CN107723826B - Method for continuously producing colored polyimide fibers by two-step method - Google Patents

Method for continuously producing colored polyimide fibers by two-step method Download PDF

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CN107723826B
CN107723826B CN201711067694.0A CN201711067694A CN107723826B CN 107723826 B CN107723826 B CN 107723826B CN 201711067694 A CN201711067694 A CN 201711067694A CN 107723826 B CN107723826 B CN 107723826B
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colored polyimide
polyimide
continuously producing
dyeing
drying
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CN107723826A (en
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张清华
甘锋
李琇廷
董杰
赵昕
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Donghua University
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    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • 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
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B15/00—Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours
    • 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
    • D06P1/44—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 using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—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 using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
    • 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
    • D06P3/02—Material containing basic nitrogen

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Coloring (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention relates to a method for continuously producing colored polyimide fibers by a two-step method, wherein the preparation process is that N is2And spinning the polyamic acid solution under the environment, forming, washing, dyeing, winding, pre-drying, and carrying out thermal cyclization/curing to obtain the colored polyimide fiber. The method is simple and effective, is convenient for industrial production, effectively solves the problem of surface inertia of polyimide, and has bright application prospect; the coating coloring adhesive has good adhesion with the polyamic acid and the polyimide body, and the curing temperature is low, so that the pigment structure is not damaged, and the polyimide fiber with various colors can be simply prepared; the prepared colored polyimide fiber does not reduce the heat resistance, solvent resistance, dielectric property and the like of the polyimide body, and does not reduce the application value of the colored polyimide fiber in a plurality of fields such as electronics, fire prevention and the like.

Description

Method for continuously producing colored polyimide fibers by two-step method
Technical Field
The invention belongs to the field of polyimide spinning, dyeing and finishing processing, and particularly relates to a method for continuously producing colored polyimide fibers by a two-step method.
Background
The polyimide fiber is a typical high-performance fiber, and based on the intrinsic property of the fiber, the polyimide fabric has the characteristics of excellent heat resistance, excellent mechanical property, solvent resistance, irradiation resistance, good dielectric property and the like, has excellent comprehensive performance, and can be used in the technical fields of composite materials, high-temperature filtration, military aerospace, fire fighting and the like.
At present, polyimide fabrics, such as clothes, non-woven fabrics and the like, have been expanded to certain scale in the fields of labor protection, fire protection, body armor and the like, are limited by factors such as single color of polyimide and the like, and the application range of the polyimide fabrics is still in a relatively narrow level. Polyimide fibers are mostly golden yellow, and some light yellow fiber varieties can be obtained through structural design, but the polyimide fibers are limited by factors such as a conjugate structure, electron cloud density and the like, so that the polyimide fibers with diversified colors are difficult to obtain through structural design. With the market demand for polyimide fabrics with diversified colors, the research on the dyeing performance of polyimide is necessary. At present, relatively few reports of polyimide fiber and fabric dyeing exist, and the existing research mainly includes that polyimide is pretreated, such as alkali etching and plasma treatment, so that affinity of the polyimide to a dye is improved, and then dyeing property of the polyimide is improved, for example, patents such as CN104532622B and CN103541214B adopt a method of alkali pretreatment of the fiber, and then the fiber is dyed. However, since polyimide has a certain hydrolyzability under alkaline conditions, the mechanical properties and heat resistance of the fiber are lost, and it is difficult to obtain a darker color by such a method, and the method has a narrow dyeing color spectrum, and is difficult to obtain white and other light-colored lights. Other methods, such as plasma etching, redox etching, are also within this category, all of which have similar disadvantages.
In addition to surface modification, pigment dyeing is also a common dyeing method. The coating dyeing is to transfer the colored coating to the fabric by padding and color fixing methods, and has the characteristics of less pollution, simple process and the like, but the coating has no affinity to polyimide fibers and poor adhesion with the fibers, and compared with the polyamide acid fibers, the polyamide acid fibers contain active groups and have stronger bonding force with the coating and the pigment.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for continuously producing and preparing colored polyimide fibers by a two-step method, the method is simple and effective, the problem of inertia of the polyimide surface is solved, the colored polyimide fibers can be prepared, and the method has wide application prospects in various fields such as electronics, fire prevention and the like.
The invention relates to a method for continuously producing colored polyimide fibers by a two-step method, which comprises the following steps:
in N2Spinning a polyamic acid solution under the environment, forming, washing, dyeing, winding, pre-drying, and performing thermal cyclization/solidification to obtain a colored polyimide fiber; wherein the dyeing is carried out in a dyeing solution comprising: binder, pigment and solvent.
The solvent of the polyamic acid solution is DMAc; the spinning is dry-jet wet spinning or wet spinning.
And (3) after washing, drying by hot air at the temperature of 60-80 ℃ to remove residual moisture on the surface.
The adhesive is transparent polyimide resin, the solid content is 1-40%, and the structural formula is as follows:
Figure BDA0001456106230000021
wherein n is 1 to 30, Ar1Is a diamine skeleton structure, Ar2Is a dianhydride skeleton structure, Ar3Is a capping agent, a monoanhydride or a monoamine.
The transparent polyimide resin is low-temperature curing resin, and the problems of colored light and structural damage of the pigment at high temperature are solved.
Ar is1The structural formula of (A) is:
Figure BDA0001456106230000022
one kind of (1).
Ar is2The structural formula of (A) is:
Figure BDA0001456106230000023
Figure BDA0001456106230000024
one kind of (1).
Ar is3The structural formula of (A) is:
Figure BDA0001456106230000031
one kind of (1).
The mass fraction of the pigment is 0.1-25%; the pigment is organic pigment or inorganic pigment; the solvent is tetrahydrofuran, ethanol, DMAc, NMP, DMF, DMSO or chloroform.
The organic pigment is one or more of azo, phthalocyanine, dioxazine, quinacridone and thioindigo.
The inorganic pigment is one or more of metal oxide, metal salt and carbon black.
The metal oxide is TiO2Or ZnO; the metal salt being Zn3(PO4)2。
The dyeing temperature is 10-100 ℃; and drying by hot air at 60-100 ℃ after dyeing.
The pre-drying is carried out in an oven, the pre-drying temperature is 40-80 ℃, and the pre-drying time is 2-12 hours.
The thermal cyclization/solidification comprises the following specific steps: keeping the temperature constant for 1-2h at the temperature of 100-120 ℃, and keeping the temperature constant for 1-2h at the temperature of 260-310 ℃.
The method for continuously producing the colored polyimide fiber by the two-step method adopts the spinning technology of the two-step method, namely, the polyamic acid solution is used for spinning to prepare the polyamic acid precursor fiber, and then the polyamic acid fiber is imidized to prepare the polyimide fiber. The polyamic acid nascent fiber is prepared by the two-step spinning method, the polyamic acid nascent fiber is colored by a dyeing bath prepared from polyimide resin and pigment, and the polyamic acid has a multi-carboxyl functional group structure, so that the polyamic acid nascent fiber has strong adsorption capacity on the resin and the pigment, the defect that the adsorption capacity of inert polyimide fiber on the pigment is poor is overcome, and in the subsequent heat treatment process, the cyclization reaction of the polyamic acid coexists with the crosslinking reaction of the attached polyimide resin, and the polyamic acid nascent fiber can be continuously produced. Therefore, by combining the polyamic acid-polyimide two-step spinning technology and the paint dyeing technology, the polyimide fiber with various colors is prepared by continuous production, and the defect that the polyimide fiber has poor affinity with pigments and adhesives is overcome.
Advantageous effects
(1) The method is simple and effective, is convenient for industrial production, effectively solves the problem of surface inertia of polyimide, and has bright application prospect;
(2) the coating coloring adhesive has good adhesion with polyamic acid and polyimide body, and low curing temperature, does not damage the pigment structure, and can simply prepare the polyimide fiber with various colors;
(3) the colored polyimide fiber prepared by the invention does not reduce the heat resistance, solvent resistance, dielectric property and the like of the polyimide body and does not reduce the application value of the colored polyimide fiber in a plurality of fields such as electronics, fire prevention and the like.
Drawings
FIG. 1 is a process flow diagram of a colored polyimide fiber of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
Adopting a two-step method dry-jet wet spinning technology, taking a polyamic acid solution (solvent is DMAc) with a solid content of 15% of pyromellitic dianhydride/4, 4' -diaminodiphenyl ether structure as a spinning stock solution, forming by a coagulating bath, wherein the coagulating bath is ethanol/water (1/1, v/v), washing by water, drying by hot air at 60 ℃, dyeing, and the dyeing solution comprises the following components: a 5% solids polyimide resin having the formula:
Figure BDA0001456106230000041
the pigment is phthalocyanine blue accounting for 2 percent of the total mass of the solution, the solvent is tetrahydrofuran, and the temperature of the dyeing solution is 30 ℃; and (3) drying by hot air after dyeing, wherein the temperature of the hot air is 80 ℃, then pre-drying for 6h under the condition of 50 ℃, cyclizing for 1h at 110 ℃, and cyclizing for 1h at 280 ℃ to obtain the blue polyimide fiber. The obtained blue polyimide fiber has the thermal decomposition temperature higher than 490 ℃ and the thermal expansion coefficient lower than 38ppm/k (the thermal expansion coefficient of uncolored fiber is 57ppm/k), and can be used for preparing outdoor jacket, cabin interior decoration, refractory materials and high-temperature resistant structural members.
Example 2
Adopting a two-step method dry-jet wet spinning technology, taking a polyamic acid solution (solvent is DMAc) with a solid content of 13.5 percent biphenyl benzene dianhydride/p-phenylenediamine structure as a spinning stock solution, forming by a coagulating bath, washing by water, drying by hot air at 70 ℃, dyeing, and using a dyeing solution as follows: a polyimide resin having a solid content of 3%, the structural formula being as follows:
Figure BDA0001456106230000042
pigment is Cosmetic Pink RC01 (pigment red 181) accounting for 1 percent of the total mass of the solution, solvent is DMAc, and the temperature of the dyeing solution is 80 ℃; and (3) drying by hot air after dyeing, wherein the temperature of the hot air is 80 ℃, then pre-drying for 8h at the temperature of 50 ℃, cyclizing for 1h at 110 ℃, and cyclizing for 1h at 310 ℃ to obtain the orange polyimide fiber. The obtained orange polyimide fiber has the thermal decomposition temperature higher than 495 ℃ (the thermal decomposition temperature of uncolored fiber is 510 ℃), the thermal stability is slightly reduced, but the thermal stability is still at a higher level and is far higher than that of acrylic resin paint, and the orange polyimide fiber can be used for preparing fire-fighting clothes.

Claims (9)

1. A method for continuously producing colored polyimide fibers by a two-step method comprises the following specific steps:
in N2Spinning a polyamic acid solution under the environment, forming, washing, dyeing, winding, pre-drying, and performing thermal cyclization/solidification to obtain a colored polyimide fiber; wherein the dyeing is carried out in a dyeing solution comprising: binders, pigments and solvents; the adhesive is transparent polyimide resin, the solid content is 1-40%, and the structural formula is as follows:
Figure FDA0002126843520000011
wherein n is 1 to 30, Ar1Is a diamine skeleton structure, Ar2Is a dianhydride skeleton structure, Ar3Is an end-capping agent.
2. The continuous process for producing colored polyimide fibers in accordance with claim 1, wherein the polyamic acid solution is prepared in the solvent of DMAc; the spinning is dry-jet wet spinning or wet spinning; washing with water, and drying with hot air at 60-80 ℃.
3. The method for continuously producing colored polyimide fibers in two steps according to claim 1, wherein Ar is1The structural formula of (A) is:
Figure FDA0002126843520000012
Figure FDA0002126843520000013
one kind of (1).
4. The method for continuously producing colored polyimide fibers in two steps according to claim 1, wherein Ar is2The structural formula of (A) is:
Figure FDA0002126843520000014
one kind of (1).
5. The method for continuously producing colored polyimide fibers in two steps according to claim 1, wherein Ar is3The structural formula of (A) is:
Figure FDA0002126843520000022
one kind of (1).
6. The method for continuously producing the colored polyimide fiber by the two-step method according to claim 1, wherein the mass fraction of the pigment is 0.1-25%; the pigment is organic pigment or inorganic pigment; the solvent is tetrahydrofuran, ethanol, DMAc, NMP, DMF, DMSO or chloroform.
7. The method for continuously producing colored polyimide fibers by a two-step process according to claim 6, wherein the organic pigment is one or more of azo, phthalocyanine, dioxazine, quinacridone and thioindigo; the inorganic pigment is one or more of metal oxide, metal salt and carbon black.
8. The method for continuously producing colored polyimide fibers by a two-step method according to claim 1, wherein the dyeing temperature is 10-100 ℃; drying with hot air at 60-100 ℃ after dyeing; the pre-drying is carried out in an oven, the pre-drying temperature is 40-80 ℃, and the pre-drying time is 2-12 hours.
9. The method for continuously producing colored polyimide fibers in two steps according to claim 1, wherein the thermal cyclization/curing is carried out by the following steps: keeping the temperature constant for 1-2h at the temperature of 100-120 ℃, and keeping the temperature constant for 1-2h at the temperature of 260-310 ℃.
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Citations (5)

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CN102587217A (en) * 2012-03-28 2012-07-18 天津工业大学 Preparation method of polyimide fiber insulating paper
CN105734710A (en) * 2016-05-06 2016-07-06 江苏奥神新材料股份有限公司 Preparation method of colored polyimide fibers
CN105780177A (en) * 2016-03-11 2016-07-20 江苏奥神新材料股份有限公司 Production method of polyimide color silk
CN106930120A (en) * 2017-03-16 2017-07-07 江苏工程职业技术学院 A kind of colouring method of polyimide fiber
CN107130445A (en) * 2017-05-19 2017-09-05 江苏先诺新材料科技有限公司 A kind of method for improving dyeing polyimide fiber mechanical property

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JP5806567B2 (en) * 2011-09-26 2015-11-10 株式会社クラレ Polyimide fiber and fiber structure using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102587217A (en) * 2012-03-28 2012-07-18 天津工业大学 Preparation method of polyimide fiber insulating paper
CN105780177A (en) * 2016-03-11 2016-07-20 江苏奥神新材料股份有限公司 Production method of polyimide color silk
CN105734710A (en) * 2016-05-06 2016-07-06 江苏奥神新材料股份有限公司 Preparation method of colored polyimide fibers
CN106930120A (en) * 2017-03-16 2017-07-07 江苏工程职业技术学院 A kind of colouring method of polyimide fiber
CN107130445A (en) * 2017-05-19 2017-09-05 江苏先诺新材料科技有限公司 A kind of method for improving dyeing polyimide fiber mechanical property

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