CN101525784A - Cationic dye deep dyeing copolyester at normal pressure and method for producing same - Google Patents
Cationic dye deep dyeing copolyester at normal pressure and method for producing same Download PDFInfo
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- CN101525784A CN101525784A CN200810018626A CN200810018626A CN101525784A CN 101525784 A CN101525784 A CN 101525784A CN 200810018626 A CN200810018626 A CN 200810018626A CN 200810018626 A CN200810018626 A CN 200810018626A CN 101525784 A CN101525784 A CN 101525784A
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Abstract
The invention relates to a cationic dye deep dyeing copolyester at normal pressure and a method for producing the same, and mainly relates to copolymerization of biologically prepared ethylene glycol, a monomer of dimethyl terephthalate, an alkali salt of isophthalic acid glycol ester-5-sulfonic acid and PEG1000. When the prepared copolyester is co-mixed with the common PET for spinning, the fluidity and the spinnability are both improved; and the deep dyeing of cationic dyes at normal pressure can be adopted, so that the defect that the PET can only be dyed by disperse dyes at high temperature and high pressure is overcome.
Description
Technical field:
The present invention relates to a kind of cationic dye deep dyeing copolyester at normal pressure and production method.
Background technology:
Polyethylene terephthalate (PET) polyester fiber is the synthetic fiber kind of present worldwide production maximum, singly in China's Mainland production capacity in 2005 just more than 1,300 ten thousand tons.And ethylene glycol is the main raw material of making the PET polyester fiber, and one ton of PET polyester fiber of every manufacturing needs 0.35 ton of ethylene glycol approximately.
And up to the present, each big production ethylene glycol enterprise of the world all is that to adopt with the oil be the technology of raw material basically, relates to petroleum more than 6 tons and make one ton of ethylene glycol.Some ethylene glycol production units of China also all are petrochemical systems.Introduction of foreign technology and complete set of equipments are synthetic and catalytic hydration production ethylene glycol mostly by the oxirane pressure (hydraulic) water.These technological processes are long, and equipment investment is big, the energy consumption height; Perhaps Preparation of catalysts complexity, problems such as instability or residual quantity are difficult to solve.And oil recovery, transportation and refining etc. all may cause problems such as serious environmental pollution.Soaring along with the minimizing of petroleum resources and oil price is that the process route of raw material obviously has been subjected to very big threat by oil.World's oilreserves sharply descends, and many chemical engineering industries are just carrying out the adjustment of raw material mix.Existing in the world at present trend thinks that the petrochemical industry route does not have competitiveness, based on the raw material of biomass resource, can take from plant, and can be converted into needed product with enzymatic isolation method.
Therefore the ethylene glycol that utilizes reproducible cereal resource to extract in the polyester industrial is the focus of studying both at home and abroad, and this promotes that to reducing the dependence of people to petroleum resources the sustainable development of polyester industry is significant.
Although the physical and mechanical property of polyester fiber and comprehensive wearing characteristics are good in addition, but because the chemical constitution of polyester macromolecule is regular, the degree of crystallinity and the degree of orientation are higher, polarity is less, lack hydrophily, between the tortuous long-chain molecule of polyester, there is not suitably to hold the gap of dye molecule, therefore the dyestuff grain is difficult to enter the fiber amorphous region, and do not possess the seat of dying on the polyester macromolecule, thereby cause its dyeability poor, can use the kind of dyestuff few, polyester fiber can only adopt methods such as DISPERSE DYES carrier dyeing, high-temp dyeing and pad-dry-cure dyeing.Therefore have only by forming the colouring problem that copolyesters could fundamentally solve polyester fiber after the modification.
Summary of the invention:
The purpose of this invention is to provide a kind of is feedstock production cationic dye deep dyeing copolyester at normal pressure and production method by biological preparing ethylene glycol.
Cationic dye deep dyeing copolyester at normal pressure section of the present invention and fiber thereof are the copolymer of dimethyl terephthalate (DMT), biological preparing ethylene glycol, ethylene m-phthalate-5-sulfonic acid alkali metal salts; Its main repetitive is: dimethyl terephthalate (DMT) and ethylene glycol, and wherein the carbon in the ethylene glycol derives from biomaterial, belongs to biological preparing ethylene glycol; Dimethyl terephthalate (DMT) monomer, biological preparing ethylene glycol monomer mole ratio are 1: 1.7～2.4 in the polymer, the monomer of ethylene m-phthalate-5-sulfonic acid alkali metal salts is 2.4%～18% molar weight of dimethyl terephthalate (DMT) monomer, and cetomacrogol 1000 (PEG1000) quality is 0.5%～2% of a dimethyl terephthalate (DMT) monomer weight.
Biomaterial of the present invention is the stalk of corn, sugarcane, wheat or other crops etc., and wherein said corn, wheat are its seed and/or stalk.These biomaterials make raw material ethylene glycol through biofermentation and/or chemical industry process, for example corn is through the bioprocess separating starch, obtain the sugar of 5 carbon and 6 carbon through processing, these sugars can be prepared multicomponent binary alcohol through the technology of hydrogenation catalyst, after the purifies and separates general procedure, just can obtain raw material dihydric alcohol ethylene glycol component of the present invention, this ethylene glycol is through heating, carry out filtration treatment with activated carbon, just obtain of the present invention in 190～350nm wave-length coverage transmitance be biological ethylene glycol more than 50%.
The carbon that also contains in the polyester derives from the binary acid of petroleum and the copolymer composition of dihydroxylic alcohols.The inherent viscosity of this cationic dye deep dyeing copolyester at normal pressure is at 0.55～0.75dl/g, and fusing point is at 240 ℃～251 ℃.
Cationic dye deep dyeing copolyester at normal pressure section of the present invention and fiber thereof are made by following method:
The interpolation mol ratio of dimethyl terephthalate (DMT) and biological preparing ethylene glycol monomer is 1: 1.7～2.4, in divalence, trivalent, the metal oxide of tetravalence and/or acetate are as catalyst, under 220～260 ℃ temperature, reacted 1～5 hour and dehydration, add ethylene m-phthalate-5-sulfonic acid alkali metal salts, copolymer-1～4 hour again under 250～300 ℃ of temperature, make the copolyester section of cation dye chromophil, wherein catalyst amount is 0.01%～0.08% of a dimethyl terephthalate (DMT) weight, the monomer of ethylene m-phthalate-5-sulfonic acid alkali metal salts is 2.4%～18% molar weight to the dimethyl terephthalate (DMT) monomer, and the PEG1000 quality is 0.5%～2% of a dimethyl terephthalate (DMT) monomer weight.Metal can be Na in the metal oxide of divalence recited above, trivalent, tetravalence
+, Ga
2+, Mn
4+, Co
2+, Zn
2+Deng.
The copolyester section of above-mentioned cation dye chromophil is done section 130～180 ℃ of dry acquisitions.
Above-mentioned section or dried section are carried out the copolyester fiber that spinning obtains cation dye chromophil in following condition: 280～320 ℃ of extruder temperatures, spinning speed 900～5000m/min, 65～180 ℃ of draft temperatures, draw ratio are 1.5～5 times.
Owing to introduced sodium group, the metal ion (Na on it in this condensate
+, K
+Deng) easily and the cation exchange in the cation dyes, dyestuff just is fixed on the polyester molecule with ionic bond, disengage salt simultaneously, because dyeing is carried out in water-bath, sodium chloride (NaCl) etc. can remove fully, balance is carried out to helping the direction that dyestuff is combined on the fiber always, thereby makes the dyeability of polyester fiber be improved.
Fiber provided by the present invention can dye with the cation dyes normal temperature and pressure.And because ethylene m-phthalate-5-sodium sulfonate (SIPE) has destroyed the macromolecular regularity of PET condensate, make the condensate crystalline rate slack-off, copolymer institute spinning fibre is soft, gloss is soft, simultaneously can give fiber highly shrinkable and anti-fluffing and anti-pilling performance by the optimizing and revising of spinning technique.
The copolyester fiber that cation dyes normal pressure of the present invention can dye is the serial fiber of a kind of multifunctionality, can be the staple fibre of cation dyes normal-temperature normal-pressure dyeable, the anti-fluffing and anti-pilling staple fibre of cation dyes normal-temperature normal-pressure dyeable or the high shrinkage short fiber of cation dyes normal-temperature normal-pressure dyeable; The low speed that is a kind of cation dyes normal-temperature normal-pressure dyeable spins drawing of fiber; Be that a kind of high-speed spinning drawing of fiber of cation dyes normal-temperature normal-pressure dyeable, the high-speed spinning of cation dyes normal-temperature normal-pressure dyeable add the height contraction long fiber of the full drawing of fiber of high-speed spinning of elastic fibre or cation dyes normal-temperature normal-pressure dyeable, a kind of cation dyes normal-temperature normal-pressure dyeable or the anti-fluffing and anti-pilling long fiber of cation dyes normal-temperature normal-pressure dyeable; The thin dawn multifilament or the monofilament of cation dyes normal-temperature normal-pressure dyeable; The special-shaped cation dyes normal-temperature normal-pressure dyeable fiber of cation dyes normal-temperature normal-pressure dyeable.
And section of the present invention can with polyester, the polyamide blended functional fiber that is spun into.The fiber of invention has the cation dyes normal-temperature normal-pressure dyeable, highly shrinkable, fabrics feel soft, characteristics such as anti-fluffing and anti-pilling, and has an environmental safety, can produce in enormous quantities effectively, can be widely used in pure spin or natural fibre blended, to obtain the wearing fabric of style varied with silk, thin,tough silk, cotton, hair, fiber crops etc.
The invention will be further described below in conjunction with embodiment.
The specific embodiment:
Embodiment
Further specify the present invention with the following example, but the present invention is not limited to these embodiment.
Biological material source ethylene glycol: great achievement group in Changchun produces, and the carbon source is corn, purity: 97%.The heating of 190 ℃ of above-mentioned ethylene glycol is carried out filtration treatment with active carbon after 2 hours, obtain transmitance at the 250nm wavelength and be 65%, the transmitance of 300nm wavelength is 90% ethylene glycol.
Terephthalic acid (TPA): sub-petrochemical iy produced, polymer grade are raised by China.
Dimethyl terephthalate (DMT): Iranian Fiber Intermediate Products Co. produces
Oil source ethylene glycol EG: raise sub-petro-chemical corporation and produce, the carbon source is oil, purity: more than 99%.
Comparative Examples:
Adopt semicontinuous polyester equipment, according to mol ratio is 1: 1.9 adding dimethyl terephthalate (DMT), add catalyst acetic acid cobalt (COA) in the time of the ethylene glycol EG in oil source, the addition of catalyst is 0.05% of a dimethyl terephthalate (DMT) weight, stir esterification 3h down at 240～250 ℃, treat that water yield reaches 90% o'clock of theoretical value, interpolation contains the ethylene isophthalate-ethylene glycol solution of 5-sodium sulfonate and 1% the PEG1000 that are equivalent to dimethyl terephthalate (DMT) 2.4 molar percentages and carries out polycondensation reaction, add other catalyst again (as antimonous oxide Sb2O3 after the stirred for several minute, cobalt acetate etc., wherein, the addition of antimonous oxide Sb2O3 is 0.03% of a dimethyl terephthalate (DMT) weight, the addition of cobalt acetate be dimethyl terephthalate (DMT) weight 0.015%) carry out polymerisation, temperature is controlled at 270～300 ℃, vacuum＜1mmHg, the inherent viscosity that can make copolymer is 0.64, and fusing point is 252 ℃.
Embodiment 1
Adopt semicontinuous polyester equipment, according to mol ratio is 1: 1.9 adding dimethyl terephthalate (DMT), add catalyst acetic acid cobalt (COA) in the time of biology preparing ethylene glycol EG, the addition of catalyst is 0.05% of a dimethyl terephthalate (DMT) weight, stir esterification 3h down at 240-250 ℃, treat that water yield reaches 90% o'clock of theoretical value, add the PEG1000 contain the ethylene glycol solution of the ethylene isophthalate-5-sodium sulfonate that is equivalent to dimethyl terephthalate (DMT) 2.4 molar percentages and to be equivalent to dimethyl terephthalate (DMT) 1% weight and carry out polycondensation reaction, add other conventional catalyst again (as antimonous oxide Sb2O3 after the stirred for several minute, cobalt acetate etc., wherein, the addition of antimonous oxide Sb2O3 is 0.03% of a dimethyl terephthalate (DMT) weight, the addition of cobalt acetate be dimethyl terephthalate (DMT) weight 0.015%) carry out polymerisation, temperature is controlled at 270～300 ℃, vacuum＜1mmHg, the inherent viscosity that can make copolymer is 0.64, and fusing point is 251 ℃.
Embodiment 2
Adopt semicontinuous polyester equipment, according to mol ratio is 1: 1.9 adding dimethyl terephthalate (DMT), add catalyst acetic acid cobalt (COA) in the time of biology preparing ethylene glycol EG, the addition of catalyst is 0.05% of a dimethyl terephthalate (DMT) weight, stir esterification 3h down at 240～250 ℃, treat that water yield reaches 90% o'clock of theoretical value, add the PEG1000 contain the ethylene glycol solution of the ethylene isophthalate-5-sodium sulfonate that is equivalent to dimethyl terephthalate (DMT) 3.6 molar percentages and to be equivalent to dimethyl terephthalate (DMT) 1% weight and carry out polycondensation reaction, add other catalyst again (as antimonous oxide Sb2O3 after the stirred for several minute, cobalt acetate etc., wherein, the addition of antimonous oxide Sb2O3 is 0.03% of a dimethyl terephthalate (DMT) weight, the addition of cobalt acetate be dimethyl terephthalate (DMT) weight 0.015%) carry out polymerisation, temperature is controlled at 270～300 ℃, vacuum＜1mmHg, the inherent viscosity of discharging copolyester section is 0.62, and fusing point is 249 ℃.
Embodiment 3
Adopt semicontinuous polyester equipment, according to mol ratio is 1: 1.9 adding dimethyl terephthalate (DMT), add catalyst acetic acid cobalt (COA) in the time of biology preparing ethylene glycol EG, the addition of catalyst is 0.05% of a dimethyl terephthalate (DMT) weight, stir esterification 3h down at 240～250 ℃, treat that water yield reaches 90% o'clock of theoretical value, add the PEG1000 contain the ethylene glycol solution of the ethylene isophthalate-5-sodium sulfonate that is equivalent to dimethyl terephthalate (DMT) 7.2 molar percentages and to be equivalent to dimethyl terephthalate (DMT) 1% weight and carry out polycondensation reaction, add other catalyst again (as antimonous oxide Sb2O3 after the stirred for several minute, cobalt acetate etc., wherein, the addition of antimonous oxide Sb2O3 is 0.03% of a dimethyl terephthalate (DMT) weight, the addition of cobalt acetate be dimethyl terephthalate (DMT) weight 0.015%) carry out polymerisation, temperature is controlled at 270～300 ℃, vacuum＜1mmHg, the inherent viscosity of discharging copolyester section is 0.58, and fusing point is 245 ℃.
Embodiment 4
Adopt semicontinuous polyester equipment, according to mol ratio is 1: 1.9 adding dimethyl terephthalate (DMT), add catalyst acetic acid cobalt (COA) in the time of biology preparing ethylene glycol EG, the addition of catalyst is 0.05% of a dimethyl terephthalate (DMT) weight, stir esterification 3h down at 240～250 ℃, treat that water yield reaches 90% o'clock of theoretical value, add the PEG1000 contain the ethylene glycol solution of the ethylene isophthalate-5-sodium sulfonate that is equivalent to dimethyl terephthalate (DMT) 10.8 molar percentages and to be equivalent to dimethyl terephthalate (DMT) 1% weight and carry out polycondensation reaction, add other catalyst again (as antimonous oxide Sb2O3 after the stirred for several minute, cobalt acetate etc., wherein, the addition of antimonous oxide Sb2O3 is 0.03% of a dimethyl terephthalate (DMT) weight, the addition of cobalt acetate be dimethyl terephthalate (DMT) weight 0.015%) carry out polymerisation, temperature is controlled at 270～300 ℃, vacuum＜1mmHg, the inherent viscosity of discharging copolyester section is 0.51, and fusing point is 242 ℃.
Embodiment 5
Adopt semicontinuous polyester equipment, according to mol ratio is 1: 2.0 adding dimethyl terephthalate (DMT), add catalyst acetic acid cobalt (COA) in the time of biology preparing ethylene glycol EG, the addition of catalyst is 0.05% of a dimethyl terephthalate (DMT) weight, stir esterification 3h down at 240～250 ℃, treat that water yield reaches 90% o'clock of theoretical value, add the PEG1000 contain the ethylene glycol solution of the ethylene isophthalate-5-sodium sulfonate that is equivalent to dimethyl terephthalate (DMT) 2.4 molar percentages and to be equivalent to dimethyl terephthalate (DMT) 1% weight and carry out polycondensation reaction, add other catalyst again (as antimonous oxide Sb2O3 after the stirred for several minute, cobalt acetate etc., wherein, the addition of antimonous oxide Sb2O3 is 0.03% of a dimethyl terephthalate (DMT) weight, the addition of cobalt acetate be dimethyl terephthalate (DMT) weight 0.015%) carry out polymerisation, temperature is controlled at 270～300 ℃, vacuum＜1mmHg, the inherent viscosity of discharging copolyester section is 0.63, and fusing point is 248 ℃.
Embodiment 6
With copolyester section in the vacuum drum drier, steam pressure 0.2MPa, vacuum≤-0.097MPa, slowly heat up, control pre-crystallizing and drying 16～20hr cool time, obtain the dried section of moisture content less than 50PPM.Adopt VD406 spinning combination machine and LVD801 after-processing combination machine, 290～320 ℃ of control extruder temperatures, winding speed 1000m/min, 25～30 ℃ of cooling wind-warm syndrome, 3.8～4.2 times of draw ratios, stretching distribution ratio 70～80%, 70 ℃ of stretch bath temperature, 90～130 ℃ of relaxation heat setting temperature, relaxation heat setting time 30～40min, obtain fibrous fracture intensity 3.8CN/dtex, elongation at break is 24.8%, and anti-fluffing and anti-pilling is 4 grades a cation dyes normal-temperature normal-pressure dyeable anti-fluffing and anti-pilling staple fibre.
Evaluation method:
Fusing point (Tm): constant temperature is 3 minutes after using differential scanning calorimeter (DSC) to be warmed up to 250 ℃ from 20 ℃ with 20 ℃ of per minutes, eliminates thermal history; Cool to 20 ℃ with 20 ℃ of per minutes again, constant temperature 3 minutes; Be warmed up to 250 ℃ with 20 ℃ of per minutes again, finish.To obtain melt temperature in heating up for the second time is fusing point.
Spinning operability: use resulting normal pressure cation dyeable polyester, carry out the spinning of 44diex/36f with direct spinning drawing process (rotation fiber elongation method), according to spinning filter pressure rising situation, spinning breaks, according to estimating to poor order, be evaluated as zero by good, △, *.
Cation dyes coloring: the tinctorial property of cation dyes, can be under Kayacryl BlueGSL-ED (Nippon Kayaku K. K's system) 3.0%owf, acetate 0.2g/l, 1: 50 condition of bath raio, dyeed 60 minutes down in atmospheric boiling temperature (98 ℃), measure the dyeing liquor absorbance of dyeing front and back.Then, calculating exhaustion rate (%) according to following formula, is that average evaluation more than 90% is ◎ with the exhaustion rate, with more than 80% and be lower than 90% and be evaluated as zero, with more than 70% and be lower than 80% and be evaluated as △, will be lower than 70% be evaluated as *.
Absorbance before exhaustion rate (%)=100 * (absorbance one dyeing back absorbance before the dyeing)/dyeing.
| Viscosity | Fusing point (℃) | The spinning operability | Dye coloring | |
| Comparative Examples | 0.64 | 252 | ○ | ◎ |
| Embodiment 1 | 0.64 | 251 | ○ | ◎ |
| Embodiment 2 | 0.62 | 247 | ○ | ◎ |
| Embodiment 3 | 0.58 | 245 | ○ | ○ |
| Embodiment 4 | 0.51 | 242 | △ | ○ |
| Embodiment 5 | 0.63 | 248 | ○ | ○ |
Claims (8)
1, a kind of cationic dye deep dyeing copolyester at normal pressure is characterized in that: ethylene glycol, dimethyl terephthalate (DMT) monomer, ethylene m-phthalate-5-sulfonic acid alkali metal salts and PEG1000 copolymerization by biological material source make.
2, cationic dye deep dyeing copolyester at normal pressure according to claim 1 is characterized in that: described biomaterial is the stalk of corn, sugarcane, wheat or other crops.
3, cationic dye deep dyeing copolyester at normal pressure according to claim 1 and 2 is characterized in that: wherein ethylene glycol content is 95%～99.9% in the biological ethylene glycol, and transmitance is more than 50% in 190～350nm wave-length coverage.
4, cationic dye deep dyeing copolyester at normal pressure according to claim 1 and 2, it is characterized in that: the monomer mole ratio of dimethyl terephthalate (DMT) monomer, ethylene glycol is 1: 1.7～2.4 in this copolyester section, the monomer of ethylene m-phthalate-5-sulfonic acid alkali metal salts is 2.4%～18% molar weight of dimethyl terephthalate (DMT) monomer, and the PEG1000 amount is 0.5%～2% of dimethyl terephthalate (DMT) monomer weight.
5, cationic dye deep dyeing copolyester at normal pressure according to claim 1 and 2 is characterized in that: the inherent viscosity of polyester is 0.55～0.75dl/g, and fusing point Tm is 240 ℃～251 ℃.
6, a kind of production method of cationic dye deep dyeing copolyester at normal pressure as claimed in claim 1, it is characterized in that: 2～4 valent metal oxides and/or acetate as catalyst under 220～260 ℃ of temperature, with the glycol monomethyl precursor reactant 1～5 hour and the dehydration of dimethyl terephthalate (DMT) and biological material source, the ethylene glycol monomer mol ratio of dimethyl terephthalate (DMT) and biological material source is 1: 1.7～2.4; Add ethylene m-phthalate-5-sulfonic acid alkali metal salts, PEG1000,, make the copolyester section of cation dyes normal pressure engrain at 250～300 ℃ of copolymer-1s-4 hour; Wherein catalyst amount is 0.01%～0.08% of a dimethyl terephthalate (DMT) weight, and the monomer of ethylene m-phthalate-5-sulfonic acid alkali metal salts is that 2.4%～18% molar weight of dimethyl terephthalate (DMT) monomer, PEG1000 are 0.5%～2% of dimethyl terephthalate (DMT) monomer weight.
7, the production method of cationic dye deep dyeing copolyester at normal pressure according to claim 6, it is characterized in that: section is carried out the copolyester fiber that spinning obtains cation dye chromophil in following condition: 280～320 ℃ of extruder temperatures, spinning speed 900～5000m/min, 65～180 ℃ of draft temperatures, draw ratio are 1.5～5 times.
8, according to the production method of claim 6 or 7 described cationic dye deep dyeing copolyester at normal pressure, it is characterized in that: described section also drying is handled, and must do section.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391486A (en) * | 2011-09-19 | 2012-03-28 | 吴江市港洋化纤有限公司 | Preparation method for polyester fibers with anti-static, anti-pilling and normal-pressure cation dyeable compound functions |
| CN102391487A (en) * | 2011-09-19 | 2012-03-28 | 吴江市港洋化纤有限公司 | Preparation method for anti-pilling, anti-ageing and normal-pressure cation dyeable polyester chips |
| CN102433604A (en) * | 2011-09-19 | 2012-05-02 | 吴江市港洋化纤有限公司 | Method for preparing polyester fiber having compound functions of pilling resistance, ageing resistance and normal-pressure cationic dyeability |
| WO2012088668A1 (en) * | 2010-12-29 | 2012-07-05 | 东华大学 | Dye bath formulation and method for dyeing copolyester fiber or product thereof to deep black using the same |
| CN103833994A (en) * | 2012-11-22 | 2014-06-04 | 东丽纤维研究所（中国）有限公司 | Alkali-soluble copolyester and its production method and use |
| CN113897695A (en) * | 2021-09-27 | 2022-01-07 | 杭州观晨实业有限公司 | Preparation method of continuous polymerization direct spinning cation dyeable high-shrinkage polyester pre-oriented yarn POY |
| CN116254629A (en) * | 2022-12-10 | 2023-06-13 | 桐昆集团股份有限公司 | Preparation method of elastic fiber easy to dye at normal temperature |
-
2008
- 2008-03-04 CN CN200810018626A patent/CN101525784A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012088668A1 (en) * | 2010-12-29 | 2012-07-05 | 东华大学 | Dye bath formulation and method for dyeing copolyester fiber or product thereof to deep black using the same |
| CN102391486A (en) * | 2011-09-19 | 2012-03-28 | 吴江市港洋化纤有限公司 | Preparation method for polyester fibers with anti-static, anti-pilling and normal-pressure cation dyeable compound functions |
| CN102391487A (en) * | 2011-09-19 | 2012-03-28 | 吴江市港洋化纤有限公司 | Preparation method for anti-pilling, anti-ageing and normal-pressure cation dyeable polyester chips |
| CN102433604A (en) * | 2011-09-19 | 2012-05-02 | 吴江市港洋化纤有限公司 | Method for preparing polyester fiber having compound functions of pilling resistance, ageing resistance and normal-pressure cationic dyeability |
| CN102391487B (en) * | 2011-09-19 | 2012-10-10 | 吴江市港洋化纤有限公司 | Preparation method for anti-pilling, anti-aging and normal-pressure cation dyeable polyester chips |
| CN103833994A (en) * | 2012-11-22 | 2014-06-04 | 东丽纤维研究所（中国）有限公司 | Alkali-soluble copolyester and its production method and use |
| CN113897695A (en) * | 2021-09-27 | 2022-01-07 | 杭州观晨实业有限公司 | Preparation method of continuous polymerization direct spinning cation dyeable high-shrinkage polyester pre-oriented yarn POY |
| CN116254629A (en) * | 2022-12-10 | 2023-06-13 | 桐昆集团股份有限公司 | Preparation method of elastic fiber easy to dye at normal temperature |
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Application publication date: 20090909 |