CN104480569B - Polyester elastic yarn and preparation method thereof - Google Patents
Polyester elastic yarn and preparation method thereof Download PDFInfo
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- CN104480569B CN104480569B CN201410852229.8A CN201410852229A CN104480569B CN 104480569 B CN104480569 B CN 104480569B CN 201410852229 A CN201410852229 A CN 201410852229A CN 104480569 B CN104480569 B CN 104480569B
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- ethylene glycol
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- 229920000728 polyester Polymers 0.000 title claims abstract description 225
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- -1 Polytrimethylene Terephthalate Polymers 0.000 claims abstract description 103
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 62
- 239000000194 fatty acid Substances 0.000 claims abstract description 62
- 229930195729 fatty acid Natural products 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 148
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 128
- 238000005886 esterification reaction Methods 0.000 claims description 114
- 230000032050 esterification Effects 0.000 claims description 104
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 95
- 238000006068 polycondensation reaction Methods 0.000 claims description 90
- 239000000047 product Substances 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 31
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- 238000004821 distillation Methods 0.000 claims description 30
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 20
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 238000004804 winding Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 12
- 229940006460 bromide ion Drugs 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- PNZVFASWDSMJER-UHFFFAOYSA-N acetic acid;lead Chemical compound [Pb].CC(O)=O PNZVFASWDSMJER-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004513 sizing Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 208000011580 syndromic disease Diseases 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 5
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical group [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 88
- 229920002215 polytrimethylene terephthalate Polymers 0.000 abstract description 22
- 238000004043 dyeing Methods 0.000 abstract description 15
- 210000004177 elastic tissue Anatomy 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 42
- 239000005020 polyethylene terephthalate Substances 0.000 description 29
- 229920000139 polyethylene terephthalate Polymers 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 19
- 229920002521 macromolecule Polymers 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- MHXFWEJMQVIWDH-UHFFFAOYSA-N 1-amino-4-hydroxy-2-phenoxyanthracene-9,10-dione Chemical compound C1=C(O)C=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C1OC1=CC=CC=C1 MHXFWEJMQVIWDH-UHFFFAOYSA-N 0.000 description 9
- 239000000986 disperse dye Substances 0.000 description 7
- NLAGNNORBYGNAV-UHFFFAOYSA-N isotriacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCC(C)C NLAGNNORBYGNAV-UHFFFAOYSA-N 0.000 description 6
- KUPLEGDPSCCPJI-UHFFFAOYSA-N n-Tetracontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC KUPLEGDPSCCPJI-UHFFFAOYSA-N 0.000 description 6
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- VHQQPFLOGSTQPC-UHFFFAOYSA-N n-Pentatriacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC VHQQPFLOGSTQPC-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- NHWDPCHMQMJMRM-UHFFFAOYSA-N 2-aminoicosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(N)C(O)=O NHWDPCHMQMJMRM-UHFFFAOYSA-N 0.000 description 3
- XEDDSVXNGSVIKY-UHFFFAOYSA-N 2-aminopentadecanoic acid Chemical compound CCCCCCCCCCCCCC(N)C(O)=O XEDDSVXNGSVIKY-UHFFFAOYSA-N 0.000 description 3
- RTBNAMFQHXHWPI-UHFFFAOYSA-N 2-tetracosylpropanedioic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCC(C(O)=O)C(O)=O RTBNAMFQHXHWPI-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- GAWDONPIRRGKHC-UHFFFAOYSA-N 2-aminopentatetracontanoic acid Chemical compound NC(CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC)C(=O)O GAWDONPIRRGKHC-UHFFFAOYSA-N 0.000 description 2
- HRWROHLOIUTEJF-UHFFFAOYSA-N 2-aminopentatriacontanoic acid Chemical compound NC(CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC)C(=O)O HRWROHLOIUTEJF-UHFFFAOYSA-N 0.000 description 2
- GHGIEIMFIMJTLX-UHFFFAOYSA-N 2-aminotetracontanoic acid Chemical compound NC(CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC)C(=O)O GHGIEIMFIMJTLX-UHFFFAOYSA-N 0.000 description 2
- CCDWXBORKKHUCD-UHFFFAOYSA-N 2-aminotriacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)C(O)=O CCDWXBORKKHUCD-UHFFFAOYSA-N 0.000 description 2
- HXKXBCBZXXQPPD-UHFFFAOYSA-N 2-bromododecanoic acid Chemical compound CCCCCCCCCCC(Br)C(O)=O HXKXBCBZXXQPPD-UHFFFAOYSA-N 0.000 description 2
- MSJPZIZRTHHRLP-UHFFFAOYSA-N 2-bromoicosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(Br)C(O)=O MSJPZIZRTHHRLP-UHFFFAOYSA-N 0.000 description 2
- MUXQOFXMCVOPPW-UHFFFAOYSA-N 2-bromopentadecanoic acid Chemical compound CCCCCCCCCCCCCC(Br)C(O)=O MUXQOFXMCVOPPW-UHFFFAOYSA-N 0.000 description 2
- BZDUBIFGRWSLRE-UHFFFAOYSA-N 2-bromotetracontanoic acid Chemical compound BrC(CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC)C(=O)O BZDUBIFGRWSLRE-UHFFFAOYSA-N 0.000 description 2
- CGTWXNZDWKWRSL-UHFFFAOYSA-N 2-bromotriacontanoic acid Chemical compound BrC(CCCCCCCCCCCCCCCCCCCCCCCCCCCC)C(=O)O CGTWXNZDWKWRSL-UHFFFAOYSA-N 0.000 description 2
- SNNLICYRIGNYGV-UHFFFAOYSA-N 2-tetratetracontylpropanedioic acid Chemical class C(CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC)(C(=O)O)C(=O)O SNNLICYRIGNYGV-UHFFFAOYSA-N 0.000 description 2
- CNRCURLHTYFOII-UHFFFAOYSA-N 2-tetratriacontylpropanedioic acid Chemical class C(CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC)(C(=O)O)C(=O)O CNRCURLHTYFOII-UHFFFAOYSA-N 0.000 description 2
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- DURCXLFMRCZCFV-UHFFFAOYSA-N 2-bromopentatetracontanoic acid Chemical compound BrC(CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC)C(=O)O DURCXLFMRCZCFV-UHFFFAOYSA-N 0.000 description 1
- XADSXJODDPASFF-UHFFFAOYSA-N 2-bromopentatriacontanoic acid Chemical compound BrC(CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC)C(=O)O XADSXJODDPASFF-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QETVFNWBXURDPO-UHFFFAOYSA-N nonacosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCN QETVFNWBXURDPO-UHFFFAOYSA-N 0.000 description 1
- AYYUCYJPSQMEDD-UHFFFAOYSA-N nonatriacontan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCN AYYUCYJPSQMEDD-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- VYRMHDHLFQRAAY-UHFFFAOYSA-N pentatetracontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC VYRMHDHLFQRAAY-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XYTULFXJTGBOBM-UHFFFAOYSA-N tetratetracontan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCN XYTULFXJTGBOBM-UHFFFAOYSA-N 0.000 description 1
- NDMKRVHBPCRHBA-UHFFFAOYSA-N tetratriacontan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCN NDMKRVHBPCRHBA-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
Abstract
The invention relates to a polyester elastic yarn and a preparation method thereof. The polyester elastic yarn is a double-component parallel composite yarn prepared from PTT (Polytrimethylene Terephthalate) and modified polyester; the elongation at break of the polyester elastic yarn is 30.0+/-3.0%, and the boiling water shrinkage is 10.0+/-0.5%; the modified polyester is prepared from polyester and amino fatty acid gylcol ester, wherein the amino fatty acid gylcol ester is dispersed among molecular chains of polyester and is in hydrogen-bond interaction with the molecular chains of polyester, therefore, the relative positions of the amino fatty acid gylcol ester and the molecular chains of polyester can be fixed. According to the polyester elastic yarn, the free volume space among molecular chains in fibers is expanded by 20-30v/v% under a temperature of 90 to 130 DEG C; the dyeing performance of polyester can be improved and the elastic damage degree of composite yarns can be reduced by adopting the polyester elastic yarn; the polyester elastic yarn is suitable for preparing elastic fibers and elastic decorative products.
Description
Technical field
The invention belongs to fibre technology field, it is related to a kind of polyester silk and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) fiber since the advent of the world, has obtained rapidly because of its excellent performance
Development, its yield has become as the hat of world's synthetic fibers.Polyester fiber has fracture strength and elastic modelling quantity is high, and resilience is fitted
In, thermal finalization is excellent, and heat-resisting light resistance is good and a series of premium properties such as acid-fast alkali-proof corrosion resistance, and fabric have anti-
The advantages of wrinkle, stiffness are good, so, polyester fiber is widely used in the fields such as clothes, home textile.
PET belongs to symmetric straight chain macromolecular, and strand does not contain side-chain radical, and regularity is very good, its main chain
Phenyl ring containing rigidity and flexible alkyl, and the ester group being directly connected with phenyl ring constitutes rigid conjugated body with phenyl ring
System, thus constrain rotating freely of its soft segment.The impact to glass transition temperature for this structure is it will be evident that increasing
The wall ridge of molecule segment motion, the glass transition temperature of PET is higher, needs to dye at very high temperatures, promotes dyestuff
Molecule is to the diffusion of fibrous inside.In addition, the strand of PET is regular, good crystallinity, strand arrangement is tight, and strand
The upper polar group not having an effect with dye molecule, makes the colouring of polyester fiber more difficult.
Difficult for solving the problems, such as PET dyeing, now mainly connect by introducing dye molecule using techniques or methods
By base or increase polyester amorphous regions amount method although the dyeability of polyester can be improved, destroy PET segment rule
Whole property, to obtain the raising of dyeability with the performance reducing polyester fiber.Do not destroying polyester fiber crystallinity and permutation degree
In the case of, the method adopting at present has three kinds of colouring methods such as support methods, high temperature and high pressure method and high temperature thermosoling.
Polyester silk is different using the percent thermal shrinkage of PET with PTT both components, by composite spinning arranged side by side, obtains
The PET/PTT composite bicomponent arranged side by side fiber that must have from crimpability, superior elasticity can be provided.Due to two component percent thermal shrinkages
Difference be released in last handling process thus creating permanent two-dimensional helical curling " the higher PTT of shrinkage factor
In the inner side of spiral, the relatively low PET of shrinkage factor is in outside spiral.The difference of two kinds of component shrinkage factors and polymeric inner factor
(as macromolecular chain chemical composition and structure is different) and external condition (as the change of stretching, heat set conditions) are relevant.Simultaneously by
Low compared with PET 10-20 DEG C in PTT dyeing temperature, the difficulty brought is to select low temperature dyeing, then contaminate not on PET；Select high temperature dye
Color, then the elasticity of composite filament is impaired.
Content of the invention
It is an object of the invention to provide a kind of polyester silk and preparation method thereof, the present invention is using amino aliphatic acid second two
In uniform temperature condition, the increasing degree of free volume is far longer than the characteristic of polyester macromolecule chain to alcohol ester, is divided by improving
Scattered dyestuff molecule enters the degree within polyester, to improve the dyeability of polyester, also can reduce dyeing temperature simultaneously
Reach Color, reduce the elastic extent of damage of composite filament；Simultaneously because in first place in amino ethylene glycol fatty acid molecule
The presence of amino, increases itself hydrogen bond action and polyester macromolecule chain between, increased the compatibility of it and polyester and is gathering
Dispersion in ester, decreases migration to greatest extent.Polyester construction regularity, crystallinity are not destroyed simultaneously, maintain poly-
The premium properties of ester.
A kind of polyester silk of the present invention, is cut into slices respectively through not threaded by PTT, modified poly ester PET, in composite component
Place carries out compound distribution spinning and obtains, and described modified poly ester is to be made up of polyester and amino ethylene glycol fatty acid, described amino
Ethylene glycol fatty acid is dispersed in the molecule interchain of described polyester, and described amino ethylene glycol fatty acid and described polyester point
There is hydrogen bond action between subchain, so that described amino ethylene glycol fatty acid and the relative position of the strand of described polyester is fixed；Institute
State polyester silk under the conditions of temperature is 90～130 DEG C, the free volume space of fibrous inside molecule interchain increases 20～
30v/v%；
The molecular structure of described amino ethylene glycol fatty acid is：
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
Wherein, n=10-50.
As preferred technical scheme：
A kind of described polyester silk, line density deviation ratio≤0.5% of described polyester silk, fracture strength >=
3.0cN/dtex, fracture strength CV value≤5.0%, elongation at break is 30.0 ± 3.0%, extension at break CV value≤10.0%,
Yarn unevenness CV≤2.00%, boiling water shrinkage 10.0 ± 0.5%, oil content 1.00 ± 0.20%.
A kind of described polyester silk, described amino ethylene glycol fatty acid accounts for the weight percent of described polyester silk
Than for 0.5～2.5%.
Present invention also offers a kind of preparation method of polyester silk, PTT, modified poly ester PET are cut into slices respectively through not
Threaded, carry out compound distribution at composite component, and extrude, cool down, oiling, stretching in composite spinneret, thermal finalization and volume
Around prepared polyester silk；
The temperature of described extrusion is 280～290 DEG C；
The wind-warm syndrome of described cooling is 20～25 DEG C；
The speed of described winding is 4000～4600m/min；
Filament number is 0.7～1.5dtex；
The preparation process of described modified poly ester includes：
(1) preparation of amino ethylene glycol fatty acid：
1）By binary of fatty acids and methyl alcohol with 1:The amount of 1.5 mol ratios adds in reactor, under the catalysis of the concentrated sulfuric acid, plus
Heat to 80～110 DEG C, refuxing esterification, cooling, separating-purifying obtains binary of fatty acids mono-methyl；Described binary of fatty acids is 12
Alkane dicarboxylic acids is one of to dopentacontane dicarboxylic acids；Reaction equation is：
HOOC(CH2)nCOOH+CH3OH→CH3OOC(CH2)nCOOH
Wherein n=10～50.
2) by described binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide in molar ratio 1:1:1 is dissolved in benzene, and wherein two
The concentration of first aliphatic acid mono-methyl is 0.05～0.1mol/L, under nitrogen atmosphere, reacts at 80～90 DEG C, backflow, when no longer
When having gas to produce, add a certain amount of dilute sulfuric acid to react 2～3 hours, be washed out, purify and be dried, obtain product bromo
Aliphatic acid；Reaction equation is：
3) by the ammoniacal liquor of bromo aliphatic acid and 15～25wt% in molar ratio 1:2 are added in reactor, and stirring, in room temperature
Lower reaction, then product is heated distillation, and absorb ammonia with cold water, the temperature of heating distillation is less than 70 DEG C, until no
Bubble produces, that is, stop distillation, then cooled down and suction filtration, and filter cake deionized water is washed till no till bromide ion, by product
Vacuum drying obtains product amino aliphatic acid；Vacuum drying temperature can adopt 60～70 DEG C；Reaction equation is：
HOOC(CH2)nBr+NH3→HOOC(CH2)nNH2+NH4Br；
4) by ethylene glycol and amino aliphatic acid in molar ratio for 1.1:2 stir, and press amino fatty acid wt 1～
3% addition concentration is the sulfuric acid of 40～50wt% is catalyst, carries out esterification, esterification reaction temperature is 160～220 DEG C,
Esterification water quantity of distillate reach theoretical value more than 90% be esterification terminal；The separated purification of product obtains amino fat
Sour glycol ester；Reaction equation is：
HOOC(CH2)nNH2+HOCH2CH2OH→
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
Described esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, after being made into uniform sizing material, carry out esterification, obtain esterification and produce
Thing；Esterification is pressurizeed in nitrogen atmosphere, and in normal pressure～0.3MPa, at 250～260 DEG C, esterification water evaporates temperature Stress control
Output reach theoretical value more than 90% be esterification terminal；
Described polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the described polycondensation reaction low vacuum stage, add catalyst and stabilizer in esterification products, under conditions of negative pressure
Start polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature control at 260～270 DEG C,
Reaction time is 30～50 minutes；
Add amino ethylene glycol fatty acid after the described polycondensation reaction low vacuum stage terminates, and stir, mixing time
15～20 minutes；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275～280 DEG C, 50～90 minutes reaction time；
Prepared modified poly ester.
The mol ratio of a kind of preparation method of polyester silk as above, described ethylene glycol and described terephthalic acid (TPA)
For 1.2～2.0:1.
A kind of preparation method of polyester silk as above, described catalyst is selected from antimony oxide, antimony glycol
One of with antimony acetate, catalyst amount is the 0.01%～0.05% of described terephthalic acid (TPA) weight.
A kind of preparation method of polyester silk as above, described stabilizer is selected from triphenyl phosphate, tripotassium phosphate
One of ester and Trimethyl phosphite, stabilizing agent dosage is the 0.01%～0.05% of described terephthalic acid (TPA) weight.
A kind of preparation method of polyester silk as above, the described concentrated sulfuric acid refers to that mass concentration is 70～80%
Sulfuric acid, concentrated sulfuric acid addition is 1～3wt% of binary of fatty acids；Described a certain amount of dilute sulfuric acid refer to mass concentration be 40～
50% sulfuric acid, dilute sulfuric acid addition is 1～3wt% of binary of fatty acids mono-methyl.
A kind of preparation method of polyester silk as above, deionized water is washed till and no adopts nitric acid till bromide ion
Silver-colored solution detection.
A kind of preparation method of polyester silk as above, described PTT slice intrinsic viscosity [η] is 1.00～
1.20dl/g；Described modified poly ester PET slicing characteristics viscosity [η] is 0.64～0.75dl/g；
A kind of preparation method of polyester silk is it is characterised in that PTT and PET weight in composite filament as above
Ratio is 4:6～6:4.
In dyeing, disperse dyes can be divided into the following four stage to the upper dye process of polyester fiber to polyester fiber：
1) disperse dyes flowing with dye liquor in dye liquor moves closer to fiber interface；2) disperse dyes are near fiber interface
Adsorbed by fiber surface rapidly；3), after disperse dyes are adsorbed to fiber surface, produce a concentration difference or inside and outside in fiber
Dyestuff chemistry potential difference, dyestuff will spread to fibrous inside；4) disperse dyes diffusion velocity and fiber unformed area content, hole or
Free volume content is relevant, and therefore the dyeing speed of disperse dyes, in addition to dyestuff solubility in the solution, further depends on
When the structure of fiber is outer and dyes, the degree of swelling of fiber is relevant.
Polyster fibre is hydrophobic synthetic fibers, lacks as cellulose or protein fibre in terylene molecular structure
Energy and dyestuff occur combine active group, terylene molecules align must compare closely, only exists less space in fiber,
Under the conditions of the humidity in dyeing, polyester fiber will not can be by acutely swelling and make space increase as cotton fiber, dyestuff divides
Son is difficult to see through fibrous inside.Therefore, improve the carrying out that the free volume between fiber molecule will be helpful to dye.
The molecular chain structure of polyester is the linear macromolecule containing benzene ring structure, the functional group's marshalling on strand,
Unbranched, macromolecular chain flexibility is poor.The regularity of polyester is good and rigidity is all larger simultaneously, and intermolecular active force is larger.
Compared with other macromolecular materials, the strand generation sliding of polyester, rotation are all more difficult, and these characteristics hinder dyestuff and enter
Enter inside polyester, thus dyeability is poor.
Amino ethylene glycol fatty acid, mainly with C-C, based on C-O key, has certain molecular weight simultaneously, that is, has certain
The strand of length, strand flexibility is larger, and the amount of crimp of amino ethylene glycol fatty acid is linearly big compared with benzene ring structure
Molecule is bigger, simultaneously strong compared with the linear macromolecule containing benzene ring structure to the sensitivity of temperature.When the temperature is changed, amino aliphatic acid
Glycol ester moves prior to the linear macromolecule containing benzene ring structure, and free volume produced by motion is far longer than containing phenyl ring
Produced by the linear macromolecule of structure.
Increase the diffusion of dyestuff by the free volume that fatty acid ester increased polyester fiber, improve polyester fiber
Dyeability, make fiber obtain high dye-uptake.
Oxygen in fatty acid ester can form hydrogen bond, but oxygen when centre position, due to space steric effect and fat
The hydrogen that the factors such as the curling of fat acid ester molecules reduce in itself and polyester macromolecule chain forms the quantity of hydrogen bond；If amino is in α position
On, i.e. amino acids, because amino and carbonyl interact, also it is unfavorable for that amino forms hydrogen with the hydrogen in polyester macromolecule chain
Key；When the end position in macromolecular for the amino of amino fatty acid ester, the curling of macromolecular affects on it less, to increased aminolipid
Amino in fat acid esters and the formation of the formation hydrogen bond of the hydrogen in polyester macromolecule chain, improve amino fatty acid ester and polyester simultaneously
Active force between macromolecular chain, decreases sliding and the migration of amino fatty acid ester.
Increased amino fatty acid ester and the compatibility of polyester and dispersion in the polyester, decrease to greatest extent and move
Move.Polyester construction regularity, crystallinity are not destroyed simultaneously, maintain the premium properties of polyester.
Beneficial effect：
1. the polyester silk of gained of the present invention, because amino ethylene glycol fatty acid is based on C-C, has one simultaneously
Determine molecular weight, that is, there is the strand of certain length, strand flexibility is larger, and amino increased the compatibility with polyester.Institute
The fiber obtaining is good with the compatibility of amino ethylene glycol fatty acid.
2., due to the presence in the first amino in amino ethylene glycol fatty acid molecule, increase with it with polyester macromolecule chain
Between hydrogen bond action, increased it with the compatibility of polyester and dispersion in the polyester, decrease migration to greatest extent.
3. the modified poly ester of gained of the present invention, because the content of amino ethylene glycol fatty acid is less, advises to polyester construction
Whole property, crystallinity are not destroyed, and maintain the premium properties of polyester.
4. the amount of crimp of amino ethylene glycol fatty acid is bigger compared with the linear macromolecule of benzene ring structure, simultaneously to temperature
Sensitive strong compared with the linear macromolecule containing benzene ring structure.When the temperature is changed, transport prior to the linear macromolecule containing benzene ring structure
Dynamic, free volume produced by the motion of amino ethylene glycol fatty acid is far longer than the institute of the linear macromolecule containing benzene ring structure
Produce, increase the diffusion of additive, to improve the feature of polyester.
5. fatty acid ester increased the free volume of the polyester fiber diffusion to increase dyestuff, by improving dispersion dye
Material molecule enters the degree within polyester, to improve the dyeability of polyester, also can reduce dyeing temperature to reach simultaneously
Color, reduces the elastic extent of damage of composite filament；
6. obtain and there is composite bicomponent fiber arranged side by side from the high PET/PTT of crimpability, superior elasticity, dye-uptake.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
A kind of polyester silk of the present invention, is cut into slices respectively through not threaded by PTT, modified poly ester PET, in composite component
Place carries out compound distribution spinning and obtains, and described modified poly ester is made up of polyester and amino ethylene glycol fatty acid, described aminolipid
Fat acid glycol ester is dispersed in the molecule interchain of described polyester, and the molecule of described amino ethylene glycol fatty acid and described polyester
Interchain has hydrogen bond action, so that described amino ethylene glycol fatty acid and the relative position of the strand of described polyester is fixed；Described
Under the conditions of temperature is 90～130 DEG C, the free volume space of fibrous inside molecule interchain increases 20～30v/ to polyester silk
V%；
The molecular structure of described amino ethylene glycol fatty acid is：
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
Wherein, n=10-50.
A kind of polyester silk as above, line density deviation ratio≤0.5% of described polyester silk, fracture strength
>=3.0cN/dtex, fracture strength CV value≤5.0%, elongation at break is 30.0 ± 3.0%, extension at break CV value≤
10.0%, yarn unevenness CV≤2.00%, boiling water shrinkage 10.0 ± 0.5%, oil content 1.00 ± 0.20%.
A kind of polyester silk as above, described amino ethylene glycol fatty acid accounts for the weight of described polyester silk
Percentage is 0.5～2.5%.
A kind of preparation method of polyester silk as above, described PTT intrinsic viscosity [η] is 1.00～
1.20dl/g；Described modified poly ester intrinsic viscosity [η] is 0.64～0.75dl/g；.
A kind of preparation method of polyester silk as above, in composite filament, the ratio of PTT and PET weight is 4:6～
6:4.
Colouring method：Dyeing disperse dyes are Disperse Red 3B, and disperse blue SE-2R disperses bright blue S-GL, and fiber exists respectively
Dye in HTHP machine.Before dye, fiber nonionic surfactant is processed 30 minutes at 60 DEG C.Dye dosage is 2.0%
(o.w.f)；Dispersant NNO1.2g/L, pH value is 5, and bath raio is 1:50,60 DEG C upper to contaminate, be warming up to 90 DEG C, 100 DEG C, 110 DEG C,
120 DEG C of each constant temperature dyeing 1h.
Dye uptake adopts raffinate colorimetric method to determine, draws appropriate dyeing stoste and dyeing residual liquid, adds N, N-2 first
Base formamide (DMF) and distilled water, are that the ratio of DMF in dye liquor to be measured and water is 70/30 (v/v), dye liquor absorbance adopts
Ultraviolet-visible spectrophotometer measures, and calculates dye uptake with following formula.
In above formula, A0 and A1 is respectively the absorbance dyeing stoste and dyeing residual liquid.
Embodiment 1
A kind of preparation method of polyester silk, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by dodecanedicarboxylic acid and methyl alcohol with 1:The amount of 1.5 mol ratios adds in reactor, under the catalysis of the concentrated sulfuric acid,
It is heated to 80 DEG C, refuxing esterification, cooling, separating-purifying obtains dodecanedicarboxylic acid mono-methyl；The described concentrated sulfuric acid refers to that quality is dense
Spend the sulfuric acid for 70%, concentrated sulfuric acid addition is the 3wt% of dodecanedicarboxylic acid；
2) described dodecanedicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein
Dodecanedicarboxylic acid mono-methyl concentration is 0.05mol/L, under nitrogen atmosphere, reacts at 80 DEG C, backflow, produces when no longer there being gas
When raw, add a certain amount of dilute sulfuric acid to react 2 hours, be washed out, purify and be dried, obtain product bromoundecane carboxylic acid；
Described a certain amount of dilute sulfuric acid refers to the sulfuric acid that mass concentration is 40%, and dilute sulfuric acid addition is dodecanedicarboxylic acid mono-methyl
3wt%；
3) by the ammoniacal liquor of bromoundecane carboxylic acid and 15wt% in molar ratio 1:2 are added in reactor, and stirring, in room temperature
Lower reaction, then product is heated distillation, and absorb ammonia with cold water, the temperature of heating distillation is 60 DEG C, until bubble-free
Produce, that is, stop distillation, then cooled down and suction filtration, filter cake deionized water is washed till no till bromide ion, using silver nitrate
Solution detects, product vacuum drying is obtained product amino-undecanoic carboxylic acid；
4) by ethylene glycol and amino-undecanoic carboxylic acid in molar ratio for 1.1:2 stir, and press amino-undecanoic carboxylic acid
1% addition concentration of weight is the sulfuric acid of 40wt%, carries out esterification, esterification reaction temperature is 160 DEG C, esterification water quantity of distillate
Reaching more than the 90% of theoretical value is esterification terminal；The separated purification of product obtains amino-undecanoic carboxylic acid ethylene glycol
Ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
Described esterification：
It is 1 using mol ratio:1.2 terephthalic acid (TPA) and ethylene glycol, as raw material, are esterified after being made into uniform sizing material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and Stress control is 250 DEG C in 0.3MPa, temperature, esterification
Water quantity of distillate reach theoretical value more than 90% be esterification terminal；
Described polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the described polycondensation reaction low vacuum stage, esterification products add the 0.01% of terephthalic acid (TPA) weight three oxidations
Two antimony and the triphenyl phosphate of terephthalic acid (TPA) weight 0.01%, start polycondensation reaction, this staged pressure under conditions of negative pressure
Below absolute pressure 500Pa is steadily evacuated to by normal pressure, at 260 DEG C, the reaction time is 50 minutes to temperature control；
Add amino-undecanoic carboxylic acid glycol ester after the described polycondensation reaction low vacuum stage terminates, and stir 15 points
Clock；Described amino-undecanoic carboxylic acid glycol ester, addition is the 0.5wt% of modified poly ester；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 90 minutes reaction time；
Prepared modified poly ester.Described polyester silk temperature be 90 DEG C under the conditions of, the freedom of fibrous inside molecule interchain
Volumetric spaces increase 20v/v%；
(3) obtain the section of modified poly ester after granulating.
The preparation of polyester silk
By PTT, modified poly ester PET section respectively through not threaded, carry out compound distribution at composite component, and compound
Spinneret is extruded, cools down, oiling, stretching, thermal finalization and winding, prepared polyester silk；
The temperature of described extrusion is 280 DEG C；
The wind-warm syndrome of described cooling is 20 DEG C；
The speed of described winding is 4300m/min；
Filament number is 1.0dtex；
A kind of polyester silk is it is characterised in that the line density deviation ratio of described polyester silk as above
0.4%, fracture strength 3.1cN/dtex, fracture strength CV value 4.8%, elongation at break is 31.0%, extension at break CV value
9.8%, yarn unevenness CV≤2.00%, boiling water shrinkage 10.0 ± 0.5%, oil content 1.00 ± 0.20%.By polyester bullet
Sex pilus is dyeed, and dye-uptake is as follows：
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 68.9 | 83.1 | 93.7 | 93.5 | 94.4 |
| General fibre | 65.7 | 78.6 | 83.4 | 91.3 | 92.2 | |
| Disperse blue SE-2R | Modified fibre | 75.5 | 88.3 | 94.0 | 96.4 | 96.8 |
| General fibre | 63.6 | 75.2 | 83.4 | 91.9 | 92.3 | |
| Disperse bright blue S-GL | Modified fibre | 68.5 | 88.8 | 94.6 | 95.1 | 96.7 |
| General fibre | 58.8 | 76.3 | 88.9 | 90.6 | 92.6 |
Embodiment 2
A kind of preparation method of polyester silk, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by dopentacontane dicarboxylic acids and methyl alcohol with 1:The amount of 1.5 mol ratios adds in reactor, in the catalysis of the concentrated sulfuric acid
Under, it is heated to 110 DEG C, refuxing esterification, cooling, separating-purifying obtains dopentacontane mono methyl dicarboxylate；The described concentrated sulfuric acid refers to
Mass concentration is 70% sulfuric acid, and concentrated sulfuric acid addition is the 3wt% of dopentacontane dicarboxylic acids；
2) described dopentacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), its
Middle dopentacontane mono methyl dicarboxylate's concentration is 0.07mol/L, under nitrogen atmosphere, reacts at 85 DEG C, backflow, when no longer there being gas
When body produces, add a certain amount of dilute sulfuric acid to react 3 hours, be washed out, purify and be dried, obtain product bromo henpentacontane
Carboxylic acid；Described a certain amount of dilute sulfuric acid refers to the sulfuric acid that mass concentration is 40%, and dilute sulfuric acid addition is dopentacontane dicarboxylic acids
The 3wt% of mono-methyl；
3) by the ammoniacal liquor of bromo henpentacontane carboxylic acid and 25wt% in molar ratio 1:2 are added in reactor, and stirring, in room
Temperature is lower to react, then product is heated distillation, and absorbs ammonia with cold water, and the temperature of heating distillation is 62 DEG C, until no gas
Bubble produces, that is, stop distillation, then cooled down and suction filtration, and filter cake deionized water is washed till no till bromide ion, using nitric acid
Silver-colored solution detection, product vacuum drying is obtained product amino henpentacontane carboxylic acid；
4) by ethylene glycol and amino henpentacontane carboxylic acid in molar ratio for 1.1:2 stir, and press amino henpentacontane
2% addition concentration of carboxylic acid weight is the sulfuric acid of 45wt%, carries out esterification, esterification reaction temperature is 220 DEG C, and esterification water evaporates
Output reach theoretical value more than 90% be esterification terminal；The separated purification of product obtains amino henpentacontane carboxylic acid
Glycol ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
Described esterification：
It is 1 using mol ratio:2.0 terephthalic acid (TPA) and ethylene glycol, as raw material, are esterified after being made into uniform sizing material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.2MPa, temperature, at 260 DEG C, is esterified Stress control
Water quantity of distillate reach theoretical value more than 90% be esterification terminal；
Described polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the described polycondensation reaction low vacuum stage, esterification products add the 0.05% of terephthalic acid (TPA) weight three oxidations
Two antimony and the triphenyl phosphate of terephthalic acid (TPA) weight 0.05%, start polycondensation reaction, this staged pressure under conditions of negative pressure
Below absolute pressure 500Pa is steadily evacuated to by normal pressure, at 270 DEG C, the reaction time is 30 minutes to temperature control；
Add amino henpentacontane carboxylic acid glycol ester after the described polycondensation reaction low vacuum stage terminates, and stir 20 points
Clock；Described amino henpentacontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.5%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 280 DEG C, 50 minutes reaction time；
Prepared modified poly ester.Described polyester silk temperature be 130 DEG C under the conditions of, the freedom of fibrous inside molecule interchain
Volumetric spaces increase 30v/v%
(3) obtain the section of modified poly ester after granulating.
The preparation of polyester silk
By PTT, modified poly ester PET section respectively through not threaded, carry out compound distribution at composite component, and compound
Spinneret is extruded, cools down, oiling, stretching, thermal finalization and winding, prepared polyester silk；
The temperature of described extrusion is 285 DEG C；
The wind-warm syndrome of described cooling is 25 DEG C；
The speed of described winding is 4600m/min；
Filament number is 0.7dtex；
A kind of polyester silk is it is characterised in that the line density deviation ratio of described polyester silk as above
0.5%, fracture strength 3.2cN/dtex, fracture strength CV value 4.6%, elongation at break is 32.0%, extension at break CV value
9.6%, yarn unevenness CV≤2.00%, boiling water shrinkage 10.0 ± 0.5%, oil content 1.00 ± 0.20%.By polyester bullet
Sex pilus is dyeed, and dye-uptake is as follows：
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 69.7 | 84.2 | 93.2 | 93.6 | 94.6 |
| General fibre | 65.7 | 78.6 | 83.4 | 91.3 | 92.2 | |
| Disperse blue SE-2R | Modified fibre | 76.3 | 88.9 | 94.8 | 96.8 | 96.9 |
| General fibre | 63.6 | 75.2 | 83.4 | 91.9 | 92.3 | |
| Disperse bright blue S-GL | Modified fibre | 69.5 | 88.7 | 95.0 | 95.4 | 96.9 |
| General fibre | 58.8 | 76.3 | 88.9 | 90.6 | 92.6 |
Embodiment 3
A kind of preparation method of polyester silk, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by pentacosane dicarboxylic acid and methyl alcohol with 1:The amount of 1.5 mol ratios adds in reactor, under the catalysis of the concentrated sulfuric acid,
It is heated to 85 DEG C, refuxing esterification, cooling, separating-purifying obtains pentacosane dicarboxylic acid mono-methyl；The described concentrated sulfuric acid refers to that quality is dense
Spend the sulfuric acid for 70%, concentrated sulfuric acid addition is the 3wt% of pentacosane dicarboxylic acid；
2) described pentacosane dicarboxylic acid mono-methyl, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein
Pentacosane dicarboxylic acid mono-methyl concentration is 0.08mol/L, under nitrogen atmosphere, reacts at 90 DEG C, backflow, produces when no longer there being gas
When raw, add a certain amount of dilute sulfuric acid to react 2.5 hours, be washed out, purify and be dried, obtain product bromotetradecane carboxylic
Acid；Described a certain amount of dilute sulfuric acid refers to the sulfuric acid that mass concentration is 50%, and dilute sulfuric acid addition is pentacosane dicarboxylic acid list first
The 3wt% of ester；
3) by the ammoniacal liquor of bromotetradecane carboxylic acid and 20wt% in molar ratio 1:2 are added in reactor, and stirring, in room temperature
Lower reaction, then product is heated distillation, and absorb ammonia with cold water, the temperature of heating distillation is 60 DEG C, until bubble-free
Produce, that is, stop distillation, then cooled down and suction filtration, filter cake deionized water is washed till no till bromide ion, using silver nitrate
Solution detects, product vacuum drying is obtained product amino tetradecane carboxylic acid；
4) by ethylene glycol and amino tetradecane carboxylic acid in molar ratio for 1.1:2 stir, and press amino tetradecane carboxylic acid
2% addition concentration of weight is the sulfuric acid of 50wt%, carries out esterification, esterification reaction temperature is 190 DEG C, esterification water quantity of distillate
Reaching more than the 90% of theoretical value is esterification terminal；The separated purification of product obtains amino tetradecane carboxylic acid ethylene glycol
Ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
Described esterification：
It is 1 using mol ratio:1.6 terephthalic acid (TPA) and ethylene glycol, as raw material, are esterified after being made into uniform sizing material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.3MPa, temperature, at 255 DEG C, is esterified Stress control
Water quantity of distillate reach theoretical value more than 90% be esterification terminal；
Described polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the described polycondensation reaction low vacuum stage, esterification products add the 0.03% of terephthalic acid (TPA) weight three oxidations
Two antimony and the triphenyl phosphate of terephthalic acid (TPA) weight 0.03%, start polycondensation reaction, this staged pressure under conditions of negative pressure
Below absolute pressure 500Pa is steadily evacuated to by normal pressure, at 265 DEG C, the reaction time is 40 minutes to temperature control；
Add amino tetradecane carboxylic acid glycol ester after the described polycondensation reaction low vacuum stage terminates, and stir 16 points
Clock；Described amino tetradecane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 1.0%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 276 DEG C, 70 minutes reaction time；
Prepared modified poly ester.Described polyester silk temperature be 95 DEG C under the conditions of, the freedom of fibrous inside molecule interchain
Volumetric spaces increase 21v/v%
(3) obtain the section of modified poly ester after granulating.
The preparation of polyester silk
By PTT, modified poly ester PET section respectively through not threaded, carry out compound distribution at composite component, and compound
Spinneret is extruded, cools down, oiling, stretching, thermal finalization and winding, prepared polyester silk；
The temperature of described extrusion is 285 DEG C；
The wind-warm syndrome of described cooling is 250 DEG C；
The speed of described winding is 4300m/min；
Filament number is 1.1dtex；
A kind of polyester silk is it is characterised in that the line density deviation ratio of described polyester silk as above
0.5%, fracture strength 3.1cN/dtex, fracture strength CV value 4.5%, elongation at break is 31.8%, extension at break CV value
9.4%, yarn unevenness CV≤2.00%, boiling water shrinkage 10.0 ± 0.5%, oil content 1.00 ± 0.20%.By polyester bullet
Sex pilus is dyeed, and dye-uptake is as follows：
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 68.9 | 81.1 | 91.6 | 92.5 | 93.6 |
| General fibre | 65.7 | 78.6 | 83.4 | 91.3 | 92.2 | |
| Disperse blue SE-2R | Modified fibre | 74.5 | 87.3 | 93.0 | 95.4 | 95.8 |
| General fibre | 63.6 | 75.2 | 83.4 | 91.9 | 92.3 | |
| Disperse bright blue S-GL | Modified fibre | 67.5 | 87.1 | 94.0 | 94.1 | 96.3 |
| General fibre | 58.8 | 76.3 | 88.9 | 90.6 | 92.6 |
Embodiment 4
A kind of preparation method of polyester silk, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by eicosane dicarboxylic acids and methyl alcohol with 1:The amount of 1.5 mol ratios adds in reactor, under the catalysis of the concentrated sulfuric acid,
It is heated to 85 DEG C, refuxing esterification, cooling, separating-purifying obtains eicosane mono methyl dicarboxylate；The described concentrated sulfuric acid refers to that quality is dense
Spend the sulfuric acid for 70%, concentrated sulfuric acid addition is the 3wt% of eicosane dicarboxylic acids；
2) described eicosane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein
Eicosane mono methyl dicarboxylate's concentration is 0.09mol/L, under nitrogen atmosphere, reacts at 80 DEG C, backflow, produces when no longer there being gas
When raw, add a certain amount of dilute sulfuric acid to react 2.1 hours, be washed out, purify and be dried, obtain product bromo nonadecane carboxylic
Acid；Described a certain amount of dilute sulfuric acid refers to the sulfuric acid that mass concentration is 43%, and dilute sulfuric acid addition is eicosane dicarboxylic acids list first
The 2wt% of ester；
3) by the ammoniacal liquor of bromo nonadecane carboxylic acid and 16wt% in molar ratio 1:2 are added in reactor, and stirring, in room temperature
Lower reaction, then product is heated distillation, and absorb ammonia with cold water, the temperature of heating distillation is 69 DEG C, until bubble-free
Produce, that is, stop distillation, then cooled down and suction filtration, filter cake deionized water is washed till no till bromide ion, using silver nitrate
Solution detects, product vacuum drying is obtained product amino nonadecane carboxylic acid；
4) by ethylene glycol and amino nonadecane carboxylic acid in molar ratio for 1.1:2 stir, and press amino nonadecane carboxylic acid
2% addition concentration of weight is the sulfuric acid of 42wt%, carries out esterification, esterification reaction temperature is 160 DEG C, esterification water quantity of distillate
Reaching more than the 90% of theoretical value is esterification terminal；The separated purification of product obtains amino nonadecane carboxylic acid ethylene glycol
Ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
Described esterification：
It is 1 using mol ratio:1.2 terephthalic acid (TPA) and ethylene glycol, as raw material, are esterified after being made into uniform sizing material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.15MPa, temperature, at 251 DEG C, is esterified Stress control
Water quantity of distillate reach theoretical value more than 90% be esterification terminal；
Described polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the described polycondensation reaction low vacuum stage, esterification products add the 0.02% of terephthalic acid (TPA) weight three oxidations
Two antimony and the triphenyl phosphate of terephthalic acid (TPA) weight 0.02%, start polycondensation reaction, this staged pressure under conditions of negative pressure
Below absolute pressure 500Pa is steadily evacuated to by normal pressure, at 262 DEG C, the reaction time is 33 minutes to temperature control；
Add amino nonadecane carboxylic acid glycol ester after the described polycondensation reaction low vacuum stage terminates, and stir 17 points
Clock；Described amino nonadecane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 1.5%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 277 DEG C, 55 minutes reaction time；
Prepared modified poly ester.Described polyester silk temperature be 100 DEG C under the conditions of, the freedom of fibrous inside molecule interchain
Volumetric spaces increase 23v/v%
(3) obtain the section of modified poly ester after granulating.
The preparation of polyester silk
By PTT, modified poly ester PET section respectively through not threaded, carry out compound distribution at composite component, and compound
Spinneret is extruded, cools down, oiling, stretching, thermal finalization and winding, prepared polyester silk；
The temperature of described extrusion is 280 DEG C；
The wind-warm syndrome of described cooling is 20 DEG C；
The speed of described winding is 4200m/min；
Filament number is 0.9dtex；
A kind of polyester silk is it is characterised in that the line density deviation ratio of described polyester silk as above
0.4%, fracture strength 3.1cN/dtex, fracture strength CV value 4.7%, elongation at break is 29.5%, extension at break CV value
9.6%, yarn unevenness CV≤2.00%, boiling water shrinkage 10.0 ± 0.5%, oil content 1.00 ± 0.20%.By polyester bullet
Sex pilus is dyeed, and dye-uptake is as follows：
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 68.7 | 83.1 | 92.9 | 93.8 | 94.6 |
| General fibre | 65.7 | 78.6 | 83.4 | 91.3 | 92.2 | |
| Disperse blue SE-2R | Modified fibre | 75.8 | 88.2 | 94.8 | 96.6 | 97.1 |
| General fibre | 63.6 | 75.2 | 83.4 | 91.9 | 92.3 | |
| Disperse bright blue S-GL | Modified fibre | 68.8 | 88.1 | 94.9 | 95.3 | 96.9 |
| General fibre | 58.8 | 76.3 | 88.9 | 90.6 | 92.6 |
Embodiment 5
A kind of preparation method of polyester silk, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by melissane dicarboxylic acids and methyl alcohol with 1:The amount of 1.5 mol ratios adds in reactor, under the catalysis of the concentrated sulfuric acid,
It is heated to 90 DEG C, refuxing esterification, cooling, separating-purifying obtains melissane mono methyl dicarboxylate；The described concentrated sulfuric acid refers to that quality is dense
Spend the sulfuric acid for 70%, concentrated sulfuric acid addition is the 3wt% of melissane dicarboxylic acids；
2) described melissane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein
Melissane mono methyl dicarboxylate's concentration for 0.10mol/L under nitrogen atmosphere, is reacted at 85 DEG C, backflow, produces when no longer there being gas
When raw, add a certain amount of dilute sulfuric acid to react 2.3 hours, be washed out, purify and be dried, obtain product bromo nonacosane carboxylic
Acid；Described a certain amount of dilute sulfuric acid refers to the sulfuric acid that mass concentration is 40%, and dilute sulfuric acid addition is melissane dicarboxylic acids list first
The 3wt% of ester；
3) by the ammoniacal liquor of bromo nonacosane carboxylic acid and 18wt% in molar ratio 1:2 are added in reactor, and stirring, in room
Temperature is lower to react, then product is heated distillation, and absorbs ammonia with cold water, and the temperature of heating distillation is 67 DEG C, until no gas
Bubble produces, that is, stop distillation, then cooled down and suction filtration, and filter cake deionized water is washed till no till bromide ion, using nitric acid
Silver-colored solution detection, product vacuum drying is obtained product amino nonacosane carboxylic acid；
4) by ethylene glycol and amino nonacosane carboxylic acid in molar ratio for 1.1:2 stir, and press amino nonacosane
2% addition concentration of carboxylic acid weight is the sulfuric acid of 48wt%, carries out esterification, esterification reaction temperature is 170 DEG C, and esterification water evaporates
Output reach theoretical value more than 90% be esterification terminal；The separated purification of product obtains amino nonacosane carboxylic acid
Glycol ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
Described esterification：
It is 1 using mol ratio:1.5 terephthalic acid (TPA) and ethylene glycol, as raw material, are esterified after being made into uniform sizing material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.3MPa, temperature, at 254 DEG C, is esterified Stress control
Water quantity of distillate reach theoretical value more than 90% be esterification terminal；
Described polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the described polycondensation reaction low vacuum stage, esterification products add the 0.01% of terephthalic acid (TPA) weight ethylene glycol
Antimony and the trimethyl phosphate of terephthalic acid (TPA) weight 0.03%, under conditions of negative pressure start polycondensation reaction, this staged pressure by
Normal pressure is steadily evacuated to below absolute pressure 500Pa, and at 266 DEG C, the reaction time is 39 minutes to temperature control；
Add amino nonacosane carboxylic acid glycol ester after the described polycondensation reaction low vacuum stage terminates, and stir 18 points
Clock；Described amino nonacosane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.5%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 278 DEG C, 60 minutes reaction time；
Prepared modified poly ester.Described polyester silk temperature be 110 DEG C under the conditions of, the freedom of fibrous inside molecule interchain
Volumetric spaces increase 24v/v%
(3) obtain the section of modified poly ester after granulating.
The preparation of polyester silk
By PTT, modified poly ester PET section respectively through not threaded, carry out compound distribution at composite component, and compound
Spinneret is extruded, cools down, oiling, stretching, thermal finalization and winding, prepared polyester silk；
The temperature of described extrusion is 280 DEG C；
The wind-warm syndrome of described cooling is 20 DEG C；
The speed of described winding is 4200m/min；
Filament number is 0.9dtex；
A kind of polyester silk is it is characterised in that the line density deviation ratio of described polyester silk as above
0.5%, fracture strength 3.0cN/dtex, fracture strength CV value 4.5%, elongation at break is 31.2%, extension at break CV value
9.9%, yarn unevenness CV≤2.00%, boiling water shrinkage 10.0 ± 0.5%, oil content 1.00 ± 0.20%.By polyester bullet
Sex pilus is dyeed, and dye-uptake is as follows：
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 69.4 | 83.9 | 93.1 | 93.7 | 94.8 |
| General fibre | 65.7 | 78.6 | 83.4 | 91.3 | 92.2 | |
| Disperse blue SE-2R | Modified fibre | 75.9 | 88.6 | 94.3 | 96.6 | 97.1 |
| General fibre | 63.6 | 75.2 | 83.4 | 91.9 | 92.3 | |
| Disperse bright blue S-GL | Modified fibre | 68.9 | 88.2 | 94.1 | 95.3 | 96.9 |
| General fibre | 58.8 | 76.3 | 88.9 | 90.6 | 92.6 |
Embodiment 6
A kind of preparation method of polyester silk, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by pentatriacontane dicarboxylic acids and methyl alcohol with 1:The amount of 1.5 mol ratios adds in reactor, in the catalysis of the concentrated sulfuric acid
Under, it is heated to 95 DEG C, refuxing esterification, cooling, separating-purifying obtains pentatriacontane mono methyl dicarboxylate；The described concentrated sulfuric acid refers to matter
Amount concentration is 70% sulfuric acid, and concentrated sulfuric acid addition is the 2wt% of pentatriacontane dicarboxylic acids；
2) described pentatriacontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), its
Middle pentatriacontane mono methyl dicarboxylate's concentration be 0.09mol/L under nitrogen atmosphere, react at 90 DEG C, backflow, when no longer there being gas
When body produces, add a certain amount of dilute sulfuric acid to react 2.6 hours, be washed out, purify and be dried, obtain product bromo 34
Alkane carboxylic acid；Described a certain amount of dilute sulfuric acid refers to the sulfuric acid that mass concentration is 45%, and dilute sulfuric acid addition is pentatriacontane dicarboxyl
The 1wt% of sour mono-methyl
3) by the ammoniacal liquor of bromo tetratriacontane carboxylic acid and 20wt% in molar ratio 1:2 are added in reactor, and stirring, in room
Temperature is lower to react, then product is heated distillation, and absorbs ammonia with cold water, and the temperature of heating distillation is 69 DEG C, until no gas
Bubble produces, that is, stop distillation, then cooled down and suction filtration, and filter cake deionized water is washed till no till bromide ion, using nitric acid
Silver-colored solution detection, product vacuum drying is obtained product amino tetratriacontane carboxylic acid；
4) by ethylene glycol and amino tetratriacontane carboxylic acid in molar ratio for 1.1:2 stir, and press amino tetratriacontane
1% addition concentration of carboxylic acid weight is the sulfuric acid of 50wt%, carries out esterification, esterification reaction temperature is 180 DEG C, and esterification water evaporates
Output reach theoretical value more than 90% be esterification terminal；The separated purification of product obtains amino tetratriacontane carboxylic acid
Glycol ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
Described esterification：
It is 1 using mol ratio:1.6 terephthalic acid (TPA) and ethylene glycol, as raw material, are esterified after being made into uniform sizing material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.4MPa, temperature, at 256 DEG C, is esterified Stress control
Water quantity of distillate reach theoretical value more than 90% be esterification terminal；
Described polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the described polycondensation reaction low vacuum stage, esterification products add the 0.04% of terephthalic acid (TPA) weight antimony acetate
With the Trimethyl phosphite of terephthalic acid (TPA) weight 0.02%, under conditions of negative pressure start polycondensation reaction, this staged pressure by
Normal pressure is steadily evacuated to below absolute pressure 500Pa, and at 267 DEG C, the reaction time is 40 minutes to temperature control；
Add amino tetratriacontane carboxylic acid glycol ester after the described polycondensation reaction low vacuum stage terminates, and stir 18 points
Clock；Described amino tetratriacontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.0%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 70 minutes reaction time；
Prepared modified poly ester.Described polyester silk temperature be 120 DEG C under the conditions of, the freedom of fibrous inside molecule interchain
Volumetric spaces increase 26v/v%
(3) obtain the section of modified poly ester after granulating.
The preparation of polyester silk
By PTT, modified poly ester PET section respectively through not threaded, carry out compound distribution at composite component, and compound
Spinneret is extruded, cools down, oiling, stretching, thermal finalization and winding, prepared polyester silk；
The temperature of described extrusion is 290 DEG C；
The wind-warm syndrome of described cooling is 20 DEG C；
The speed of described winding is 4200m/min；
Filament number is 0.9dtex；
A kind of polyester silk is it is characterised in that the line density deviation ratio of described polyester silk as above
0.3%, fracture strength 3.3cN/dtex, fracture strength CV value 4.5%, elongation at break is 31.8%, extension at break CV value
9.1%, yarn unevenness CV≤2.00%, boiling water shrinkage 10.0 ± 0.5%, oil content 1.00 ± 0.20%.By polyester bullet
Sex pilus is dyeed, and dye-uptake is as follows：
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 68.7 | 83.0 | 92.2 | 93.2 | 94.0 |
| General fibre | 65.7 | 78.6 | 83.4 | 91.3 | 92.2 |
| Disperse blue SE-2R | Modified fibre | 75.2 | 88.0 | 93.3 | 95.4 | 96.3 |
| General fibre | 63.6 | 75.2 | 83.4 | 91.9 | 92.3 | |
| Disperse bright blue S-GL | Modified fibre | 68.1 | 87.5 | 94.2 | 94.8 | 96.5 |
| General fibre | 58.8 | 76.3 | 88.9 | 90.6 | 92.6 |
Embodiment 7
A kind of preparation method of polyester silk, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by tetracontane dicarboxylic acids and methyl alcohol with 1:The amount of 1.5 mol ratios adds in reactor, under the catalysis of the concentrated sulfuric acid,
It is heated to 100 DEG C, refuxing esterification, cooling, separating-purifying obtains tetracontane mono methyl dicarboxylate；The described concentrated sulfuric acid refers to that quality is dense
Spend the sulfuric acid for 70%, concentrated sulfuric acid addition is the 3wt% of tetracontane dicarboxylic acids；
2) described tetracontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), wherein
Tetracontane mono methyl dicarboxylate's concentration for 0.06mol/L under nitrogen atmosphere, is reacted at 80 DEG C, backflow, produces when no longer there being gas
When raw, add a certain amount of dilute sulfuric acid to react 2.7 hours, be washed out, purify and be dried, obtain product bromo nonatriacontane carboxylic
Acid；Described a certain amount of dilute sulfuric acid refers to the sulfuric acid that mass concentration is 48%, and dilute sulfuric acid addition is tetracontane dicarboxylic acids list first
The 2wt% of ester；
3) by the ammoniacal liquor of bromo nonatriacontane carboxylic acid and 22wt% in molar ratio 1:2 are added in reactor, and stirring, in room
Temperature is lower to react, then product is heated distillation, and absorbs ammonia with cold water, and the temperature of heating distillation is 60 DEG C, until no gas
Bubble produces, that is, stop distillation, then cooled down and suction filtration, and filter cake deionized water is washed till no till bromide ion, using nitric acid
Silver-colored solution detection, product vacuum drying is obtained product amino nonatriacontane carboxylic acid；
4) by ethylene glycol and amino nonatriacontane carboxylic acid in molar ratio for 1.1:2 stir, and press amino nonatriacontane
2% addition concentration of carboxylic acid weight is the sulfuric acid of 46wt%, carries out esterification, esterification reaction temperature is 190 DEG C, and esterification water evaporates
Output reach theoretical value more than 90% be esterification terminal；The separated purification of product obtains amino nonatriacontane carboxylic acid
Glycol ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
Described esterification：
It is 1 using mol ratio:1.8 terephthalic acid (TPA) and ethylene glycol, as raw material, are esterified after being made into uniform sizing material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.2MPa, temperature, at 258 DEG C, is esterified Stress control
Water quantity of distillate reach theoretical value more than 90% be esterification terminal；
Described polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the described polycondensation reaction low vacuum stage, esterification products add the 0.05% of terephthalic acid (TPA) weight antimony acetate
With the trimethyl phosphate of terephthalic acid (TPA) weight 0.03%, start polycondensation reaction under conditions of negative pressure, this staged pressure is by normal
Flatten and be surely evacuated to below absolute pressure 500Pa, at 268 DEG C, the reaction time is 45 minutes to temperature control；
Add amino nonatriacontane carboxylic acid glycol ester after the described polycondensation reaction low vacuum stage terminates, and stir 16 points
Clock；Described amino nonatriacontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 1.5%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 275 DEG C, 75 minutes reaction time；
Prepared modified poly ester.Described polyester silk temperature be 125 DEG C under the conditions of, the freedom of fibrous inside molecule interchain
Volumetric spaces increase 27v/v%
(3) obtain the section of modified poly ester after granulating.
The preparation of polyester silk
By PTT, modified poly ester PET section respectively through not threaded, carry out compound distribution at composite component, and compound
Spinneret is extruded, cools down, oiling, stretching, thermal finalization and winding, prepared polyester silk；
The temperature of described extrusion is 275 DEG C；
The wind-warm syndrome of described cooling is 20 DEG C；
The speed of described winding is 4300m/min；
Filament number is 1.0dtex；
A kind of polyester silk is it is characterised in that the line density deviation ratio of described polyester silk as above
0.4%, fracture strength 3.2cN/dtex, fracture strength CV value 4.6%, elongation at break is 29%, extension at break CV value
9.6%, yarn unevenness CV≤2.00%, boiling water shrinkage 10.0 ± 0.5%, oil content 1.00 ± 0.20%.By polyester bullet
Sex pilus is dyeed, and dye-uptake is as follows：
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 68.9 | 83.3 | 92.9 | 93.6 | 94.6 |
| General fibre | 65.7 | 78.6 | 83.4 | 91.3 | 92.2 | |
| Disperse blue SE-2R | Modified fibre | 75.7 | 88.5 | 94.2 | 96.6 | 96.9 |
| General fibre | 63.6 | 75.2 | 83.4 | 91.4 | 92.3 | |
| Disperse bright blue S-GL | Modified fibre | 68.8 | 87.9 | 94.8 | 95.3 | 96.9 |
| General fibre | 58.8 | 76.3 | 88.9 | 90.6 | 92.6 |
Embodiment 8
A kind of preparation method of polyester silk, comprises the following steps：
(1) preparation of amino ethylene glycol fatty acid：
1) by pentatetracontane dicarboxylic acids and methyl alcohol with 1:The amount of 1.5 mol ratios adds in reactor, in the catalysis of the concentrated sulfuric acid
Under, it is heated to 110 DEG C, refuxing esterification, cooling, separating-purifying obtains pentatetracontane mono methyl dicarboxylate；The described concentrated sulfuric acid refers to
Mass concentration is 70% sulfuric acid, and concentrated sulfuric acid addition is the 2wt% of pentatetracontane dicarboxylic acids；
2) described pentatetracontane mono methyl dicarboxylate, lead tetraacetate and lithium bromide are dissolved in benzene (mol ratio 1:1:1), its
Middle pentatetracontane mono methyl dicarboxylate's concentration is 0.07mol/L, under nitrogen atmosphere, reacts at 88 DEG C, backflow, when no longer there being gas
When body produces, add a certain amount of dilute sulfuric acid to react 2.3 hours, be washed out, purify and be dried, obtain product bromo 44
Alkane carboxylic acid；Described a certain amount of dilute sulfuric acid refers to the sulfuric acid that mass concentration is 45%, and dilute sulfuric acid addition is pentatetracontane dicarboxyl
The 2wt% of sour mono-methyl；
3) by the ammoniacal liquor of bromo tetratetracontane carboxylic acid and 25wt% in molar ratio 1:2 are added in reactor, and stirring, in room
Temperature is lower to react, then product is heated distillation, and absorbs ammonia with cold water, and the temperature of heating distillation is less than 70 DEG C, until
Bubble-free produces, that is, stop distillation, then cooled down and suction filtration, and filter cake deionized water is washed till no till bromide ion, adopts
Silver nitrate solution detects, product vacuum drying is obtained product amino tetratetracontane carboxylic acid；
4) by ethylene glycol and amino tetratetracontane carboxylic acid in molar ratio for 1.1:2 stir, and press amino tetratetracontane
1% addition concentration of carboxylic acid weight is the sulfuric acid of 50wt%, carries out esterification, esterification reaction temperature is 210 DEG C, and esterification water evaporates
Output reach theoretical value more than 90% be esterification terminal；The separated purification of product obtains amino tetratetracontane carboxylic acid
Glycol ester；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
Described esterification：
It is 1 using mol ratio:2.0 terephthalic acid (TPA) and ethylene glycol, as raw material, are esterified after being made into uniform sizing material
Reaction, obtains esterification products；Esterification is pressurizeed in nitrogen atmosphere, and in 0.3MPa, temperature, at 260 DEG C, is esterified Stress control
Water quantity of distillate reach theoretical value more than 90% be esterification terminal；
Described polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the described polycondensation reaction low vacuum stage, esterification products add the 0.02% of terephthalic acid (TPA) weight ethylene glycol
Antimony and the trimethyl phosphate of terephthalic acid (TPA) weight 0.05%, under conditions of negative pressure start polycondensation reaction, this staged pressure by
Normal pressure is steadily evacuated to below absolute pressure 500Pa, and at 270 DEG C, the reaction time is 50 minutes to temperature control；
Add amino tetratetracontane carboxylic acid glycol ester after the described polycondensation reaction low vacuum stage terminates, and stir 20 points
Clock；Described amino tetratetracontane carboxylic acid glycol ester addition is the percentage by weight of modified poly ester is 2.0%；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, makes reaction pressure
Power is down to absolute pressure and is less than 100Pa, and reaction temperature controls at 280 DEG C, 85 minutes reaction time.
Under the conditions of temperature is 128 DEG C, the free volume space of fibrous inside molecule interchain increases described polyester silk
The section of modified poly ester is obtained after 29v/v% (3) granulation.
The preparation of polyester silk
By PTT, modified poly ester PET section respectively through not threaded, carry out compound distribution at composite component, and compound
Spinneret is extruded, cools down, oiling, stretching, thermal finalization and winding, prepared polyester silk；
The temperature of described extrusion is 275 DEG C；
The wind-warm syndrome of described cooling is 20 DEG C；
The speed of described winding is 4300m/min；
Filament number is 1.0dtex；
A kind of polyester silk is it is characterised in that the line density deviation ratio of described polyester silk as above
0.4%, fracture strength 3.2cN/dtex, fracture strength CV value 4.6%, elongation at break is 29%, extension at break CV value
9.6%, yarn unevenness CV≤2.00%, boiling water shrinkage 10.0 ± 0.5%, oil content 1.00 ± 0.20%.By polyester bullet
Sex pilus is dyeed, and dye-uptake is as follows：
The dye uptake (%) of fiber
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 68.8 | 83.3 | 92.7 | 93.6 | 94.6 |
| General fibre | 65.7 | 78.6 | 83.4 | 91.3 | 92.2 | |
| Disperse blue SE-2R | Modified fibre | 75.6 | 88.5 | 94.2 | 96.6 | 96.9 |
| General fibre | 63.6 | 75.2 | 83.4 | 91.4 | 92.3 | |
| Disperse bright blue S-GL | Modified fibre | 68.8 | 87.9 | 94.8 | 95.3 | 96.9 |
| General fibre | 58.8 | 76.3 | 88.9 | 90.6 | 92.6 |
Claims (10)
1. a kind of polyester silk, is characterized in that：Described polyester silk is PTT and the double-component of modified poly ester is combined side by side
Silk, the elongation at break of described polyester silk is 30.0 ± 3.0%, boiling water shrinkage 10.0 ± 0.5%；Described modified poly ester
It is made up of with amino ethylene glycol fatty acid polyester, described amino ethylene glycol fatty acid is dispersed in the strand of described polyester
Between, and described amino ethylene glycol fatty acid has hydrogen bond action with the molecule interchain of described polyester, makes described amino aliphatic acid second
The relative position of diol ester and the strand of described polyester is fixed；Described polyester silk polyester is 90～130 DEG C of bars in temperature
Under part, the free volume space of fibrous inside molecule interchain increases 20～30v/v%；
The molecular structure of described amino ethylene glycol fatty acid is：
H2N(CH2)nCOOCH2CH2OOC(CH2)nNH2；
Wherein, n=10-50.
2. a kind of polyester silk according to claim 1 is it is characterised in that the line density deviation of described polyester silk
Rate≤0.5%, fracture strength >=3.0cN/dtex, fracture strength CV value≤5.0%, extension at break CV value≤10.0%, bar is done
Irregularity CV≤2.00%, oil content 1.00 ± 0.20%.
3. a kind of polyester silk according to claim 1 is it is characterised in that described amino ethylene glycol fatty acid accounts for institute
The percentage by weight stating polyester silk is 0.5～2.5%.
4. a kind of preparation method of polyester silk as claimed in claim 1, is characterized in that：PTT and modified poly ester are carried out
Composite spinning side by side, prepared polyester silk；The main technologic parameters of described composite spinning arranged side by side are：
The temperature of extrusion is 280～290 DEG C；
The wind-warm syndrome of cooling is 20～25 DEG C；
The speed of winding is 4000～4600m/min
Filament number is 0.7～1.5dtex；
The preparation process of described modified poly ester includes：
(1) preparation of amino ethylene glycol fatty acid：
1) by binary of fatty acids and methyl alcohol with 1:The amount of 1.5 mol ratios adds in reactor, under the catalysis of the concentrated sulfuric acid, is heated to
80～110 DEG C, refuxing esterification, cooling, separating-purifying obtains binary of fatty acids mono-methyl；Described binary of fatty acids is dodecane two
Carboxylic acid is one of to dopentacontane dicarboxylic acids；
2) by described binary of fatty acids mono-methyl, lead tetraacetate and lithium bromide in molar ratio 1:1:1 is dissolved in benzene, wherein binary fat
The concentration of fat acid mono-methyl is 0.05～0.1mol/L, under nitrogen atmosphere, reacts at 80～90 DEG C, backflow, when no longer there being gas
When body produces, add a certain amount of dilute sulfuric acid to react 2～3 hours, be washed out, purify and be dried, obtain product bromo fat
Acid；
3) by the ammoniacal liquor of bromo aliphatic acid and 15～25wt% in molar ratio 1:2 are added in reactor, stirring, at room temperature instead
Should, then product is heated distillation, and absorb ammonia with cold water, the temperature of heating distillation is less than 70 DEG C, until bubble-free
Produce, that is, stop distillation, then cooled down and suction filtration, filter cake deionized water is washed till no till bromide ion, by product vacuum
It is dried to obtain product amino aliphatic acid；
4) by ethylene glycol and amino aliphatic acid in molar ratio for 1.1:2 stir, and press the 1～3% of amino fatty acid wt
The sulfuric acid adding concentration to be 40～50wt%, carries out esterification, and esterification reaction temperature is 160～220 DEG C, esterification water quantity of distillate
Reaching more than the 90% of theoretical value is esterification terminal；The separated purification of product obtains amino ethylene glycol fatty acid；
(2) preparation of modified poly ester, including esterification and polycondensation reaction：
Described esterification：
Using terephthalic acid (TPA) and ethylene glycol as raw material, carry out esterification after being made into uniform sizing material, obtain esterification products；Ester
Change reaction to pressurize in nitrogen atmosphere, in normal pressure～0.3MPa, at 250～260 DEG C, esterification water quantity of distillate reaches temperature Stress control
It is esterification terminal to more than the 90% of theoretical value；
Described polycondensation reaction：
Including polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig：
In the described polycondensation reaction low vacuum stage, in esterification products, add catalyst and stabilizer, start under conditions of negative pressure
Polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature control, at 260～270 DEG C, is reacted
Time is 30～50 minutes；
Add amino ethylene glycol fatty acid after the described polycondensation reaction low vacuum stage terminates, and stir；
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and so that reaction pressure is dropped
It is less than 100Pa to absolute pressure, reaction temperature controls at 275～280 DEG C, 50～90 minutes reaction time；
Prepared modified poly ester.
5. a kind of polyester silk according to claim 4 preparation method it is characterised in that described ethylene glycol with described
The mol ratio of terephthalic acid (TPA) is 1.2～2.0:1；Described catalyst is selected from antimony oxide, antimony glycol and antimony acetate
One kind, catalyst amount is the 0.01%～0.05% of described terephthalic acid (TPA) weight.
6. a kind of preparation method of polyester silk according to claim 4 is it is characterised in that described stabilizer is selected from phosphorus
One of triphenyl phosphate ester, trimethyl phosphate and Trimethyl phosphite, stabilizing agent dosage is described terephthalic acid (TPA) weight
0.01%～0.05%.
7. a kind of preparation method of polyester silk according to claim 4 is it is characterised in that add amino aliphatic acid second
Stirring after diol ester, the time is 15～20 minutes；Deionized water is washed till no till bromide ion using silver nitrate solution detection.
8. a kind of preparation method of polyester silk according to claim 4 is it is characterised in that described PTT characteristic sticks
Degree [η] is 1.00～1.20dl/g；Described modified poly ester intrinsic viscosity [η] is 0.64～0.75dl/g；
9. a kind of polyester silk according to claim 4 preparation method it is characterised in that in composite filament PTT with change
Property weight polyester ratio be 4:6～6:4.
10. a kind of preparation method of polyester silk according to claim 4 is it is characterised in that the described concentrated sulfuric acid refers to
Mass concentration is 70～80% sulfuric acid, and concentrated sulfuric acid addition is 1～3wt% of binary of fatty acids；Described a certain amount of dilute sulphur
Acid refers to the sulfuric acid that mass concentration is 40～50%, and dilute sulfuric acid addition is 1～3wt% of binary of fatty acids mono-methyl.
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| CN105274637A (en) * | 2015-11-13 | 2016-01-27 | 福建经纬新纤科技实业有限公司 | Injected melt direct-spinning production process for PET-PTT composite elastic fibers |
| CN105463610B (en) * | 2015-12-29 | 2018-05-18 | 江苏恒力化纤股份有限公司 | A kind of fire-retardant polyester fibre and preparation method thereof |
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| CN1276444A (en) * | 1999-06-08 | 2000-12-13 | 东丽株式会社 | Soft stretch yarn and its mfg method |
| JP2006002321A (en) * | 2004-06-17 | 2006-01-05 | Hyosung Corp | Conjugate fiber and method for producing the same |
| CN101117750A (en) * | 2007-09-18 | 2008-02-06 | 中国人民解放军总后勤部军需装备研究所 | Polyester multiplex yarns doubling type widthwise elastic wool fabric and method for making same |
| CN101357980A (en) * | 2007-08-01 | 2009-02-04 | 北京服装学院 | A kind of novel elastic fiber and its manufacturing method |
| CN101372768A (en) * | 2007-08-22 | 2009-02-25 | 东丽纤维研究所（中国）有限公司 | Polyester composite light weight fibre and production method thereof |
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| CN1276444A (en) * | 1999-06-08 | 2000-12-13 | 东丽株式会社 | Soft stretch yarn and its mfg method |
| JP2006002321A (en) * | 2004-06-17 | 2006-01-05 | Hyosung Corp | Conjugate fiber and method for producing the same |
| CN101357980A (en) * | 2007-08-01 | 2009-02-04 | 北京服装学院 | A kind of novel elastic fiber and its manufacturing method |
| CN101372768A (en) * | 2007-08-22 | 2009-02-25 | 东丽纤维研究所（中国）有限公司 | Polyester composite light weight fibre and production method thereof |
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