CN104593898B

CN104593898B - The preparation method of coloring para-aramid fiber before a kind of

Info

Publication number: CN104593898B
Application number: CN201410825134.7A
Authority: CN
Inventors: 唐凯; 孙茂健; 马千里; 于宏广
Original assignee: YANTAI TAYHO ADVANCED MATERIALS CO Ltd
Current assignee: Taihe New Material Group Co ltd
Priority date: 2014-12-27
Filing date: 2014-12-27
Publication date: 2016-08-17
Anticipated expiration: 2034-12-27
Also published as: CN104593898A

Abstract

Before a kind of, the preparation method of coloring para-aramid fiber, comprises step: spin the preparation of front coloring liquid: coloring pigment and sulphuric acid are together added and be ground in grinding, dispersion machine and disperse；The preparation of spinning polymer: spin spinning polymer according to what existing technology prepared para-aramid fiber；The preparation of spinning solution: front coloring liquid spinning polymer will be spun and be sufficiently mixed by double screw extruder and dissolve；Spinning solution carries out melting, deaeration, dry-jet wet-spinning spinning, then through solidification, washing, alkali cleaning, drying, the most post-treated after obtain before coloring para-aramid fiber.Compared with prior art, increasing form and aspect saturation, color is more gorgeous；The coloring pigment of the most panchromatic system tone can be obtained, enrich the range of application of para-aramid fiber；Color fastness is high；The loss of para-aramid fiber physical characteristic is minimum.

Description

The preparation method of coloring para-aramid fiber before a kind of

Technical field

The present invention relates to aramid fiber preparation method field, particularly relate to the preparation of a kind of front coloring para-aramid fiber Method.

Background technology

P-aramid fiber has light weight, high-strength and high-modulus, the characteristic such as high temperature resistant and fire-retardant, is mainly used in flak jackets, the helmet, aviation The aspects such as space material, tyre framework material, reinforcing material.Along with para-aramid fiber ex hoc genus anne and downstream product are in the world The expansion of chemical fibre reinforcing material range of application, on market, research and development have also been deepened in the coloring to para-aramid fiber, to meet Product appearance needs.But owing to p-aramid fiber shows high orientation, molecular structure is tight, and degree of crystallinity is high, in prior art Mostly take poststaining mode, on the basis of traditional dyeing and finishing, change dyeing condition, as improved staining reagent by acid-alkali treatment Ability, nonetheless, Color still exists and is off color irregular, and color fastness is low, and dye bath ratio requirement is accurate, seriously polluted Etc. problem, and this dyeing directly affects the physical characteristic of fiber so that it strengthens characteristic and declines relatively big, for picture The such high-strength high-modulus fibre of p-aramid fiber, dyeing is loosely and physical characteristic own is lowered, the restriction being applied to beyond doubt, There is hidden danger simultaneously.

The patent of E.I.Du Pont Company's Publication No. CN1031736A discloses dye technology scheme before one, takes pigment and gathers Compound is added simultaneously to the mode in oleum, but still suffers from certain defect: owing to pigment and polymer are added simultaneously to In oleum, easily cause pigment dispersion irregular, cause product colour developing deviation, but also cause the fluctuation of stock solution proportioning, impact The quality of finished fiber.

The patent of Japan Tokai Senko K. K. Publication No. CN 103459710A, after its technical scheme is simulation Dyeing technique, and complex procedures, pollute relatively big, and product of dying still there are the defect of aforementioned after stain.

The applicant uses multi-walled carbon nano-tubes to carry out contaminating black life in previous Publication No. CN102839444A patent Produce, CNT specification etc. is defined becoming antenatal, and when same production line changes the process of colour system, due to carbon The characteristic of nanotube, cleans up more for waste stock solution, and CNT can only contaminate black processed simultaneously, for other colour systems not It is suitable for.

Summary of the invention

It is an object of the invention to the deficiency for existing p-aramid fiber staining technique, it is provided that before a kind of panchromatic system, colour para-position The method of aramid fiber.Present invention provide the technical scheme that

The preparation method of coloring para-aramid fiber before a kind of, comprises step:

A) preparation of front coloring liquid is spun: coloring pigment and sulphuric acid are together added and grinding, dispersion machine are ground and divide Dissipate；

B) preparation of spinning polymer: prepare the spinning polymer of para-aramid fiber according to existing technology；

C) preparation of spinning solution: the spinning polymer spinning front coloring liquid and step b) of step a) is squeezed by twin screw Go out machine be sufficiently mixed and dissolve；

D) carry out the spinning solution of step c) melting, deaeration, dry-jet wet-spinning spinning, then through solidification, washing, alkali cleaning, baking Dry, the most post-treated after obtain before coloring para-aramid fiber.

Further, described coloring pigment include phthalein green grass or young crops class, Anthraquinones, be, phenyl amines, azo, diketone pyrroles And one in pyroles, bisazo class, isoindoline ketone, quinacridine ketone, diazines, pucherite type disperse dye or Several.

Further, the concentration of described sulphuric acid is 95%-105%.

Further, the spinning solution that prepared by step c) spins front coloring liquid and accounts for 0.05%-6%.

Further, in the spinning solution that prepared by step c), stereoplasm content is at 18.5%-21%.

Compared with prior art, coloring pigment is passed through grinder or sand mill, ball mill in early stage by the present invention, disperses Front coloring liquid is spun in the dissolution/dispersion formation that dispersion machine or mulser etc. are allowed to the most rapidly and sufficiently, accelerates pigment Homodisperse degree, shortens the holding time in oleum, also makes more coloring pigment can join para-position The preparation process of aramid fiber, increases the form and aspect saturation of para-aramid fiber, makes para-aramid fiber color more gorgeous；And Carry out mixing colorant match by the coloring pigment of two or more variety classes and form and aspect, the most panchromatic system tone can be obtained Coloring pigment, enrich the range of application of para-aramid fiber；Simultaneously because coloring pigment is and spinning solution depth integration, The para-aramid fiber made is from outward appearance to inner essence consistent, thus color fastness is high；And owing to coloring pigment is and the spinning solution degree of depth Merge and make the loss of para-aramid fiber physical characteristic minimum.

Accompanying drawing explanation

The process chart of Fig. 1: the present invention.

Detailed description of the invention

In the para-aramid fiber that following instance is produced:

Prepared by spinning polymer: added the p-phenylenediamine under solubilising salt environment and paraphthaloyl chloride two-step method low temperature by NMP Polycondensation produces and obtains, and inherent character viscosity is at 5.5-8dL/g, and outward appearance is yellow powder granule.

Spin the preparation of front coloring liquid: to use pigment be phthalein green grass or young crops class, Anthraquinones, be, phenyl amines, azo, diketone pyrroles And it is a kind of in pyroles, bisazo class, isoindoline ketone, quinacridine ketone, diazine, pucherite class, other disperse dyes Or several, according to the color that obtains of plan, select suitable pigment split to obtain coloring pigment, by coloring pigment and 95%-105% sulfur Acid together adds in grinding distribution machine and is ground and emulsifying.

The preparation of spinning solution: carry out being sufficiently mixed and dissolve by twin screw and above-mentioned spin front coloring liquid and spinning poly Compound；Spinning solution spins front coloring liquid and accounts for 0.05%-6%；Stereoplasm content is at 18.5%-21%.

The two-step method spinning that spinning process employing is the most ripe, i.e. spinning solution store and put into and carry out dissolving, melting Melt, stretch, solidify, post processing, the step such as thermal finalization processing.Washing neutralizes alkali concn 0.01%-1.5%, and setting temperature is generally Less than 200 degree, spinning speed 200-400 rice per minute, (instron3343 high-strength and high-modulus fixture is examined to produce para-aramid fiber intensity Survey) in more than 19cn/dtex, modulus 80-120GPa.

Through detecting, the testing result of embodiment 1-4 such as following table:

The method have the characteristics that pigment increases grinder and grinds before using, improve its dissolution velocity in sulfuric acid solvent And effect, increase dispersion machine dispersion steps and uniform for quantitative coloring pigment rapid dispersion is reached designated color pair in sulfuric acid solvent Answer concentration to spin front coloring liquid with obtain being suitable for, by advance pigment being selected and polish, in the short time, can configure out Gao Pin Matter spin front coloring liquid, the color silk of desired color can be produced through fine setting.

The feature of the present invention also resides in use double screw extruder makes the two uniformly mixing, the degree of depth dissolve.The method operates Simplicity, and there is no any relatively large deviation that can cause fluctuation, the fiber produced is post-treated, one-step shaping, color even, color Fastness is high, and physical property strengths and precursor comparision of production difference are minimum.

And traditional poststaining technique, acid-alkali treatment is many, and ratio requirement is accurate, and the relatively front coloring of color fastness is low, physical property Can reduce relatively big, and this technique reduces power consumption and discharge of wastewater, cost-effective, the physical characteristic of this high-strength high-modulus fibre is affected Less, it is the process invention of the improvement color silk manufacture of energy-conserving and environment-protective.

Claims

1. colour the preparation method of para-aramid fiber before one kind, it is characterised in that: comprise step:

A) preparation of front coloring liquid is spun: coloring pigment and sulphuric acid are together added and grinding, dispersion machine are ground and disperse；

B) preparation of spinning polymer: added the p-phenylenediamine under solubilising salt environment and paraphthaloyl chloride two-step method low temperature by NMP Polycondensation produces the spinning polymer obtaining para-aramid fiber；

C) preparation of spinning solution: the spinning polymer spinning front coloring liquid and step b) of step a) is passed through double screw extruder It is sufficiently mixed and dissolves；

D) carry out the spinning solution of step c) melting, deaeration, dry-jet wet-spinning spinning, then through solidification, washing, alkali cleaning, drying, By coloring para-aramid fiber before obtaining after post processing.

The preparation method of a kind of front coloring para-aramid fiber the most according to claim 1, it is characterised in that: described Color pigment include phthalein green grass or young crops class, Anthraquinones, be, phenyl amines, azo, diketopyrrolo-pyrrole class, bisazo class, isoindoline One or more in ketone, quinacridine ketone, diazines, pucherite type disperse dye.

The preparation method of a kind of front coloring para-aramid fiber the most according to claim 1, it is characterised in that: described sulphuric acid Concentration be 95%-105%.

The preparation method of a kind of front coloring para-aramid fiber the most according to claim 1, it is characterised in that: step c) The spinning solution of preparation spins front coloring liquid and accounts for 0.05%-6%.

The preparation method of a kind of front coloring para-aramid fiber the most according to claim 1, it is characterised in that: step c) In the spinning solution of preparation, stereoplasm content is at 18.5%-21%.