Background technology:
Terylene be with polyethylene terephthalate (PET) through the fiber that melt spinning makes, be one of principal item of synthetic fiber.Its fabric has obtained using widely with well-pressed, non-ironing, mildew-resistant, advantage such as mothproof.But, owing to lack the functional group that directly combines in the PET molecule with dyestuff, and structure is tight, and unformed area is few, can only use disperse dyeing under high temperature, high pressure, and to the equipment and the technological requirement harshness of dyeing, cost is also than higher.For improving the dyeability of polyester fiber, adopt the molecular structure or the supramolecular structure of the method change polyester fiber of physics or chemical modification usually, introduce dye molecule and accept base or increase the space that holds dye molecule.Pass through to add third and fourth monomer, the cationic dyeable polyester fiber that copolymerization method obtains (CDP) and cation dyes normal pressure dyeable dacron (ECDP) as people.CDP needs dyeing under high pressure, and ECDP makes fiber strength reduce owing to add the 4th monomer polyethers, the heat endurance variation.Though cation dyeable polyester has obtained certain development, present most of polyester fibers still need adopt disperse dyeing.The method of disperse dyeing mainly contains two kinds of high-temperature and high pressure dyeing process and carrier boiling dyeing at normal pressure methods.Under the pressure of environmental protection pressure, carrier dyeing process steps down from the stage of history gradually, and high-temperature and high pressure dyeing process has become main flow.But there is the energy consumption height in high-temperature and high pressure dyeing process, is difficult to the industrial shortcoming of serialization, and is difficult to and fiber co-bathing dyeings such as the spandex of non-refractory, wool, so world textile bound pair disperse dye normal pressure is boiled, and to dye MODIFICATION OF POLYESTER FIBER research very active.
People such as nearest Ma Jinghong have reported the patent of invention (CN200410024652.5) of " a kind of polyester/phyllosilicate nano-composite material and preparation method ", system is made up of aromatic binary carboxylic acid or aromatic dicarboxylic dimethyl phthalate, dihydroxylic alcohols, the aromatic binary carboxylic acid that contains sulfonic acid group or its ester, phyllosilicate, by in the building-up process of polyester, adding the 3rd monomer and the organo montmorillonite that contains ionic group, prepare and both contain sulfonic acid group, contain the copolyesters of nano size montmorillonoid again.This copolyesters can be prepared the copolyester fiber of dyed easily by disperse dye by melt spinning by melt spinning or with this copolyesters after as master batch and PET blend.Imvite can have been played the effect of dying seat in the fiber in strand, and DISPERSE DYES can penetrate into the gap of the argillic horizon of clay particle.Some chemical group on the organo montmorillonite has also improved the compatibility of polyester fiber to dyestuff simultaneously, makes fiber to adopt disperse dyes dyeing under the boiling dyeing at normal pressure condition.And ionic group in the copolyesters and imvite have cooperative effect, and the dye-uptake of fiber is improved, and can also improve dyeing rate.
Summary of the invention:
The purpose of this invention is to provide a kind of dyed easily by disperse dye copolyester fiber.
Purpose of the present invention also provides a kind of manufacture method of above-mentioned copolyester fiber.
The copolyester section of dyed easily by disperse dye of the present invention can directly carry out the long filament and the staple fibre of melt spinning, stretching, spinning dyed easily by disperse dye after drying.
Preparation method of the present invention is to be that polyester/phyllosilicate nano-composite material copolymer with the copolymerization of the described polymerization intercalation of CN200410024652.5 is a master batch with above-mentioned a kind of dyed easily by disperse dye copolyester fiber, form with polyethylene terephthalate (PET) blend, wherein the weight ratio of master batch and PET is 5~50: 50~95.Carry out the copolyester fiber that melt spinning is made dyed easily by disperse dye after drying.
The polyester/phyllosilicate nano-composite material copolymer of above-mentioned polymerization intercalation copolymerization by following weight than forming:
Aromatic binary carboxylic acid or aromatic dicarboxylic dimethyl phthalate 50~73, dihydroxylic alcohols 20~45, the aromatic binary carboxylic acid or its ester 1~25 that contain sulfonic acid group, phyllosilicate 0.5~15 also contains catalyst 0.001~1.0 in case of necessity or/and additive 0.001~1.0.
Described aromatic binary carboxylic acid can be terephthalic acid (TPA), M-phthalic acid or 2, the 6-naphthalenedicarboxylic acid.Described aromatic binary carboxylic acid ester can be dimethyl terephthalate (DMT), dimethyl isophthalate or 2, the 6-naphthalene diformic acid dimethyl ester.Described dihydroxylic alcohols monomer can be ethylene glycol, butanediol or 1, ammediol etc.The described aromatic binary carboxylic acid ester that contains sulfonic acid group with between the 5-sulfonic acid alkali metal salts (to) rutgers is good.
The additive that contains in case of necessity among the present invention mainly is a stabilizing agent commonly used, comprises phosphorus (phosphine) acid esters compound of triphenyl phosphate, triphenyl phosphite etc.
Described phyllosilicate is imvite or saponite.Be preferably in carry out direct esterification polycondensation or ester exchange polycondensation before, imvite or saponite are handled through organic intercalation agent.Organic intercalation agent is the organic cation amine salt, as lauryl amine, hexadecylamine, hexamethylene diamine, lauric acid amine, triethanolamine, dodecyl trimethyl amine bromide, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl amine bromide and octadecyl benzyl dimethyl amine bromide etc.
Described catalyst is the oxide of Sb, Ge, Ti or Sn or the acetate of acetate and Zn, Mn, Mg, Ca or Co.
Manufacture method of the present invention is that wherein the polyester/phyllosilicate nano-composite material copolymer of polymerization intercalation copolymerization and polyethylene terephthalate weight ratio are 5~50: 50~95 with the polyester/phyllosilicate nano-composite material copolymer of the polymerization intercalation copolymerization of last art and polyethylene terephthalate (PET) section blend.Carry out melt spinning after drying, making the copolyester fiber of dyed easily by disperse dye.
This fiber can dye under 100 ℃ of conditions of normal pressure with disperse dyes, makes fiber dye middle dark color.And manufacture method is easy, cheap.
The present invention will be helped further to understand by following embodiment, but content of the present invention can not be limited.
The specific embodiment:
Embodiment 1
Will be through the imvite 11g of hexadecyl trimethyl ammonium bromide organic intercalation, join in the ethylene glycol, high-speed stirred 0.5 hour joins in the mixture of 185g dimethyl terephthalate (DMT), 130g ethylene glycol and 9g5-sodium sulfonate dimethyl isophthalate, and adding the 0.1g zinc acetate is catalyst.Under 200 ℃, carried out the normal pressure ester exchange reaction 2~4 hours.Ester exchange reaction finishes the back and adds 0.12g antimonous oxide and 0.1g triphenyl phosphate, and the reaction system intensification of reducing pressure was gradually reacted 1~3 hour under 255~290 ℃ of vacuum 70Pa, promptly obtained polyester/phyllosilicate nano-composite material.
As master batch and PET blend, the blend ratio is master batch: PET=15 with this polyester/phyllosilicate nano-composite material: 85 (weight ratios).Carry out melt spinning after drying, spinning speed is 800m/min, and draw ratio is 3.8 times, obtains the copolyester fiber of dyed easily by disperse dye.The mechanical property and the dyeability of fiber are listed in table 1 and the table 2.
Embodiment 2
Will be through the imvite 11g of hexadecyl trimethyl ammonium bromide organic intercalation, join in the ethylene glycol, high-speed stirred 0.5 hour joins in the mixture of 185g dimethyl terephthalate (DMT), 130g ethylene glycol and 12g5-sodium sulfonate dimethyl isophthalate, and adding the 0.1g zinc acetate is catalyst.Under 200 ℃, carried out the normal pressure ester exchange reaction 2~4 hours.Ester exchange reaction finishes the back and adds 0.12g antimonous oxide and 0.1g triphenyl phosphate, and the reaction system intensification of reducing pressure was gradually reacted 1~3 hour under 255~290 ℃ of vacuum 70Pa, promptly obtained polyester/phyllosilicate nano-composite material.
With this polyester/phyllosilicate nano-composite material as master batch and PET blend, the blend ratio is master batch: PET=15: 85 (weight ratios) are carried out melt spinning after drying, spinning speed is 800m/min, and draw ratio is 3.8 times, obtains the copolyester fiber of dyed easily by disperse dye.The mechanical property and the dyeability of fiber are listed in table 1 and the table 2.
Embodiment 3
Will be through the imvite 11g of hexadecyl trimethyl ammonium bromide organic intercalation, join in the ethylene glycol, high-speed stirred 0.5 hour joins in the mixture of 185g dimethyl terephthalate (DMT), 130g ethylene glycol and 15g5-sodium sulfonate dimethyl isophthalate, and adding the 0.1g zinc acetate is catalyst.Under 200 ℃, carried out the normal pressure ester exchange reaction 2~4 hours.Ester exchange reaction finishes the back and adds 0.12g antimonous oxide and 0.1g triphenyl phosphate, and the reaction system intensification of reducing pressure was gradually reacted 1~3 hour under 255~290 ℃ of vacuum 70Pa, promptly obtained polyester/phyllosilicate nano-composite material.
With this polyester/phyllosilicate nano-composite material as master batch and PET blend, the blend ratio is master batch: PET=15: 85 (weight ratios) are carried out melt spinning after drying, spinning speed is 800m/min, and draw ratio is 3.8 times, obtains the copolyester fiber of dyed easily by disperse dye.The mechanical property and the dyeability of fiber are listed in table 1 and the table 2.
Embodiment 4
Will be through the imvite 11g of hexadecyl trimethyl ammonium bromide organic intercalation, join in the ethylene glycol, high-speed stirred 0.5 hour joins in the mixture of 185g dimethyl terephthalate (DMT), 130g ethylene glycol and 18g5-sodium sulfonate dimethyl isophthalate, and adding the 0.1g zinc acetate is catalyst.Under 200 ℃, carried out the normal pressure ester exchange reaction 2~4 hours.Ester exchange reaction finishes the back and adds 0.12g antimonous oxide and 0.1g triphenyl phosphate, and the reaction system intensification of reducing pressure was gradually reacted 1~3 hour under 255~290 ℃ of vacuum 70Pa, promptly obtained polyester/phyllosilicate nano-composite material.
With this polyester/phyllosilicate nano-composite material as master batch and PET blend, the blend ratio is master batch: PET=15: 85 (weight ratios) are carried out melt spinning after drying, spinning speed is 800m/min, and draw ratio is 3.8 times, obtains the copolyester fiber of dyed easily by disperse dye.The mechanical property and the dyeability of fiber are listed in table 1 and the table 2.
Embodiment 5
Will be through the imvite 11g of hexadecyl trimethyl ammonium bromide organic intercalation, join in the ethylene glycol, high-speed stirred 0.5 hour joins in the mixture of 185g dimethyl terephthalate (DMT), 130g ethylene glycol and 15g5-sodium sulfonate dimethyl isophthalate, and adding the 0.1g zinc acetate is catalyst.Under 200 ℃, carried out the normal pressure ester exchange reaction 2~4 hours.Ester exchange reaction finishes the back and adds 0.12g antimonous oxide and 0.1g triphenyl phosphate, and the reaction system intensification of reducing pressure was gradually reacted 1~3 hour under 255~290 ℃ of vacuum 70Pa, promptly obtained polyester/phyllosilicate nano-composite material.
With this polyester/phyllosilicate nano-composite material as master batch and PET blend, the blend ratio is master batch: PET=10: 90 (weight ratios) are carried out melt spinning after drying, spinning speed is 800m/min, and draw ratio is 3.8 times, obtains the copolyester fiber of dyed easily by disperse dye.The mechanical property and the dyeability of fiber are listed in table 1 and the table 2.
Embodiment 6
Will be through the imvite 11g of hexadecyl trimethyl ammonium bromide organic intercalation, join in the ethylene glycol, high-speed stirred 0.5 hour joins in the mixture of 185g dimethyl terephthalate (DMT), 130g ethylene glycol and 15g5-sodium sulfonate dimethyl isophthalate, and adding the 0.1g zinc acetate is catalyst.Under 200 ℃, carried out the normal pressure ester exchange reaction 2~4 hours.Ester exchange reaction finishes the back and adds 0.12g antimonous oxide and 0.1g triphenyl phosphate, and the reaction system intensification of reducing pressure was gradually reacted 1~3 hour under 255~290 ℃ of vacuum 70Pa, promptly obtained polyester/phyllosilicate nano-composite material.
With this polyester/phyllosilicate nano-composite material as master batch and PET blend, the blend ratio is master batch: PET=20: 80 (weight ratios) are carried out melt spinning after drying, spinning speed is 800m/min, and draw ratio is 3.8 times, obtains the copolyester fiber of dyed easily by disperse dye.The mechanical property and the dyeability of fiber are listed in table 1 and the table 2.
Embodiment 7
Will be through the imvite 11g of hexadecyl trimethyl ammonium bromide organic intercalation, join in the ethylene glycol, high-speed stirred 0.5 hour joins in the mixture of 185g dimethyl terephthalate (DMT), 130g ethylene glycol and 15g5-sodium sulfonate dimethyl isophthalate, and adding the 0.1g zinc acetate is catalyst.Under 200 ℃, carried out the normal pressure ester exchange reaction 2~4 hours.Ester exchange reaction finishes the back and adds 0.12g antimonous oxide and 0.1g triphenyl phosphate, and the reaction system intensification of reducing pressure was gradually reacted 1~3 hour under 255~290 ℃ of vacuum 70Pa, promptly obtained polyester/phyllosilicate nano-composite material.
With this polyester/phyllosilicate nano-composite material as master batch and PET blend, the blend ratio is master batch: PET=30: 70 (weight ratios) are carried out melt spinning after drying, spinning speed is 800m/min, and draw ratio is 3.8 times, obtains the copolyester fiber of dyed easily by disperse dye.The mechanical property and the dyeability of fiber are listed in table 1 and the table 2.
Embodiment 8
Will be through the imvite 11g of hexadecyl trimethyl ammonium bromide organic intercalation, join in the ethylene glycol, high-speed stirred 0.5 hour joins in the mixture of 185g dimethyl terephthalate (DMT), 130g ethylene glycol and 15g5-sodium sulfonate dimethyl isophthalate, and adding the 0.1g zinc acetate is catalyst.Under 200 ℃, carried out the normal pressure ester exchange reaction 2~4 hours.Ester exchange reaction finishes the back and adds 0.12g antimonous oxide and 0.1g triphenyl phosphate, and the reaction system intensification of reducing pressure was gradually reacted 1~3 hour under 255~290 ℃ of vacuum 70Pa, promptly obtained polyester/phyllosilicate nano-composite material.
With this polyester/phyllosilicate nano-composite material as master batch and PET blend, the blend ratio is master batch: PET=50: 50 (weight ratios) are carried out melt spinning after drying, spinning speed is 800m/min, and draw ratio is 3.8 times, obtains the copolyester fiber of dyed easily by disperse dye.The mechanical property and the dyeability of fiber are listed in table 1 and the table 2.
Table 1
The TENSILE STRENGTH elongation at break
The embodiment spinnability
(CN/dtex) (%)
1 3.47 25.4
2 3.39 23.8
3 3.37 24.7
4 3.33 24.7
5 3.59 21.9
6 3.30 26.3
7 general 3.21 20.7
8 general 3.05 19.8
Table 2
Dye-uptake (%)
Embodiment
The disperse red disperse yellow
Pure PET fiber 49 28
1 72.6 67.9
2 81.9 75.5
3 84.0 80.4
4 87.8 83.6
5 82.1 72.8
6 90.1 85.3
7 91.4 88.7
8 91.3 89.5