base ester; And the di(2-ethylhexyl)phosphate aryl ester, for example, the di(2-ethylhexyl)phosphate phenylester, etc.In above-mentioned phosphate, more preferably wherein n represents general formula (IV) phosphate of integer 1, i.e. phosphoric acid-Arrcostab and phosphoric acid-aryl ester.
Can be used for the mixture that phosphorus compound composition of the present invention (D) can comprise two or more general formulas (IV) phosphorus compound, the mixture of preferably phosphoric acid mono alkyl ester and phosphate dialkyl ester, the perhaps mixture of phosphoric acid-phenyl ester and diphenyl phosphate.Preferably, in described mixture, the content of mono alkyl phosphate is 50% (by mass) or higher, and more preferably 90% (by mass) or higher is benchmark in the gross mass of mixture.
The preparation of the product of aforesaid titanium compound composition (C) and phosphorus compound composition (D) is implemented as follows: make composition (C) and (D) be mixed with each other and heat the gained mixture in glycol.That is, when solution in glycol of heating titanium compound composition (C) and phosphorus compound composition (D), the product of composition (C) and composition (D) deposits, formation white casse glycol solution.Collect deposit and be used as the catalyst of producing polyester polymers.
Can be used for preparing the glycol of above-mentioned product, preferably identical with the diol component that is used for producing in the presence of as the product of catalyst polyester polymers.For example, when the polyester polymers of producing is polyethylene terephthalate polymer, preferably making spent glycol, is poly terephthalic acid 1 at it, during the ammediol ester, preferably use 1, ammediol and it are poly terephthalic acids 1, during the 4-butanediol ester, preferably use 1, the 4-butanediol.
The product (2) that is used for polycondensation catalyst of the present invention can prepare by another kind of method, wherein, titanium compound composition (C), phosphorus compound composition (D) and glycol are mixed with each other simultaneously and heat the gained mixture.In this method, react when making the gained product deposition that is insoluble to glycol by heating at titanium compound composition (C) and phosphorus compound composition (D), preferably the course of reaction before deposition takes place is evenly carried out.So, in order to obtain the product deposit, preferably prepare deposit, wherein by following method with high efficiency, the independent solution and the solution of phosphorus compound composition (D) in glycol of preparation titanium compound composition (C) in glycol makes gained solution be mixed with each other then and heats the gained mixture.
The reaction of composition (C) and composition (D) is preferably carried out under 50～200 ℃ of reaction temperatures, and the reaction time is 1min～4hr.If reaction temperature is too low, described reaction is not perhaps finished, and perhaps must just can finish described reaction for a long time, so the target deposit can not make with homogeneous reaction and with high efficiency.
When titanium compound composition (C) and phosphorus compound composition (D) carried out thermal response in glycol, the consumption of preferred phosphorus compound composition (D) was pressed the molar ratio computing of phosphorus atoms and titanium atom, is 1.0～3.0, and more preferably 1.5～2.5.When at composition (C) and (D) using by above-mentioned scope, titanium compound composition (C) and phosphorus compound composition (D) be complete reaction basically each other, does not contain the incomplete reaction product in product.So, can directly use the gained product without refining, and the gained polyester polymers has good tone.In addition, the gained product does not contain unreacted general formula (IV) phosphorus compound substantially, therefore presents the high catalytic activity for polycondensation, and with high yield productive target polyester polymers.
The product (2) that is used for the polycondensation catalyst of the present invention's application contains the compound of general formula (V) representative
Shown in the general formula (V), R
9And R
10Irrelevant each other representative respectively is selected from the R by the general formula (I) of the alkoxytitanium that is used for titanium compound composition (C) in representative
1, R
2, R
3And R
4With R by the general formula (IV) of the phosphorus compound that is used for phosphorus compound composition (D) in representative
8The element of the alkyl group of deriving and its contain 1～10 carbon atom, R
9And R
10Also irrelevant each other representative respectively is selected from by the R in representing the general formula of phosphorus compound (IV)
8The element of the aromatic yl group of deriving and its contain 6～12 carbon atoms.
Has high catalytic activity by product general formula (V) expression, titanium compound and general formula (III) or phosphorus compound (IV).In addition, show good tone (low b by the polyester polymers that adopts general formula (V) product to produce
*Be worth), and the content of acetaldehyde, residual metal and cyclic trimer is in fact all low sufficiently.And in fact has a satisfied performance.
Product shown in the general formula (IV) preferably with a certain content (by mass) or contain more, and more preferably 70% (by mass) or more is benchmark in the polycondensation catalyst gross mass.
In the presence of product (2) in aromatic dicarboxylic acid ester's the polycondensation, product (2) deposit that makes with said method, can be under the condition of not carrying out reaction product isolated (2) deposit and glycol from the glycol liquid of the product (2) that contains deposition, as the catalyst of producing polyester polymers.Alternatively, the deposit of product (2) can be handled or filter and separate from the glycol liquid that contains deposition reaction product (2) by centrifugal deposition, institute's isolated product (2) deposit is recrystallized such as recrystallization reagent such as acetone, methyl alcohol and/or water by employing and makes with extra care, and then refining product (2) is used as polycondensation catalyst.The chemical constitution that is used for the product (2) of polycondensation catalyst can be carried out the metal quantitative analysis by solid-state nuclear magnetic resonance (NMR) and X ray microanalysis (XMA) and be determined.
Can be used for polyester polymers of the present invention by in the presence of a kind of catalyst, aromatic dicarboxylic acid ester's polycondensation being made, described catalyst package titanium-containing compound composition (A) and the mixture (1) of phosphorus compound (phosphonate compound) composition (B) and/or the product of titanium compound composition (C) and phosphorus compound composition (D).In the present invention, the aromatic dicarboxylic acid ester is preferably from aromatic dicarboxylic acid diester composition and aliphatic diol composition.
In the present invention, the aromatic dicarboxylic acid composition preferably comprises the terephthalic acid (TPA) as main component.More particularly, the aromatic dicarboxylic acid composition preferably contains 70mol% or more terephthalic acid (TPA)s, is benchmark in the integral molar quantity of aromatic dicarboxylic acid composition.Other aromatic acid except terephthalic acid (TPA) is preferably from phthalic acid, M-phthalic acid, naphthalenedicarboxylic acid, diphenyl dicarboxylic acid and biphenylyloxy ethane dicarboxylic acids.
The aliphatic diol composition preferably comprises aklylene glycol, is selected from, for example, ethylene glycol, 1, ammediol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol and ten dimethylene glycol.Especially preferably make spent glycol.
In the present invention, the preferred polyester polymer comprises, as main repetitive, from the Polyethyleneglycol Terephthalate unit of terephthalic acid (TPA) and ethylene glycol formation.In this case, the Polyethyleneglycol Terephthalate repetitive preferably contains the proportional 70mol% or higher that is.Total mole number amount in repetitive in polyester polymers is a benchmark.
Can be used for polyester polymers of the present invention can be by making the copolyester polymer of one or more comonomer copolymerization that can be used as polyester polymers acid composition and/or diol component.
The carboxylic acid that can be used as the copolyester polymer comonomer comprises that two functional carboxylic acid and its form the derivative of ester, for example, and above-mentioned aromatic dicarboxylic acid, aliphatic dicarboxylic acid, for example, adipic acid, decanedioic acid, azelaic acid and decane dicarboxylic acid; The cycloaliphatic dicarboxylic acid, for example, cyclohexane dicarboxylic acid.
The diol compound that can be used as comonomer comprises above-mentioned aliphatic diol compound, the cycloaliphatic diol compound, for example, cyclohexanedimethanol, and aromatic diol compound, for example, bis-phenol, quinhydrones and 2, two (4-β-hydroxy ethoxy phenyl) propane of 2-.
In addition, by using the polyfunctional compound as comonomer, for example, other copolyester polymer of trimellitic acid, trimethylolethane, Pehanorm and pentaerythrite preparation can be used in the present invention.
Above-mentioned polyester polymers and copolyester polymer can be used separately or use with the form of its two or more mixture.
In the present invention, preferably, will be from the aromatic dicarboxylic acid ester's of as mentioned above aromatic dicarboxylic acid and aliphatic diol preparation polycondensation product as polyester polymers.The aromatic dicarboxylic acid ester can be by aromatic dicarboxylic acid and aliphatic diol two esterifications reaction, perhaps, the ester exchange reaction of dialkyl and aliphatic diol by aromatic dicarboxylic acid prepares.Be through the advantage of the method for ester exchange reaction as initiation material, described ester at the aromatic dicarboxylic acid dialkyl: compare through the method for two esterifications reaction as initial compounds with aromatic dicarboxylic acid, the dissipation that joins the phosphorus compound in the polycondensation system as the phosphorus stabilizer agent during polycondensation reaction is slight.
Also have, preferred, before ester exchange reaction begins, sneak in the reaction system, so that utilize the catalysts of titanium compound composition as ester exchange reaction and polycondensation reaction with part or all of titanium compound composition (A) or (C).This method makes at end product, that is, the content of the titanium compound that contains in the polyester polymers descends.Under the situation of polyethylene terephthalate, specifically, comprise as the dialkyl of the aromatic dicarboxylic acid composition of principal component terephthalic acid (TPA) and the ester exchange reaction of ethylene glycol, preferably in the presence of the titanium compound composition (A) of the part that comprises at least a product (b) that is selected from aromatic polycarboxylic acid shown in alkoxytitanium (a) shown in the general formula (I) and general formula (I) alkoxytitanium and the general formula (II) or its acid anhydride, carry out.Then, will be by above-mentioned ester exchange reaction reactant mixture preparation, that comprise the diester of aromatic dicarboxylic acid and ethylene glycol, with the composition (B) that comprises the phosphorus compound (phosphonate compound) shown in the general formula (III), perhaps, product with titanium compound composition (C) and phosphorus compound composition (D), mix, so that carry out polycondensation reaction.
Ester exchange reaction is depressed at ambient air usually and is carried out.Yet, if being reflected under 0.05～0.20MPa pressure, this carries out, catalytic action in view of titanium compound composition (A), described reaction is further helped catalysis, and prevent that the accessory substance that comprises a large amount of diethylene glycol (DEG)s from producing, therefore the gained polyester polymers presents further improved performance, for example, and high thermal stability.Preferably under 160～260 ℃, carry out ester exchange reaction.
In the present invention, adopting under the situation of terephthalic acid (TPA) as aromatic dicarboxylic acid, using terephthalic acid (TPA) and dimethyl terephthalate (DMT) as the polyester polymers initial compounds.In this case, can use reuse dimethyl terephthalate (DMT) or reuse terephthalic acid (TPA) by the hydrolysis of reuse dimethyl terephthalate (DMT) is made by the polyalkylene terephthalates depolymerization is made.
In view of efficent use of resources, the preferred especially polymer chip that reclaims PET bottle, recycled fiber product, reclaims the polyester film product and produce in these product processes of manufacturing that uses is as the raw material of making polyester.
Polycondensation reaction can be carried out in single reactor or in turn carry out in a plurality of reactors.By the polyester polymers that polycondensation process is as mentioned above made, extrude with the wire-form melt usually, through supercooling, be shaped then (cut-out) is particle (section) shape.
Optional by the polyester polymers that polycondensation process is made further through solid state polymerization processes.
Solid phase is implemented with at least one step, at 190～230 ℃ of temperature, 1kPa～200kPa pressure, in containing just like the inertia of nitrogen, argon or carbon dioxide or non-reactive gas atmosphere.
Section shape polyester polymers by the manufacturing of above-mentioned solid phase polymerization process is optional to be stood by making polymer chips contact the water treatment of carrying out with non-reacted (inertia) gas of water, steam, moisture vapor or the air of moisture vapor again, thereby makes the catalyst structure of staying in the polymer chips.
The polyester polymers production method that comprises esterif iotacation step and condensation polymerization step can be come example with batch process, semi-continuous process or continuous process.
Can be used for polyester polymers of the present invention preferably from polyethylene terephthalate, poly terephthalic acid 1, ammediol ester and poly terephthalic acid 1,4-butanediol ester.
Can be used for the polyester polymers of making by said process of the present invention, preferred characteristics viscosity is 0.40～0.80, more preferably 0.45～0.75, also more preferably 0.50～0.70.If inherent viscosity is less than 0.40, the mechanical strength of gained polyester fiber can be not enough.In addition, if inherent viscosity greater than 0.80, this too high inherent viscosity can cause the gained polyester polymers that the forms polyester fiber shortcoming at economic aspect.
Can be used for that polyester polymers of the present invention is optional also to contain a small amount of additive, described additive comprises at least a following part that is selected from: antioxidant, ultra-violet absorber, fire retardant, fluorescent whitening agent, delustering agent, color and luster conditioning agent, defoamer, age resister (antistatingagent), antiseptic, light stabilizer, heat stabilizer and opacifier.Specifically, delustering agent is made up of titanium dioxide, preferably contains antioxidant in polyester polymers, and it uses as stabilizing agent.
Fine grained, content that preferred titanium dioxide is particle mean size 0.01～2 μ m were 0.01～10% (by mass).In the polyester amount is benchmark.
The Ti content of the catalyst that contains in the comfortable polyester polymers do not comprise the titanium that contains in the comfortable polyester polymers as the titanium dioxide of delustering agent.
When titanium dioxide is contained in the polyester polymers as delustering agent, for measuring the content of catalysis titanium, can only from the polyester matter sample, remove titanium dioxide as delustering agent, its method comprises: with the polyester polymers sample dissolution in hexafluoroisopropanol; Gained solution is handled through centrifugation, thereby in solution, only separated and deposit titanium dioxide granule; Separate and collection supernatant liquid body portion by method of tilting; Collected part evaporates solvent through evaporation process, thereby the drying sample of measuring usefulness is provided.
As antioxidant, preferably use the steric hindrance phenol type antioxidant.Preferably, antioxidant is with the content in polymer 1% (by mass) or lower, and more preferably 0.005～0.5% (by mass) mixed.If antioxidant content is greater than 1% (by mass), anti-oxidant action can be saturated, and tend to produce scum silica frost in polyester polymers melt-spun process.The steric hindrance phenol type antioxidant can use with thioether type auxiliary antioxidant.
To antioxidant is sneaked in the polyester polymers method without limits.Can begin and any stage of polycondensation reaction between stopping joins antioxidant in the reaction system in ester exchange reaction.
In the present invention, the method that the autopolyester polymer is made fiber without limits.Can use the conventional melt spinning method that is used for polyester.For example, with above-mentioned polyester polymers fusion, under 270 ℃～300 ℃ of temperature, and carry out melt spinning.In this melt spinning process, the melt-spun filaments yarn preferably batches with speed 2500～4500m/min, more preferably 2500～3500m/min.When coiling speed was above-mentioned scope, the gained long filament presented enough mechanical strengths and can stably reel under described coiling speed.In addition, the polyester filament by the manufacturing of melt-spun process can present 0.03～0.06 refractive index (Δ n) under above-mentioned coiling speed.Such polyester filament can and produce the few mode of lousiness with the long filament little breakage and carry out the Drawing and false twisting distortion.
Polyester fiber of the present invention preferably has: the uniformity, U%～0.8% or lower, density 1.345～1.370g/cm
3, shrink 25～55% at 65 ℃ of following hot water, high-tensile strength 1.5～3.0cN/dtex.Ultimate elongation 90～160%, initial yield stress 0.25～0.70cN/dtex, thermal stress peak value 0.1～0.2cN/dtex, and thermal stress peak temperature is on the glass transition temperature (Tg) of the polyester polymers that obtains polyester fiber 0～10 ℃.Polyester fiber with above-mentioned performance presents stable Drawing and false twisting deformation performance, and can form the equalization with improvement and the false twist textured yarn of good physical.
Polyester fiber of the present invention can pass through, and for example, following method is produced.
The polyester polymers that can be used for forming polyester fiber of the present invention is selected from has inherent viscosity 0.40～0.80, its inherent viscosity to the polyester polymers of the general fibre that can be used for fabric is similar, and described inherent viscosity is measured under 35 ℃ by adopting the solution of polymer in o-chlorphenol.With regard to the polyester fiber that production has little single fiber fiber number 0.1～1.0dtex, preferred use that to have the inherent viscosity scope be 0.50～0.6% polyester polymers.
In producing polyester fiber, with the polyester polymers granulation; Gained polyester polymers pellet in the conventional melt-spun equipment of screw extruder is housed, under the temperature that is higher than 40～70 ℃ of the fusing points of polyester polymers (Tm), carries out drying and fusion; Make the filter course of gained polyester polymers melt in being contained in melt-spun device (assembly) filter and extrude through spinnerets.Determine that the time of staying of polyester polymers melt in filter course is preferably feasible, after the cooling of polyester polymers melt and solidifying, the inherent viscosity (η of resulting polymers
f) be 0.50～0.60, more preferably 0.55～0.58.In addition, preferably, the cross-sectional area of each spinneret orifice of spinnerets is 7 * 10
-5～2 * 10
-4Cm
2, the ratio (L/D) of spinneret orifice length (L) and orifice diameter (D) is 4～10, is 0.06～0.20g/min through the polyester polymers rate of extrusion of each spinneret orifice.Under above-mentioned melt extrusion condition, the polymer melt of being extruded can be stablized by the fluidisation situation.
Then, make melt filament shape bundle that melt extrudes make the atmospheric atmosphere that melt filament shape bundle does not cool off by the control temperature, it adopts the cooling air draught (preferably having about 25 ℃ of temperature) from the supply of side-blown type melt-spun path to carry out cooling curing then, the gained long filament carries out finish and oils at the oil draw-off godet of boundling equipment of metal ring nozzle type, the long filament that oils becomes yarn beam through boundling, tow is by adopting interlacing nozzle interlacing, and the filament yarn that gained is handled through interlacing batches with above-mentioned coiling speed.
In said process, by following method the melt-spun process is carried out under highly stable situation, that is, the atmospheric temperature that adds in thermal control blowing filament plate exit face 0～40mm length areas is 100～300 ℃, can postpone the cooling of the thread bundle of polyester polymers melt like this.
In addition, by make the silk boundling that is spun from spinnerets exit face 350～500mm place, and the long filament shape bundle of being extruded is not almost waved, and the gained polyester fiber uniformity increases, the so-called uniformity is monofilament cross section U%.
Polyester fiber of the present invention can drawn-false twisting-distortion be produced the false twist texturing filament yarn that does not have lousiness substantially and be possessed of good qualities.
False twist textured yarn preferably has total percentage (TC) 2～5% that curls, and hot water shrinks (FS) 2.5～4.5%, TENSILE STRENGTH 2.5～4.5cN/dtex and ultimate elongation 15～35%.
False twist textured yarn with above-mentioned performance even fiber number is very little, does not almost have lousiness, end twisting spot yet, and presents high levelling property (inhomogeneities does not almost have aspect dyeability).
In producing above-mentioned false twist textured yarn, the preferred method that adopts equipment shown in Figure 1 of utilizing.In this case, preferably be implemented in draw false twisting deformation technique under the following condition.
Referring to Fig. 1, last stretched polyester multifilament textile 1 is by a pair of roll dies 3 of feeding, from being fed into the interlacing device 4 that has such as silk interlacing equipment such as the air nozzles that is used for tangling yarn through unwinding yarn deflector roll 2 and 2a around the coiling package 1a unwinding of rotating shaft 1b rotation.In interlacing device 4, the individual thread in the multifilament textile is interlacing each other.The multifilament textile of handling through interlacing 1 is fed in stretching-false twisting-anamorphic attachment for cinemascope, the latter is by constituting with lower member, for example, a pair of line feeding roller 3a, stretching-false twisting heater 5, godet roller 2b, coldplate 6, false twisting frictional disk equipment 7, godet roller 2c and a pair of first conveying roller 8.In false-twisting device, the interlacing multifilament textile stretches between hello the roll dies 3a and first conveying roller 8, and carries out false twisting by false twisting frictional disk equipment 7.Promptly, make multifilament textile 1 through feeding roll dies 3a feeding false-twisting device and being heated to following degree at heater 5, making the time of staying of yarn in heater is 0.052～0.300 second, preferred 0.060～0.150 second, and at heater outlet, the multifilament textile temperature is reached form on the glass transition temperature (Tg) of polyester polymers of long filament 90～140 ℃ level, preferred 110～130 ℃.In this step, filament yarn owing to feed difference between the roll dies 3a and first conveying roller 8, is 1.40～1.70 stretching and be subjected to draw ratio, preferred 1.5～1.6.The length of preferred heater 5 is 1.0～2.5mm.
Multifilament textile 1 advances to coldplate 6 through godet roller 2b from heater 5, by contacting the temperature that is cooled to be suitable for the friction false twist process with coldplate 6, for example, under the Tg of polyester polymers 10～50 ℃.Then, make the multifilament textile feeding false twisting frictional disk equipment 7 of cooling, and stand the friction false twist process.
Stretching and friction false twist process make gained false twist texturing multifilament textile not produce non-twist spot on yarn, have so just eliminated the irregular reason of yarn dyeing.
The temperature that is positioned at the multifilament textile of stretching-false-twisting device heater outlet can be measured by noncontact scanning thermometer (for example, H-7508 type, Supreme Being people's engineering corporate system is made).
By the false twist texturing multifilament textile of above-mentioned draw false twisting deformation process preparation, be fed forward to finish roll 10 from false-twisting device output with through second conveying roller 9 through first conveying roller 8.At finish roll 10, finish is applied on the gained yarn, and oiled then yarn is reeled through godet roller 11 by take up roll 13 and formed the package 14 of draw-textured yarn.Randomly, heat setting device and interlacing device (not shown in Figure 1) are contained between first conveying roller 8 and second conveying roller 9.In addition, middle part 12 places of the tension force of yarn between finish roll 10 and thread guide 11 measure, and are applied to winding tension on the gained yarn with control.
The amount that is applied to the finish of draw false twisting distortion polyester filament yarn preferably is controlled at about 0.5～about 1% (by mass), is benchmark in the quality of draw false twisting textured yarn.Finish is selected from the mineral oil person of containing as main component usually.False twist texturing filament yarn individual thread fiber number be the radical of silk in 0.5dtex or the littler and yarn be 100 or more situation under, preferred finish applied amount was preferably for 1.3～3.0% (by mass), 1.5～2.3% (by mass) more preferably, quality in false twist textured yarn is a benchmark, so that make the circumferential surface of each threads be coated with oil agent equably.By adopting finish evenly to be coated with long filament as mentioned above, can make the gained yarn at yarn twisting, warping, knitting and woven each inappropriate degree step-down of reelability in the process successively, less traction can also be controlled the scum silica frost accumulation that derives from the finish around the thread guide.Finish oil applies by roll-type oil feeder or measuring jet formula oil feeder.
False twist textured yarn of the present invention under winding tension 0.05～0.30cN/dtex, preferred 0.12～0.23cN/dtex, with winding speed 500～1200m/min, preferred 600～1000m/min reels, winding tension 12 places, position in Fig. 1 measure.This coiling condition can make yarn package compression, its reason be the winding tension height, can also prevent the cardboard core fragmentation, can be controlled at the generation of the difference between the inside and outside yarn qualities of false twist textured yarn coiling package like this.In addition, above-mentioned coiling condition helps to prevent bound edge (serging) phenomenon of yarn, and this phenomenon is called the rolling (rolling) of yarn on false twist apparatus, thereby yarn is reeled regularly.In addition, also suppressed the generation of the non-twist spot on yarn.
As can be used for stretching-friction false twisting device of false twist texturing process, preferably use false twisting frictional disk equipment, wherein, polyurethane resin dish hardness is 75～95 degree, and thickness is 5～12mm, and described resin disk is installed with three axial manner.
In this false twist texturing machine, multifilament textile is preferably with the rotating shaft of dish or the feeding of the position of 30～miter angle and by false twisting.In addition, be 25 when definite false twisting condition makes yarn false twisting number (is unit with sth. made by twisting/rice), 000/F
To 35,000/F
The time, wherein F represents the fiber number of target false twist textured yarn, is unit with dtex, can be suppressed on the gained false twist textured yarn and produce lousiness.
False twist textured yarn of the present invention preferably presents L
*Value and b
*The difference of value is 91.0～99.0, more preferably 93.0～99.0, and according to L
*, a
*, b
*Color and luster standard (JIS Z 8729) is measured, and its reason is to use the special catalyst role in making polyester polymers.
Embodiment
Now further explain the present invention by the following example.
In an embodiment, determine the performance or the feature of polyester polymers, catalyst, melt-spun process, polyester fiber and false twist texturing filament yarn according to following determination method.
(1) inherent viscosity
The inherent viscosity of polyester polymers is measured under 35 ℃ in the solvent of being made up of o-chlorphenol.
(2) titanium and the phosphorus content in polyester polymers
In the mensuration of carrying out remainder catalyst tenor in polyester, with sample heating and melting on aluminium sheet, the molding sample that has plane surface by the compression press manufacturing, then by adopting the x-ray fluorescence analysis device, the 3270E type, Rigaku Electric Industrial Co., Ltd makes, and measures the tenor in the molding sample.
(3) content of diethylene glycol (DEG) (DEG) in polyester polymers
Adopt the hydrazine hydrate decomposing copolymer, (model 263-70, Hitachi company makes) measures the diethylene glycol (DEG) content in the catabolite by gas chromatograph.
(4) the foreign matter layer height that on spinnerets, forms
With carry out continuous melt-spun process 3,6 or 9 days as the described method of each embodiment and condition after, spray remover facing to the spinnerets exit surface, the polyester polymers of extruding is not adhered on the exit surface, dismantle spinnerets then.Then, the employing measurement microscope adheres to and is accumulated in each extrusion cavities foreign matter height on every side.For all extrusion cavities and opinion is all measured the foreign matter layer height, and evaluation mean value.Foreign matter layer height on spinnerets is represented by mean value.
(5) birefringence (Δ n)
The birefringence of polyester fiber is determined from the filamentary hysteresis value of polyester and the fiber number value that adopt petrographic microscope (model: BH-2, Olympus company makes) to measure by the compensator method.
(6) density
The density of polyester polymers adopts prepared normal heptane/tetrachloromethane mixture to measure by the density gradient column method, and the density value of measuring like this is 1.276～1.416.
(7) broken end of silk in the melt-spun process
Use melt-spun device one week of continued operation under the operating condition of each embodiment of single spinnerets, be reported in one operating period in week silk the broken end number of times, but because except the broken end that manually-operated or mechanical reason produce.From the gained data, calculate the broken end number of times of the silk of each spinnerets every day.The broken end number of times of silk is represented with gained result of calculation in the melt-spun process.
(8) polyester polymers glass transition temperature (Tg)
Be added in the aluminium sample disc fixed amount polyester polymers and sealing, place the DSC determinator then, be heated to 280 ℃ from room temperature to rise wet 10 ℃/min of speed.In nitrogen current, keep said temperature 2min, from determinator, take out immediately then, thereby and in nitrogen atmosphere rapidly cooling the sample disc that the polyester polymers that solidifies with amorphous state is housed is provided.Heating gained sample under condition same as described above, temperature rise curve simultaneously draws.Glass transition temperature (Tg) from gained curve calculation polyester polymers.
(9) the divide a word with a hyphen at the end of a line temperature of filament yarn
The temperature of the filament yarn by stretching-false twisting heater outlet is measured by the non-contact thermometer (model: H-7508, Supreme Being people's engineering corporate system is made) that employing is used for mobile goods.
(10) interlacing degree
The interlacing number of the silk in polyester mutifilament yarn of every meter yarn is measured by adopting Rochelld type interlacing instrument.Repeat this mensuration ten times, calculate measurement result mean value.The interlacing degree of filament yarn is represented with the mean value that is calculated.
(11) lousiness
Make the false twist texturing filament yarn stand to appear at the METHOD FOR CONTINUOUS DETERMINATION of the lousiness number on the filament yarn, this is measured and adopts lousiness counting device (model: DT-104, Dong Li company makes) to carry out 20min with 500m/min speed.Lousiness number on the filament yarn is with per 10
6The lousiness numerical table of m filament yarn shows.
(12) curl total percentage (TC) (%)
With superfine false twist texturing filament yarn under 0.044cN/dtex (50mg/ dawn) tension force around the strand frame around so that the strand of the about 3300dtex of fiber number to be provided.The 0.00177cN/dtex+0.177cN/dtex (2mg/d+200mg/d) that will load is applied to the lower end of strand, after applying load 1 minute, measure to twist long L
0, be unit with cm.Removing load 0.177cN/dtex (200mg/d) afterwards from strand, the gained strand is being handled 20min in 100 ℃ of boiling water.After boiling water treating, remove load 0.00177cN/dtex (2mg/d) from strand, with uncharge strand air dry 24hr under zero load condition.Make the strand load 0.00177cN/dtex+0.177cN/dtex (2mg/d+200mg/d) of air dry, applying load 1min, measure the long L of strand
1(cm).Then, strand is removed load 0.177cN/dtex (200mg/d) certainly, after removing load 1min, measures the long L of strand
2(cm).
Calculate the curling percentage of filament yarn according to following formula:
Percentage (%)=((L curls
1-L
2)/L
0) * 100
Replication ten times calculates measurement result mean value.The curling percentage of representing the false twist texturing filament yarn with mean value.
(13) TENSILE STRENGTH and ultimate elongation
Make yarn samples adopt cupping machine (tensiometer, SHIMAZU SEISAKUSHO company) to stand tension test with sample length 20cm, extension speed 20%/min, load-deformation curve draws.From the gained curve, calculate TENSILE STRENGTH and ultimate elongation.
(14) broken end of false twist texturing filament yarn (broken end number/ton)
False twist texturing machine is 1 week of continued operation under the condition identical with each embodiment, in operation, makes the stretched polyester yarn package of each 10kg be transformed into the false twist textured yarn package of two 5kg through the false twist texturing process.Be recorded in the Yarn break number that produces in the false twist texturing process, except the broken end that takes place because of manually-operated and mechanical reason.
The Yarn break number shows with (1000kg) per ton Yarn break numerical table.
(15) (L
*-b
*) value
Polyester fibers is the sheet knit goods of 30cm by adopting No. 12 knitting needle circular knitting machines to carry out knitting (take-knit) thereby length is provided.Provide gained knit goods to carry out L
*Value and b
*PH-value determination pH, described mensuration adopt Hunter color difference meter (model: CR-200, MINOLTA company makes) to carry out, from gained L
*And b
*Calculate poor (L
*-b
*).
Embodiment 1
In the stainless steel reactor that can under band press strip spare, react, add mixture, add 0.009 part of (by mass) tetra-n-butyl titanate then by 100 parts of (by mass) dimethyl terephthalate (DMT)s and 70 parts of (by mass) ethylene glycol.Make the gained reactant mixture under pressure 0.07MPa, stand ester exchange reaction, be heated to 140 ℃～240 ℃ simultaneously.After reaction is finished, 0.035 part of phosphine acyl acetic acid triethyl group ester is sneaked in the product.
The product that will contain the diethyl terephthalate places polycondensation reactor, at high vacuum 26.67Pa or lowlyer be heated to 290 ℃, carrying out the polycondensation reaction of diethyl terephthalate, the preparation inherent viscosity is 0.60, diethylene glycol (DEG) content is 1.5% polyester polymers.Polyester polymers is molded as the section shape.The P elements M of polyester polymers
PValue is 30, titanium elements M
TiValue is 5, M
P/ M
TiRatio be 6, M
P+ M
TiSum is 35.
Make polyester polymers section drying, feeding is equipped with in the melt-spun device of screwe-type xtruder, and fusion in extruder.In the nozzle block with 315 ℃ of melt feeding maintenances, filter, extrude through 288 circular extrusion cavities then, in spinnerets, be configured as thread bundle with the 39g/min rate of extrusion with 0.15mm diameter through filament spinning component.
Make the thread bundle of extruding of polymer melt by remain on 230 ℃, the spinnerets exit surface and the hot-zone that between the 30mm place of spinnerets exit surface, forms and with 25 ℃ of temperature, cool off from the cooling air draught of lateral blowing type spinning shaft supply.Make gained solidify the long filament boundling, oil to silk with finish simultaneously, the finish supply is positioned at the measuring jet type of locating from spinnerets exit surface 420mm (boundling length) deflector roll that oils from being installed in.
The gained endless tow through a pair of be that the godet roller of 3000m/min rotation batches with the peripheral speed, and adopt up-coiler to reel, thus provide have birefringence 0.047, the not stretched polyester multifilament textile of density 1.346, fineness of yarn 130.5dtex/288 rhizoid.
In the melt-spun process, around spinnerets, adhere to 3 days the time after melt-spun begins and the foreign matter floor height of accumulation is 1.8 μ m, and melt-spun is 3.0 μ m 9 days the time after beginning.In addition, after melt-spun begins 9 days the time, the Yarn break number of each spinnerets every day is 0.14 time.That is, Yarn break takes place hardly.Gained polyester mutifilament yarn lousiness number is 0.01/10
6M or lower, (L
*-b
*) value is 95.0.
The stretched polyester multifilament textile does not feed draw false twisting Texturing Machines (model: HTS-15V, Supreme Being worker SEIKI company makes) from the package unwinding, and the latter is equipped with the contactless flute profile heater of length 1.04m.In this machine, each rhizoid in the yarn is to carry out the air interlacing each other by air nozzle air supplied air-flow, and the interlacing degree that forms silk is 65.Make the interlacing multifilament textile feeding that does not stretch use the false twist texturing program of false twisting frictional disk equipment, wherein polyurethane dish hardness is that 90 degree, thickness are 9mm, diameter is 58mm, install with three direction of principal axis, the yarn feeding angle is counted 40 degree from the rotating shaft of dish, thereby make multifilament textile Drawing and false twisting distortion simultaneously, wherein (twisting count) * (fiber number of false twist textured yarn (dtex))
Be 30,000, the filament yarn temperature of advancing is 200 ℃ (on Tg 133 ℃), and the time of staying is 0.089 second in heater, and draw ratio is 1.57.The gained false twist textured yarn (contains with finish oil, as principal component, 90% mineral oil) oil with 1.8% (by mass), in the filament yarn quality is benchmark, then, make have fineness of yarn 85.0dtex/288 rhizoid, the false twist texturing filament yarn that oils of individual thread fiber number 0.29dtex, under winding tension 0.18cN/dtex, winding speed 700m/min, reel, form yarn package.
In the draw false twisting deforming process, the broken end number of yarn is 3.1 times/ton.Total percentage (TC) that curls of gained false twist texturing filament yarn is 2.9%, and TENSILE STRENGTH is 26.0% for the 3.4cN/dtex ultimate elongation, and the lousiness number is 0.02/10
6M, (L
*-b
*) difference be 94.9.
Comparative example 1
In the stainless steel reactor that can under band press strip spare, react, add mixture, and then add 0.064 part of (by mass) calcium acetate hydrate by 100 parts of (by mass) dimethyl terephthalate (DMT)s and 70 parts of (by mass) ethylene glycol.Make the gained reactant mixture under pressure 0.07MPa, stand ester exchange reaction, be heated to 140 ℃～240 ℃ simultaneously.In reactant mixture, sneak into 0.044 part of (by mass) 56% (by mass) phosphate aqueous solution, so that reaction is finished.
The product that will contain mixture places polycondensation reactor, at high vacuum 26.67Pa or lowlyer be heated to 290 ℃, simultaneously antimonous oxide is sneaked in the reactant mixture, so that the polycondensation reaction of diethyl terephthalate is carried out.Obtain inherent viscosity and be 0.630 polyester polymers.Polyester polymers is molded as the section shape.
With the process melt spinning identical with embodiment 1, just the section of the polyester polymers of embodiment 1 is replaced by above-mentioned polyester polymers section with polyester polymers section.
The fineness of yarn of gained polyester mutifilament yarn (partially oriented filament yarn) is the 130.0dtex/288 rhizoid.
In this comparative example, along with the passing of melt-spun time, the foreign matter around the spinnerets adheres to and accumulation takes place rapidly, and along with the increase of bending, swing and the rotation of the thread bundle of extruding of melt, spinning broken end number increases sharply.In this connection, after the beginning melt-spun 3 days, the foreign matter layer height that forms around the spinnerets reached 28.0 μ m, and the spinning number that breaks end is each spinnerets every day 16.0 times, is difficult to proceed normal melt-spun process like this.Therefore the melt-spun process stops.Gained not stretched polyester long filament lousiness number is 0.06/10
6M or still less, (L
*-b
*) difference be 91.7.
Make gained package form not stretched polyester filament yarn (partially oriented filament yarn) through with stretching, the false twist texturing process of embodiment 1 same way as and condition.Obtaining fineness of yarn is the false twist texturing filament yarn of 84dtex/288 rhizoid.
In this false twist texturing process, false twist texturing yarn breakage number is 8.3 times/ton.Total percentage (TC) that curls of gained false twist texturing filament yarn is 3.0 in addition, and TENSILE STRENGTH is 3.5cN/dtex, and ultimate elongation is 25.8%, and the lousiness number is 0.82/10
6M, (L
*-b
*) difference be 90.9.
Preparation of Catalyst
919g ethylene glycol and 10g acetate are mixed.The gained mixture is mixed with 71g four fourth alkoxytitaniums, the clear solution of titanium compound in ethylene glycol is provided.In addition, 34.5g phosphoric acid one lauryl is sneaked in the 656g ethylene glycol, be heated to 100 ℃ and stirring simultaneously, clear solution is provided.
Above-mentioned two kinds of clear solutions are mixed with each other at 100 ℃, the gained mixture was stirred 1 hour, white opacity liquid is provided.In this reaction, the mixing ratio of two kinds of clear solutions of control, the amount that makes the phosphorus atoms in transparent compound titanium solution is 2.0 moles of every mole of titanium atoms in transparent phosphorus compound solution.Collect the gained white deposits by filtering, and wash and drying.Desciccate is called the TPI-2.0 catalyst as catalyst.
The polyester polymers preparation
225 parts of (by mass) diglycol terephthalate oligomer, adjustment are depressed at 255 ℃, ambient air to being equipped with, in the reactor of nitrogen atmosphere, with the slurry of constant rate of feeding feeding by 179 parts of (by mass) high purity terephthalic acids and 95 parts of (by mass) ethylene glycol are mixed with mutually, and in reactor, stir and make compound carry out esterification each other, distill out the accessory substance that comprises water and ethylene glycol, make this esterification continue to carry out 4hr, thereby reaction is finished.In the result of this reaction, esterification degree is 98% or higher, and the degree of polymerization of gained oligomer is about 5～about 7.
To place the polycondensation container by 225 parts of (by mass) oligomer that above-mentioned esterification provides, and with 3.34 parts of (by mass) TPI-2.0 catalyst mix.Heating gained polycondensation system, temperature progressively reach 280 ℃ from 255 ℃, and progressively pressurizeing reaches 60Pa from ambient atmosphere pressure, stirs simultaneously, removes the accessory substance that produces by reaction, for example water and ethylene glycol from the polycondensation system.
The degree that polycondensation reaction is carried out is checked by the load of monitoring stirring arm in reaction system, and when the degree of polymerization of polyester polymers reached desired level, reaction finished.Then, make the product in the polycondensation system extrude the formation wire through the extrusion cavities that in polycondensation reactor, forms continuously.Make polymer strands cooling of extruding and the pellet that is cut into the about 3mm of diameter.The inherent viscosity of gained polyethylene terephthalate polymer is 0.64.
The production of polyester false twist texturing filament yarn
Make polyester polymers section drying, feeding is equipped with in the melt-spun device of screwe-type xtruder, and fusion in extruder.Melt is fed in the nozzle block that remains on 315 ℃, filter, extrude through 288 circular extrusion cavities then, in spinnerets, be configured as thread bundle with the 39g/min rate of extrusion with 0.15mm diameter through filament spinning component.
The thread bundle of extruding of polymer melt is passed through at the spinnerets exit surface with in the hot-zone that forms between the 30mm place of spinnerets exit surface.The hot-zone temperature remains on 230 ℃.Then, thread bundle temperature is that cooling air draught 25 ℃, that supply from lateral blowing type spinning shaft cools off.Gained solidifies multifilament, by being installed in the measuring jet type that is positioned at from the spinnerets exit surface 420mm place deflector roll that oils, oils with finish, simultaneously with silk boundling formation endless tow.
The gained endless tow through a pair of be that the godet roller of 3000m/min rotation batches with the peripheral speed, and adopt up-coiler to reel, thus provide have birefringence 0.045, the not stretched polyester multifilament textile of density 1.345, fineness of yarn 130dtex/288 rhizoid.
In the melt-spun process, the foreign matter floor height that adheres to accumulation after melt-spun begins 3 days the time around spinnerets is 2.0 μ m, and melt-spun is 2.8 μ m 9 days the time after beginning.In addition, after melt-spun begins 9 days the time, the Yarn break number of each spinnerets every day is 0.14 time.That is, Yarn break takes place hardly.Gained polyester mutifilament yarn lousiness number is 0.01/10
6M or lower, (L
*-b
*) value is 95.6.
The stretched polyester multifilament textile does not feed draw false twisting Texturing Machines (model: HTS-15V, Supreme Being worker SEIKI company makes) from the package unwinding, and the latter is equipped with the contactless flute profile heater of length 1.04m.In this machine, each rhizoid in the yarn is to carry out the air interlacing each other by air nozzle air supplied air-flow, and the interlacing degree that forms silk is 65.Make the interlacing multifilament textile feeding that does not stretch use the false twist texturing program of false twisting frictional disk equipment, wherein polyurethane dish hardness is that 90 degree, thickness are 9mm, diameter is 58mm, install with three direction of principal axis, the yarn feeding angle is counted 40 degree from the rotating shaft of dish, thereby make multifilament textile Drawing and false twisting distortion simultaneously, wherein (twisting count) * (fiber number of false twist textured yarn (dtex))
Be 30,000, the filament yarn temperature of advancing is 206 ℃ (on Tg 133 ℃), and the time of staying is 0.089 second in heater, and draw ratio is 1.58.The gained false twist textured yarn (contains with finish oil, as principal component, 90% mineral oil) oil with 1.8% (by mass), in the filament yarn quality is benchmark, then, make have fineness of yarn 83.5dtex/288 rhizoid, the false twist texturing filament yarn that oils of individual thread fiber number 0.29dtex, under winding tension 0.18cN/dtex, winding speed 700m/min, reel, form yarn package.
In the draw false twisting deforming process, the broken end number of yarn is 2.2 times/ton yarns.Total percentage (TC) that curls of gained false twist texturing filament yarn is 3.1%, and TENSILE STRENGTH is 26.5% for the 3.2cN/dtex ultimate elongation, and the lousiness number is 0.01/10
6M, (L
*-b
*) difference be 94.5.
Comparative example 2
The polyethylene terephthalate of inherent viscosity 0.630 is by by antimonous oxide (Sb
2O
3) polycondensation catalyst formed exists down, makes dimethyl terephthalate (DMT) and ethylene glycol carry out that polycondensation prepares.
With the polyethylene terephthalate polymer granulation, make the gained pellet under method identical and condition with embodiment 2 through the melt spinning process, make fineness of yarn (partially oriented) and be the polyester filament yarn of 130dtex/288 rhizoid.
In this comparative example, the foreign matter that produces around spinnerets becomes big rapidly along with the delay of melt-spun time, impels the filament yarn bending of extruding.Wave and rotate, so the filament yarn broken end increases sharply.Like this, after the melt-spun process begins three days, the foreign matter layer height that forms on spinnerets reached 28.0 μ m, and the filament yarn of extruding broken end number reaches each spinnerets every day 16 times.The melt-spun process can not be carried out regularly continuously now, so this process stops to carry out.Gained polyester filament yarn lousiness number is 0.06/10
6M, (L
*-b
*) difference is 91.7.
Make gained (partially oriented) polyester mutifilament yarn that do not stretch stand the draw false twisting deforming process, make the false twist textured yarn that fineness of yarn is the 84dtex/288 rhizoid with method and the condition identical with embodiment 2.
In the false twist texturing process, filament yarn broken end number is yarn per ton 8.3 times.Total percentage (TC) that curls of gained false twist textured yarn is 3.0%, and TENSILE STRENGTH is 3.5cN/dtex, and ultimate elongation is 25.8%, and the lousiness number is 0.82/10
6M, (L
*-b
*) difference be 90.9.
Commercial Application
Can provide according to the present invention that to have good colour and draw false twisting deformation process stability high Polyester fiber. Polyester fiber does not have lousiness substantially, can produce to have good color and be in harmonious proportion very high The false twist textured yarn of quality. This textured yarn can be advantageously used in high-quality fabric, indoor Modify textile material, therefore have high practical application.
Claims (9)
1. polyester fiber comprises the polyester polymers as principal component, and it has 0.1～1.0dtex filament fiber number,
Wherein:
Polyester polymers is the polymer that aromatic dicarboxylic acid ester's polycondensation is made by in the presence of catalyst,
Described catalyst comprises mixture (1) or the product of stipulating below (2),
Being used for mixture of catalysts (1) comprises
(A) and (B), and (A) mix with (B);
(A) a kind of titanium compound composition comprises and is selected from least a in (b):
(b) product of the aromatic polycarboxylic acid shown in the alkoxytitanium of general formula (I) and the general formula (II):
In described general formula (I), R
1, R
2, R
3And R
4Represent the alkyl or phenyl that contains 1～20 carbon atom independently of one another respectively, m represents integer 1～4, when m represents integer 2,3 or 4, and 2,3 or 4 R
2And R
3Can be respectively mutually the same or differ from one another,
In general formula (II), n represents integer 2～4; The perhaps product of the acid anhydride of the acid of the alkoxytitanium of general formula (I) and general formula (II);
(B) phosphorus compound composition comprises at least a phosphorus compound by general formula (III) expression:
In described general formula (III), R
5, R
6And R
7Represent the alkyl group that contains 1～4 carbon atom, X representative-CH independently of one another respectively
2-group or-CH (Y)-group, wherein Y represents phenyl,
The consumption that is used for the mixture (1) of polycondensation catalyst should satisfy following relationship formula (i) and (ii) represented requirement:
1≤M
P/M
Ti≤15 (i)
With
10≤M
P+M
Ti≤100 (ii)
Wherein, M
TiThe ratio of the mM value of the titanium elements that representative contains in titanium compound composition (A) and aromatic dicarboxylic acid ester's mole value is represented with percentage, and M
PThe ratio of the mM value of the P elements that representative contains in phosphorus compound composition (A) and aromatic dicarboxylic acid ester's mole value is represented with percentage; With
The product (2) that is used for catalyst comprises (C) and (D), and (C) and (D) reacts;
Wherein:
(C) titanium compound composition comprises and is selected from least a in following (c):
(c) alkoxytitanium of representing by general formula (I);
In described general formula (I), R
1, R
2, R
3And R
4Represent the alkyl or phenyl that contains 1～20 carbon atom independently of one another respectively, m represents integer 1～4, when m represents integer 2,3 or 4, and 2,3 or 4 R
2And R
3Can be respectively mutually the same or differ from one another,
(D) phosphorus compound composition comprises at least a phosphorus compound by general formula (IV) expression,
In described general formula (IV), R
8Representative contains the alkyl of 1～20 carbon atom or contains the aryl of 6～20 carbon atoms, and p represents integer 1 or 2.
2. the polyester fiber of claim 1, wherein, be used for the product of catalyst (2), the reacting dose proportion of composition (D) and composition (C), during with ratio (P/Ti) expression of the molar weight of the titanium atom that contains in the molar weight of the phosphorus atoms that contains in the composition (D) and the composition (C), it is 1: 1 to 3: 1.
3. the polyester fiber of claim 1, wherein, general formula (IV) phosphorus compound that is used for product (2) is selected from mono alkyl phosphate.
4. the polyester fiber of claim 1, wherein, the aromatic dicarboxylic acid dialkyl is that to carry out ester exchange reaction by the dialkyl of aromatic dicarboxylic acid and aklylene glycol in the presence of titanium-containing catalyst prepared.
5. the polyester fiber of claim 1, wherein the aromatics dicarboxylester is selected from terephthalic acid (TPA), 1,2-naphthalenedicarboxylic acid, phthalic acid, M-phthalic acid, diphenyl dicarboxylic acid and biphenoxyl ethane dicarboxylic acids; Aklylene glycol is selected from ethylene glycol, 1,4-butanediol, 1, ammediol, propylene glycol, neopentyl glycol, 1,6-hexylene glycol and ten dimethylene glycol.
6. the polyester fiber of claim 1, wherein, polyester polymers is selected from polyethylene terephthalate, poly terephthalic acid 1, ammediol ester and poly terephthalic acid 1,4-butanediol ester.
7. the polyester fiber of any one in the claim 1～6, wherein, the inherent viscosity of polyester polymers is 0.45～0.70, this value is to measure under 35 ℃ in the solution of o-chlorphenol.
8. false twist textured yarn comprises in the claim 1～7 any one polyester fiber.
9. the false twist textured yarn of claim 8, wherein, the L of false twist texturing polyester fibers
*And b
*The difference of value is 91.0～99.0.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003008161A JP2004218158A (en) | 2003-01-16 | 2003-01-16 | Polyester fiber and false twisted yarn made thereof |
| JP8161/2003 | 2003-01-16 | ||
| JP70083/2003 | 2003-03-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1692188A CN1692188A (en) | 2005-11-02 |
| CN100338276C true CN100338276C (en) | 2007-09-19 |
Family
ID=32898046
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801003524A Expired - Fee Related CN100338276C (en) | 2003-01-16 | 2003-12-26 | Polyester fiber and false twisted yarn made thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2004218158A (en) |
| CN (1) | CN100338276C (en) |
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|---|---|---|---|---|
| CN108484895B (en) * | 2018-04-09 | 2020-06-30 | 福建锦兴环保科技有限公司 | Phosphorus-titanium composite polyester catalyst and preparation process thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5443295A (en) * | 1977-09-13 | 1979-04-05 | Teijin Ltd | Production of polyester |
| JPS5445397A (en) * | 1977-09-19 | 1979-04-10 | Teijin Ltd | Preparation of polyester |
| US4254018A (en) * | 1977-03-01 | 1981-03-03 | Akzona Incorporated | Linear polyesters containing phosphonate heat stabilizers |
| JP2000319370A (en) * | 1999-05-13 | 2000-11-21 | Teijin Ltd | Production of polyester |
| US20010056173A1 (en) * | 2000-05-17 | 2001-12-27 | Jae-Young Jeon | Method for preparing polyester resin copolymerized with 1,4-cyclohexanedimethanol |
| JP2003160655A (en) * | 2001-11-28 | 2003-06-03 | Teijin Ltd | Method for producing polyester, and polyester fiber |
| JP2003160656A (en) * | 2001-11-28 | 2003-06-03 | Teijin Ltd | Method of manufacturing polyester and fiber |
| JP2003293222A (en) * | 2002-04-01 | 2003-10-15 | Teijin Ltd | High-whiteness polyester fiber |
-
2003
- 2003-01-16 JP JP2003008161A patent/JP2004218158A/en active Pending
- 2003-12-26 CN CNB2003801003524A patent/CN100338276C/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4254018A (en) * | 1977-03-01 | 1981-03-03 | Akzona Incorporated | Linear polyesters containing phosphonate heat stabilizers |
| JPS5443295A (en) * | 1977-09-13 | 1979-04-05 | Teijin Ltd | Production of polyester |
| JPS5445397A (en) * | 1977-09-19 | 1979-04-10 | Teijin Ltd | Preparation of polyester |
| JP2000319370A (en) * | 1999-05-13 | 2000-11-21 | Teijin Ltd | Production of polyester |
| US20010056173A1 (en) * | 2000-05-17 | 2001-12-27 | Jae-Young Jeon | Method for preparing polyester resin copolymerized with 1,4-cyclohexanedimethanol |
| JP2003160655A (en) * | 2001-11-28 | 2003-06-03 | Teijin Ltd | Method for producing polyester, and polyester fiber |
| JP2003160656A (en) * | 2001-11-28 | 2003-06-03 | Teijin Ltd | Method of manufacturing polyester and fiber |
| JP2003293222A (en) * | 2002-04-01 | 2003-10-15 | Teijin Ltd | High-whiteness polyester fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1692188A (en) | 2005-11-02 |
| JP2004218158A (en) | 2004-08-05 |
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