CN106008941A - Imidazolyl dyeable modified copolyester for anionic dye and preparation and application of imidazolyl dyeable modified copolyester - Google Patents

Imidazolyl dyeable modified copolyester for anionic dye and preparation and application of imidazolyl dyeable modified copolyester Download PDF

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CN106008941A
CN106008941A CN201610334450.3A CN201610334450A CN106008941A CN 106008941 A CN106008941 A CN 106008941A CN 201610334450 A CN201610334450 A CN 201610334450A CN 106008941 A CN106008941 A CN 106008941A
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modified copolyester
anionic dye
contaminate
imidazole radicals
type modified
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CN106008941B (en
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夏于旻
罗斌
倪建华
王依民
王燕萍
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Donghua University
National Dong Hwa University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6856—Dicarboxylic acids and dihydroxy compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention provides imidazolyl dyeable modified copolyester for anionic dye and preparation and application of the imidazolyl dyeable modified copolyester. The imidazolyl dyeable modified copolyester for the anionic dye is characterized in that comonomers of the imidazolyl dyeable modified copolyester comprise terephthalic acid, ethylene glycol, N-2-(3, 5-dicarboxyl phenyl) ethyl-N'-methylimidazole chloride and 2-methyl-1, 4-butylene glycol, and a molar ratio of the terephthalic acid to the ethylene glycol to the N-2-(3, 5-dicarboxyl phenyl) ethyl-N'-methylimidazole chloride to the 2-methyl-1, 4-butylene glycol is 1:1.2-2.5:0.01-0.08:0.03-0.25. The imidazolyl dyeable modified copolyester can be used for slicing and yarn releasing or can be directly spun to prepare filament or staple fibers. The imidazolyl dyeable modified copolyester for the anionic dye, the preparation and the application have the advantages that the fibers prepared by the aid of the prepared imidazolyl dyeable modified copolyester are excellent in anionic dye dyeability and can be subjected to normal-temperature and normal-pressure dyeing or normal-pressure boiling dyeing, and the dye-uptake can reach 90% at least; the fibers, wool and real silk can be subjected to mixed-bath dyeing or one-bath dyeing, the dye is difficult to leak, and the imidazolyl dyeable modified copolyester can be applied to the field of clothing, home textiles and industry.

Description

A kind of imidazole radicals anionic dye can contaminate type modified copolyester and preparation thereof and application
Technical field
The present invention relates to a kind of copolyesters and its preparation method and application field, specifically, refer to one Imidazole radicals anionic dye can contaminate type modified copolyester and its preparation method and application.
Background technology
Textile industry is the conventional column industry of Chinese national economy and important people's livelihood industry.Wherein polyester fiber It it is textile fabric most widely used in textile industry, that yield is maximum.Polyester fiber has a series of premium properties, Such as elastic modelling quantity and fracture strength height, resilience is moderate, thermal finalization is excellent, heat-resisting light resistance is good, Gu Qiguang General it is applied to the fields such as clothing, home textile and industry.The excellent physical and mechanical properties of polyester fiber depends on regular Molecular structure and higher degree of crystallinity, but this also makes dyeing polyester fibers difficulty simultaneously.Due in its molecular structure Lack the active group being bonded with dyestuff, can only be with disperse dyes in High Temperature High Pressure or the condition that has carrier Lower dyeing.For studying the modification of polyester fiber, occur in that copolymerization, be blended and the method such as surface chemical reaction, its Middle copolymerization method is one of important chemical modification means.Dyeing, modifying copolyesters currently mainly has the dye of positive ion Dyeable copolyester (include high-temp and-pressure cation dyeable copolyester (CDP) and boiling dyeing at normal pressure type sun from Sub-dye capable of dyeing copolyesters (ECDP)) and anionic dye dyeable copolyester (ADP).At present, China is Form the production of CDP and ECDP of certain batch, and the industrialization of ADP be still restricted, its research and During exploitation is the most constantly carried out.
Anionic dye dyeable copolyester (ADP) is a kind of dye to anionic dye with preferable dyeability Color modified copolyester.Owing to anionic dye is cheap, chromatograph is complete, bright in colour, and ADP can With with the co-bathing dyeing such as Pilus Caprae seu Ovis, silk, simplify dyeing, colouring uniformly, therefore ADP have wide should Use prospect.But owing in acid stain structure, dye radical is the relatively large sulfonate radical anion of volume, and The intermolecular space of polyester fiber is little, and does not contains the group to anionic dye with affinity, and dyestuff is difficult to ooze Enter, therefore be difficulty with anionic dye dyeing.
Through the literature search of prior art is found, prepare anionic dye currently with copolymerization method and can contaminate copolymerization The approach of ester mainly uses nitrogenous comonomer when polymerization.Easily generate quaternary ammonium compound due to nitrogen, connect Receiving the hydrion in acid medium and positively charged, this positive charge concentrates on the basic group of main polymer chain On, as the seat absorbing anionic dye.General used modifying agent is amide containing class modifying agent, containing primary, Secondary, tertiary amines modifying agent, nitrogen heterocyclic ring class modifying agent, such as Isosorbide-5-Nitrae-bis-aminopropyl piperazines, 2,2,6,6-tetramethyl piperazines Pyridine, triazole, butyl glycol amine etc..Canadian Patent (Reid William M, Shaw Barry M.Acid dyeable polyester.CANP, 974340,1975-09-09.) in, make with Isosorbide-5-Nitrae-bis-aminopropyl piperazines For modifying agent, generate salt prior to p-phthalic acid, fatty acid response, be then added in reactor carry out polycondensation, The modified dacron obtained has good dye-uptake to acid stain.United States Patent (USP) (Tanikella Murty S, Von Susani Odorich.Acid dyeable fibers of polyester modified with tetramethyl piperidine Polyether glycols.USP, 4001190,1977-01-04.) in, with tetramethylpiperidinol as modifying agent, when washing When in synthetic fibre, the mass fraction of nitrogen is 0.05%～0.25%, the modified dacron obtained dyes in acid dye bath, obtains Obtain gratifying effect.Fourth gold tinkling of pieces of jade et al. is at " synthetic fibers " o. 11th page 4 in 2008 extremely in recent years Having delivered " preparation of acid-dyeable modified poly ester and performance thereof " by page 8, this article author utilizes acyl in oneself The method of amine monomers and nylon 6 oligomer and polyethylene terephthalate copolymer prepares acid-dyeable PET.Although More existing researchs and report in this field, but for the rarest report of research of imidazole radicals comonomer.
Summary of the invention
It is an object of the invention to provide a kind of imidazole radicals anionic dye and can contaminate type modified copolyester and preparation thereof Methods and applications, the fiber of this copolyesters has good anionic dye stainability, can dye with normal temperature and pressure Or boiling dyeing at normal pressure, dye-uptake is up to more than 90%, and dyestuff is difficult to leakage, and fiber fluffy, resilience are good.
In order to achieve the above object, the invention provides a kind of imidazole radicals anionic dye and can contaminate type modified copolymer Ester, it is characterised in that its comonomer includes: mol ratio be 1: 1.2～2.5: 0.01～0.08: 0.03～0.25 right Phthalic acid, ethylene glycol, N-2-(3,5-dicarboxyphenyi) ethyl-N '-Methylimidazole. villaumite and 2-methyl isophthalic acid, 4- Butanediol.
Further, described imidazole radicals anionic dye can contaminate the structural formula of type modified copolyester:
Terephthalic acid units, ethylene glycol unit, N-2-(3,5-dicarboxyphenyi) ethyl-N '-methyl in structural formula Imidazoles villaumite unit and 2-methyl isophthalic acid, the mol ratio of 4-butanediol unit is X: m: Y: n.
Further, described imidazole radicals anionic dye can contaminate type modified copolyester intrinsic viscosity be 0.3～0.7, capillary tube viscosity method record, fusing point is 205 DEG C～245 DEG C.
Present invention also offers above-mentioned imidazole radicals anionic dye and can contaminate the preparation method of type modified copolyester, its It is characterised by, including:
Step a: p-phthalic acid and ethylene glycol are added in the first esterifying kettle, adds heat stabilizer and catalyst, Carry out esterification；
Step b: then, enters second esterification kettle by the material of esterification gained in step a, adds N-2-(3,5-dicarboxyphenyi) ethyl-N '-Methylimidazole. villaumite and 2-methyl isophthalic acid, 4-butanediol, carry out further ester Change reaction；
Step c: subsequently, enters polycondensation vessel by the material of esterification gained further in step b, contracts Poly-reaction；
Step d: discharging, pelletizing, be drying to obtain imidazole radicals anionic dye and can contaminate type modified copolyester；
Wherein, described p-phthalic acid, ethylene glycol, N-2-(3,5-dicarboxyphenyi) ethyl-N '-Methylimidazole. Villaumite and 2-methyl isophthalic acid, the mol ratio of 4-butanediol is 1: 1.2～2.5: 0.01～0.08: 0.03～0.25.
Preferably, the described esterification in step a, its reaction temperature is 230 DEG C～260 DEG C, its reaction Time is 2～4h.
Preferably, the described catalyst in step a is containing in Sb, Mn, Ca, Zn or Co compound One or more, it is 0.01%～0.08% that catalyst accounts for the percent of terephthalic acid monomers weight.
Preferably, the described heat stabilizer in step c is triphenyl phosphate or trimethyl phosphate, heat stabilizer The percent accounting for terephthalic acid monomers weight is 0.03%～0.07%.
Preferably, the further esterification in described step b, its reaction temperature is 230 DEG C～260 DEG C, Its response time is 1～3h.
Preferably, the described polycondensation reaction in step c, its reaction temperature is 260 DEG C～290 DEG C, vacuum Less than 30Pa, its response time is 2～4h.
Preferably, described the first esterifying kettle, second esterification kettle and polycondensation vessel constitute continuous polymerization device.
Present invention also offers above-mentioned imidazole radicals anionic dye and can contaminate the application process of type modified copolyester, its It is characterised by, including: above-mentioned imidazole radicals anionic dye can be contaminated type modified copolyester direct fabrics or section Chopped fiber or long filament are made in spinning；Wherein, described direct fabrics or the technological parameter of slice spinning be: spinning Extruder temperature is 260 DEG C～310 DEG C, and spinning speed is 800m/min～4500m/min, and draw roll temperature is 65 DEG C～190 DEG C, drafting multiple is 1.1～5.5 times.
The Nitrogen ion of the positively charged in the imidazole group easily sulfonate ion in anionic dye molecule is combined, Even if at normal temperatures, also can form firm ionic bond, and show hydrophobicity.Using imidazole radicals copolymerization list In the fiber of modified copolyester prepared by body, anionic dye molecule can be secured firmly to polyester fiber molecule On, and will not reveal in water.Therefore imidazole radicals anionic dye can contaminate type modified copolyester and have good the moon Ionic dyeing performance and dyestuff anti-leak performance.The most how to utilize commercialization raw material, use simple method system Standby exploitation imidazole radicals anionic dye can contaminate type modified copolyester and have great importance.
The anionic dye stainability of the present invention can come from the 3rd comonomer (N-2-(3, the 5-dicarboxyls of employing Phenyl) ethyl-N '-Methylimidazole. villaumite) and the 4th comonomer (2-methyl isophthalic acid, 4-butanediol).3rd copolymerization In monomer, on imidazole group, the nitrogen-atoms of positively charged can be combined closely rapidly with the sulfonate ion of anionic dye, And reduce the hydrophilic of anionic dye molecule, so that anionic dye molecule is tied with polyester fiber molecule in close Close, and anionic dye molecule is difficult to reveal.Meanwhile, the addition of the 4th comonomer result in macromolecular chain Irregularity, hinders copolyesters and forms regular and close lattice, and polymer crystallinity is low, molecular structure pine Dissipating, beneficially in dyeing course, anionic dye molecule is diffused into fibrous inside and is combined with dye radical.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention is the 3rd comonomer with N-2-(3,5-dicarboxyphenyi) ethyl-N '-Methylimidazole. villaumite, with 2-methyl isophthalic acid, 4-butanediol is the 4th comonomer, and having prepared a kind of novel imidazole base anionic dye can contaminate Type modified copolyester.The fiber of this copolyesters has good anionic dye stainability, can contaminate with normal temperature and pressure Color or boiling dyeing at normal pressure, dye-uptake is up to more than 90%, and dyestuff is difficult to reveal, and bright in colour, chromatograph is complete.Its Fiber can change two bath process with Pilus Caprae seu Ovis, silk blend with bathing dye, reduce environmental contaminants discharge.Do not terminate in This, its fibers at low temperature can contaminate, it is possible to post-treatment dyeing cost is greatly reduced.Above-mentioned copolyesters is with low cost, Convieniently synthesized, reaction controllability is good, and its fiber can be applicable to the fields such as clothing, home textile and industry.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum that the imidazole radicals anionic dye that embodiment 1 prepares can contaminate type modified copolyester.
Fig. 2 is the infrared spectrum that the imidazole radicals anionic dye that embodiment 2 prepares can contaminate type modified copolyester.
Fig. 3 is the infrared spectrum that the imidazole radicals anionic dye that embodiment 2 prepares can contaminate type modified copolyester.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate The present invention rather than restriction the scope of the present invention.In addition, it is to be understood that read the present invention lecture content it After, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within this equally Application appended claims limited range.
Embodiment 1
A kind of imidazole radicals anionic dye can contaminate type modified copolyester, and its structure is formula (I), its comonomer bag Include: mol ratio be 1: 1.6: 0.05: 0.07 p-phthalic acid, ethylene glycol, N-2-(3,5-dicarboxyphenyi) Ethyl-N '-Methylimidazole. villaumite and 2-methyl isophthalic acid, 4-butanediol.
Use described in continuous polymerization device (including: the first esterifying kettle, second esterification kettle and polycondensation vessel) synthesis Imidazole radicals anionic dye can contaminate type modified copolyester, and its preparation method is:
Step a: add in the first esterifying kettle by 500 grams of p-phthalic acids and 300 grams of ethylene glycol, adds 0.2 Gram triphenyl phosphate and 0.3 gram of antimony oxide, carry out esterification, and its reaction temperature is 250 DEG C, reaction Time is 3h；
Step b: then, enters second esterification kettle by the material of esterification gained in step a, adds quite In the 2-methyl isophthalic acid of the 7mol% of p-phthalic acid, 4-butanediol and be equivalent to the 5mol% of p-phthalic acid N-2-(3,5-dicarboxyphenyi) ethyl-N '-Methylimidazole. villaumite, further esterification, reaction temperature is 240 DEG C, the response time is 2h；
Step c: subsequently, enters polycondensation vessel by the material of esterification gained further in step b, contracts Poly-reaction, reaction temperature is 270 DEG C, and gradually decompression is until vacuum is less than 125Pa, reacts 3h；
Step d: discharging, pelletizing, be dried, obtain imidazole radicals anionic dye and can contaminate type modified copolyester.
It is 0.62 (by capillary tube viscosity method that imidazole radicals anionic dye can contaminate type modified copolyester pelletizing intrinsic viscosity Record), fusing point is 225 DEG C.Fig. 1 is that the imidazole radicals anionic dye that embodiment 1 prepares can contaminate type and changes The infrared spectrum of property copolyesters.
With dry sliced as raw material, melted high-speed spinning FDY, extruder temperature: 272 DEG C；Spinning speed: 4000m/min, spinning specification is 113dtex/72F, and heat-stretching roller 1 temperature is 85 DEG C, heat-stretching roller 2 temperature Being 135 DEG C, drafting multiple is 2.4 times.
Fibrous fracture intensity is 2.72cN/dtex, and elongation at break is 26%.At normal pressure and 90 DEG C, cloudy from The dye-uptake of sub-methyl orange is 90%.
Embodiment 2
A kind of imidazole radicals anionic dye can contaminate type modified copolyester, and its structure is formula (I), its comonomer bag Include: mol ratio be 1: 1.6: 0.06: 0.06 p-phthalic acid, ethylene glycol, N-2-(3,5-dicarboxyphenyi) Ethyl-N '-Methylimidazole. villaumite and 2-methyl isophthalic acid, 4-butanediol.
Use described in continuous polymerization device (including: the first esterifying kettle, second esterification kettle and polycondensation vessel) synthesis Imidazole radicals anionic dye can contaminate type modified copolyester, and its preparation method is:
Step a: add in the first esterifying kettle by 400 grams of p-phthalic acids and 240 grams of ethylene glycol, adds 0.15 Gram triphenyl phosphate and 0.2 gram of antimony oxide, carry out esterification, and its reaction temperature is 255 DEG C, reaction Time is 3h；
Step b: then, enters second esterification kettle by the material of esterification gained in step a, adds quite In the 2-methyl isophthalic acid of the 6mol% of p-phthalic acid, 4-butanediol and be equivalent to the 6mol% of p-phthalic acid N-2-(3,5-dicarboxyphenyi) ethyl-N '-Methylimidazole. villaumite, further esterification, reaction temperature is 250 DEG C, the response time is 2h；
Step c: subsequently, enters polycondensation vessel by the material of esterification gained further in step b, contracts Poly-reaction, reaction temperature is 280 DEG C, and gradually decompression is until vacuum is less than 130Pa, reacts 3.5h；
Step d: discharging, pelletizing, be dried, obtain imidazole radicals anionic dye and can contaminate type modified copolyester.
It is 0.56 (by capillary tube viscosity method that imidazole radicals anionic dye can contaminate type modified copolyester pelletizing intrinsic viscosity Record), fusing point is 230 DEG C.Fig. 2 is that the imidazole radicals anionic dye that embodiment 2 prepares can contaminate type and changes The infrared spectrum of property copolyesters.
With dry sliced as raw material, melted high-speed spinning FDY, extruder temperature: 281 DEG C；Spinning speed: 4000m/min, spinning specification is 125dtex/72F, and heat-stretching roller 1 temperature is 90 DEG C, heat-stretching roller 2 temperature Degree is 125 DEG C, and drafting multiple is 2.3 times.
Fibrous fracture intensity is 2.61cN/dtex, and elongation at break is 28%.At normal pressure and 25 DEG C, cloudy from The dye-uptake of sub-methyl orange is 91%.
Embodiment 3
A kind of imidazole radicals anionic dye can contaminate type modified copolyester, and its structure is formula (I), its comonomer bag Include: mol ratio be 1: 1.78: 0.045: 0.08 p-phthalic acid, ethylene glycol, N-2-(3,5-dicarboxyl benzene Base) ethyl-N '-Methylimidazole. villaumite and 2-methyl isophthalic acid, 4-butanediol.
Use described in continuous polymerization device (including: the first esterifying kettle, second esterification kettle and polycondensation vessel) synthesis Imidazole radicals anionic dye can contaminate type modified copolyester, and its preparation method is:
Step a: add in the first esterifying kettle by 600 grams of p-phthalic acids and 400 grams of ethylene glycol, adds 0.3 Gram triphenyl phosphate and 0.3 gram of antimony oxide, carry out esterification, and its reaction temperature is 252 DEG C, reaction Time is 2.5h；
Step b: then, enters second esterification kettle by the material of esterification gained in step a, adds quite In the 2-methyl isophthalic acid of the 8mol% of p-phthalic acid, 4-butanediol and be equivalent to the 4.5mol% of p-phthalic acid N-2-(3,5-dicarboxyphenyi) ethyl-N '-Methylimidazole. villaumite, further esterification, reaction temperature is 250 DEG C, the response time is 2.5h；
Step c: subsequently, enters polycondensation vessel by the material of esterification gained further in step b, contracts Poly-reaction, reaction temperature is 271 DEG C, and gradually decompression is until vacuum is less than 120Pa, reacts 3.5h；
Step d: discharging, pelletizing, be dried, obtain imidazole radicals anionic dye and can contaminate type modified copolyester.
It is 0.64 (by capillary tube viscosity method that imidazole radicals anionic dye can contaminate type modified copolyester pelletizing intrinsic viscosity Record), fusing point is 220 DEG C.Fig. 3 is that the imidazole radicals anionic dye that embodiment 3 prepares can contaminate type and changes The infrared spectrum of property copolyesters.
With dry sliced as raw material, melted high-speed spinning FDY, extruder temperature: 280 DEG C；Spinning speed: 4000m/min, spinning specification is 110dtex/72F, and heat-stretching roller 1 temperature is 87 DEG C, heat-stretching roller 2 temperature Being 132 DEG C, drafting multiple is 2.5 times.
Fibrous fracture intensity is 2.66cN/dtex, and elongation at break is 27%.At normal pressure and 95 DEG C, cloudy from The dye-uptake of sub-methyl orange is 91.5%.

Claims (10)

1. an imidazole radicals anionic dye can contaminate type modified copolyester, it is characterised in that its comonomer bag Include: mol ratio is 1: 1.2～2.5: 0.01～the p-phthalic acid of 0.08: 0.03～0.25, ethylene glycol, N-2-(3,5-bis- Carboxyl phenyl) ethyl-N '-Methylimidazole. villaumite and 2-methyl isophthalic acid, 4-butanediol.
2. imidazole radicals anionic dye as claimed in claim 1 can contaminate type modified copolyester, it is characterised in that Described imidazole radicals anionic dye can contaminate the structural formula of type modified copolyester:
Terephthalic acid units, ethylene glycol unit, N-2-(3,5-dicarboxyphenyi) ethyl-N '-methyl miaow in structural formula Azoles villaumite unit and 2-methyl isophthalic acid, the mol ratio of 4-butanediol unit is X: m: Y: n.
3. imidazole radicals anionic dye as claimed in claim 1 can contaminate type modified copolyester, it is characterised in that Described imidazole radicals anionic dye can contaminate type modified copolyester intrinsic viscosity be 0.3～0.7, by capillary tube Viscosity method records, and fusing point is 205 DEG C～245 DEG C.
4. the imidazole radicals anionic dye according to any one of claim 1-3 can contaminate the system of type modified copolyester Preparation Method, it is characterised in that including:
Step a: p-phthalic acid and ethylene glycol are added in the first esterifying kettle, adds heat stabilizer and catalyst, Carry out esterification；
Step b: then, enters second esterification kettle by the material of esterification gained in step a, adds N-2-(3,5- Dicarboxyphenyi) ethyl-N '-Methylimidazole. villaumite and 2-methyl isophthalic acid, 4-butanediol, carry out further esterification；
Step c: subsequently, enters polycondensation vessel by the material of esterification gained further in step b, contracts Poly-reaction；
Step d: discharging, pelletizing, be drying to obtain imidazole radicals anionic dye and can contaminate type modified copolyester；
Wherein, described p-phthalic acid, ethylene glycol, N-2-(3,5-dicarboxyphenyi) ethyl-N '-Methylimidazole. Villaumite and 2-methyl isophthalic acid, the mol ratio of 4-butanediol is 1: 1.2～2.5: 0.01～0.08: 0.03～0.25.
5. imidazole radicals anionic dye as claimed in claim 4 can contaminate the preparation method of type modified copolyester, It is characterized in that, the described esterification in step a, its reaction temperature is 230 DEG C～260 DEG C, its reaction Time is 2～4h.
6. imidazole radicals anionic dye as claimed in claim 4 can contaminate the preparation method of type modified copolyester, It is characterized in that, the described catalyst in step a is containing in Sb, Mn, Ca, Zn or Co compound One or more, it is 0.01%～0.08% that catalyst accounts for the percent of terephthalic acid monomers weight.
7. imidazole radicals anionic dye as claimed in claim 4 can contaminate the preparation method of type modified copolyester, It is characterized in that, the described heat stabilizer in step c is triphenyl phosphate or trimethyl phosphate, heat stabilizer The percent accounting for terephthalic acid monomers weight is 0.03%～0.07%.
8. imidazole radicals anionic dye as claimed in claim 4 can contaminate the preparation method of type modified copolyester, It is characterized in that, the further esterification in described step b, its reaction temperature is 230 DEG C～260 DEG C, Its response time is 1～3h.
9. imidazole radicals anionic dye as claimed in claim 4 can contaminate the preparation method of type modified copolyester, It is characterized in that, the described polycondensation reaction in step c, its reaction temperature is 260 DEG C～290 DEG C, vacuum Less than 30Pa, its response time is 2～4h.
10. the imidazole radicals anionic dye according to any one of claim 1-3 can contaminate type modified copolyester Application process, it is characterised in that including: above-mentioned imidazole radicals anionic dye can be contaminated type modified copolyester Chopped fiber or long filament are made in direct fabrics or slice spinning；Wherein, described direct fabrics or the work of slice spinning Skill parameter is: spinning screw temperature is 260 DEG C～310 DEG C, and spinning speed is 800m/min～4500m/min, leads Stretching roll temperature is 65 DEG C～190 DEG C, and drafting multiple is 1.1～5.5 times.
CN201610334450.3A 2016-05-19 2016-05-19 A kind of imidazole radicals anionic dye can contaminate type modified copolyester and its preparation and application Active CN106008941B (en)

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CN112176446A (en) * 2020-10-16 2021-01-05 邓颖菁 Antibacterial polyester fiber and preparation method thereof

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CN108676173A (en) * 2018-05-18 2018-10-19 东华大学 Using ionic bond as poly ion liquid of skeleton and preparation method thereof
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CN112176446A (en) * 2020-10-16 2021-01-05 邓颖菁 Antibacterial polyester fiber and preparation method thereof

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