CN105133378A - Dyeing carrier for dyeing polyimide fiber product by virtue of disperse dyes - Google Patents

Abstract

The invention relates to a dyeing carrier for dyeing a polyimide fiber product by virtue of disperse dyes, and belongs to the technical field of dyeing. The dyeing carrier is convenient, effective, safe, ecological, environment-friendly and high in boiling point and applicable to high-temperature high-pressure dyeing, can promote the swelling of polyimide fibers, increase the dissolved load of the dyes, increase the dyeing rate of the dyes, has a function of promoting the dyeing of the polyimide fibers so as to obtain a deep color, can realize the high-temperature high-pressure dyeing of the polyimide, is high in color yield and excellent in dyeing fastness, conforms to the national standard, and facilitates the implementation of industrialization of the polyimide dyeing.

Description

A kind of polyimide fiber goods disperse dyeing dyeing accelerant

Technical field

The present invention relates to a kind of polyimide fiber goods disperse dyeing dyeing accelerant, belong to dyeing and finishing technique field.

Background technology

Polyimides (PI) refers to the class high-performance polymer containing imide ring on main chain, and its molecular structural formula is as follows:

Fiber is natural yellowish-brown, has good thermo oxidative stability, and excellent mechanical performance, radiation resistance and insulating properties, Application Areas is very extensive.PI fiber has the characteristics such as excellent high temperature resistant, radiation hardness and high-strength and high-modulus, has good integrated application, its limited oxygen index > 38%, have the characteristic of not melting compared with aramid fiber, polyphenylene sulfide fibre etc., and from fire from putting out; High-low temperature resistant, can stablize use in high and low temperature environment; Thermal protective performance is excellent; Low temperature thermal property is excellent; Chemical-resistance is excellent.Can be used for developing various protective clothes, comprise fire-entry suit, insulated cold wear, and the multiple fire resistant polyimide fiber and its products such as fire resistant polyimide fiber filter cotton, fire resistant polyimide fiber high temperature filter felt, fire resistant polyimide fiber high temperature filter cotton, urgent in Application Areas demands such as Aero-Space, environmental protection, fire prevention.

Polyimide fiber is as a kind of important high-performance fiber.Its resistance to elevated temperatures is remarkable, is one of organic synthetic fibers that current serviceability temperature is the highest, can uses continuously, can not produce mechanical degradation phenomenon under 260 DEG C of conditions, vitrification point up to 376 DEG C, heat decomposition temperature 600 DEG C.For the fiber that vitrification point is high, the most frequently used dyestuff is DISPERSE DYES, and it is water-soluble little, in dye liquor by be dissolved into molecule with dispersity on contaminate and go to fiber.The disperse dyeing method of normal employing is high-temperature and high pressure dyeing process, and easy to operate, Color is good.But because the supramolecular structure stereospecificity of polyimides is good, vitrification point is high, under conventional high temperature high pressure dyeing condition, dyeing temperature (130 DEG C) is well below the vitrification point of polyimides, and dye molecule is difficult to enter on fibrous inside and contaminates fiber.

At present, have been reported employing and first modification or alkali treatment are carried out to polyimide fiber, and then adopt high-temperature and high pressure dyeing process to dye in conjunction with carrier dyeing process.The method needs to carry out complicated preliminary treatment to polyimide fiber, and technique is loaded down with trivial details, add dyeing cost, add waste water handling problem, and industrial applications difficulty.

Summary of the invention

In order to overcome the problems referred to above, the invention provides a kind of dyeing accelerant, in high-temperature pressure dyeing process, add the glass transition temperature that this dyeing accelerant effectively can reduce the high fibrous material of vitrification point, improve DISPERSE DYES to the dyeing rate of fibrous material and dye-uptake, be particularly useful for the dyeing of polyimide fiber.Dyeing accelerant of the present invention, affinity is had and low toxicity, cheapness, short dye are effective to fiber and dyestuff, in dyeing course, dyeing accelerant Small molecular can enter fiber, and be combined with fiber with hydrogen bond or Van der Waals force mode, slacken the adhesion between strand in fiber, increase the probability that macroscopic cavitation produces, dye diffusion speed improves, and dye uptake increases; When dyeing simultaneously, dyeing accelerant is adsorbed on fiber surface and forms one deck liquid dyeing accelerant layer, again because the solvability of dyeing accelerant to dyestuff is stronger, therefore the dense dye liquor layer of one deck can be formed at fiber surface, which enhance the concentration gradient of dyestuff at fibrous inside, the dyeing rate of dyestuff can be accelerated.

Polyimide fiber goods of the present invention, refer to the bulk fibre containing polyimides, or yarn, knitted fabric or the woven fabric containing polyimides.

First object of the present invention is to provide a kind of dyeing accelerant, and described dyeing accelerant is mixed by two or more in n-octyl alcohol, 2-ethyl butanol, DMF (DMF), cyclohexanol, methyl isobutyl carbinol.

Described dyeing accelerant is for promoting DISPERSE DYES contaminates polyimide fiber, and the solubility parameter of dyeing accelerant is 0.9-1.1 times of the solubility parameter of polyimides.

In one embodiment of the invention, the solubility coefficient of described dyeing accelerant is 20.2-23.4 (J/cm ³) ^1/2.

In one embodiment of the invention, the Group Contribution Method that described solubility parameter Hoftyzer-VanKrevelen proposes calculates, and calculates to obtain the solubility parameter δ of polyimide fiber _t=21.2 (J/cm ³) ^1/2;

In one embodiment of the invention, the solubility parameter of described n-octyl alcohol, 2-ethyl butanol, DMF (DMF), cyclohexanol, methyl isobutyl carbinol calculates by Group Contribution Method, is respectively 21 (J/cm ³) ^1/2, 21.4 (J/cm ³) ^1/2, 24.7 (J/cm ³) ^1/2, 23.3 (J/cm ³) ^1/2, 19.8 (J/cm ³) ^1/2.

In one embodiment of the invention, described dyeing accelerant is made up of n-octyl alcohol and 2-ethyl butanol.

In one embodiment of the invention, described solubility parameter is according to formula: δ _t=Σ Φ _iδ _icalculate, wherein Φ _ithe volume fraction of=each component, δ _ithe solubility parameter of=each component; The solubility parameter δ of each component _iobtain according to Group Contribution Method.

Second object of the present invention is to provide a kind of method promoting DISPERSE DYES contaminates polyimide fiber, is to use dyeing accelerant of the present invention, adopts high-temperature and high pressure dyeing process to carry out disperse dyeing to polyimide fiber.

Described method does not need to carry out pre-treatment to polyimide fiber, and directly the working solution of configuration containing dyeing accelerant, then adds wetting polyimide fiber, directly carry out high-temperature pressure dyeing.

In one embodiment of the invention, the dyeing prescription of described disperse dyeing: DISPERSE DYES 2-5%o.w.f, dyeing accelerant 50-100g/L, acetic acid 0.5g/L (pH4-6), bleeding agent 2mL/L, bath raio 1:20-50; Dyeing comprises: room temperature enters dye, and 2-3 DEG C/min is warming up to 125-135 DEG C, and constant temperature 0.5h-1h, 3-4 DEG C/min is cooled to 75-85 DEG C, and dyeing terminates; Take out fiber, washing, reduction cleaning, then wash, dry.

High-temperature and high pressure dyeing process refers in temperature higher than 100 DEG C, the dyeing carried out under being greater than 1 atmospheric condition of pressure.In one embodiment of the invention, refer at 125-135 DEG C, pressure about 0.27MP.

In one embodiment of the invention, the reduction cleaning after described dyeing also comprises washing, wash again, baking step.

In one embodiment of the invention, described bleeding agent is fatty alcohol-polyoxyethylene ether (penetrating agent JFC).

In one embodiment of the invention, described reduction cleaning condition is: sodium hydrosulfite 2g/L, sodium carbonate 2g/L, bath raio 1:50, temperature 80 DEG C, time 10min.

Beneficial effect of the present invention:

(1) dyeing accelerant of the present invention, when carrying out high temperature and high pressure method dyeing: dyestuff dye-uptake reaches 70-90%, easily contaminates to obtain comparatively dark colour; Can dyeing be completed at 125-135 DEG C, economize energy, reduce energy consumption; Simultaneously do not need pre-treatment, from terminate to dyeing, can complete in 2h, shorten the production cycle; Require low to dyeing installation simultaneously;

(2) dyeing accelerant of the present invention, polyimides can be realized in 125-135 DEG C of dyeing, fill up the blank of polyimides colouring art, when utilizing dyeing accelerant of the present invention to carry out disperse dyeing, without the need to using levelling agent, retarding agents etc., also modification or alkali treatment need not be carried out to polyimide fiber, little to fibrous material performance impact, and Recipe is simple, colouring method convenient;

(3) dyeing accelerant of the present invention does not affect the COLOR FASTNESS of polyimides fabric, and after adding dyeing accelerant dyeing, every fastness can reach 3-4 level, meets national standard.And low toxicity, environmental protection, low cod value, be a kind of environmental protection dyeing accelerant;

(4) dyeing accelerant composition is simple, and raw material sources are convenient, and each constituent content easily calculates, and is suitable for the polyimides dyeing of dyeing and finishing factory, can realizes suitability for industrialized production.

Accompanying drawing explanation

Fig. 1: add dyeing accelerant and urge the dispersed blue dye coloration result after contaminating;

Fig. 2: add dyeing accelerant and urge the dispersive red dye coloration result after contaminating;

Fig. 3: add dyeing accelerant and urge the disperse yellow dye coloration result after contaminating.

Detailed description of the invention

Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not by the restriction of embodiment.

Embodiment 1: the preparation of dyeing accelerant

Polyimides Hansen solubility parameter δ _tthe Group Contribution Method proposed with Hoftyzer-VanKrevelen calculates, and calculates to obtain the solubility parameter δ of polyimide fiber _t=21.2 (J/cm ³) ^1/2.Calculate group contribution constant needed for polyimides solubility parameter in table 1; Main equation is as follows: ${\mathrm{\δ}}_t=\sqrt{{{\mathrm{\δ}}_d}^2+{{\mathrm{\δ}}_p}^2+{{\mathrm{\δ}}_h}^2}---\left(1\right)$

${\mathrm{\δ}}_d=\frac{{\mathrm{\ΣF}}_{di}}{V_m}---\left(2\right)$

${\mathrm{\δ}}_p=\frac{\sqrt{{{\mathrm{\ΣF}}^2}_{pi}}}{V_m}---\left(3\right)$

${\mathrm{\δ}}_h=\frac{\sqrt{{\mathrm{\ΣE}}_{hi}}}{V_m}---\left(4\right)$

In formula: V _mfor the molal volume of material molecule; F _di, F _piand E _hibe respectively the dispersion term of group contribution constant, dipole term, hydrogen bond item; δ _d, δ _pand δ _hwith the dispersion term, dipole term, the hydrogen bond item that are respectively the Hansen solubility parameter that Group Contribution Method calculates.

The group contribution scale of table 1 solubility parameter component

Dyeing accelerant of the present invention selects according to the solubility parameter of polyimide fiber and different dyeing accelerant component, according to similar compatibility principle, the dyeing accelerant of solubility parameter close to polyimides has larger affinity to fiber, is conducive to dyestuff to the diffusion of fiber and upper dye.Require that this dyeing accelerant has the higher boiling meeting high-temperature pressure dyeing condition simultaneously, therefore the mixing dyeing accelerant of the present invention's optional two kinds and two or more different component, thus obtain the solubility parameter similar or identical with polyimides, n-octyl alcohol as similar to polyimides in solubility parameter and 2-ethyl butanol; Dyeing accelerant solubility parameter in the present invention and boiling point are in table 2.The solubility parameter δ of mixing dyeing accelerant _tcalculate by formula (5):

δ _t＝ΣΦ _iδ _i(5)

In formula: Φ _ithe volume fraction of=each component, δ _ithe solubility parameter of=each component.

The solubility parameter of each dyeing accelerant component of table 2 and boiling point

Embodiment 2:

Under bath raio 1:20, dispersed blue dye consumption is 3.5%o.w.f, dyeing accelerant consumption is 75g/L, bleeding agent consumption is 2mL/L, acetic acid consumption is 0.5g/L (pH=5-6), pour into after dye liquor is prepared in dye cup, add through the wetting polyimide fiber of deionized water or fabric, the dye cup of good seal is placed in dyeing machine and carries out high-temperature pressure dyeing.Wherein dyeing accelerant is that n-octyl alcohol and 2-ethyl butanol are mixed to get by a certain percentage, and mixed solubility parameter is 21.3 (J/cm ³) ^1/2left and right.

Dyeing is: room temperature enters dye, is incubated 30min after being warming up to 130 DEG C with 3 DEG C/min, then takes out after being down to 80 DEG C with 4 DEG C/min, washing, reduction cleaning, and washing is dried.Reduction cleaning technique is: sodium hydrosulfite 2g/L, sodium carbonate 2g/L, bath raio 1:50, temperature 80 DEG C, time 10min.

Embodiment 3:

Under bath raio 1:20, dispersive red dye consumption is 3.5%o.w.f, dyeing accelerant consumption is 75g/L, bleeding agent consumption is 2mL/L, acetic acid consumption is 0.5g/L (pH=5-6), pour into after dye liquor is prepared in dye cup, add through the wetting polyimide fiber of deionized water, the dye cup of good seal is placed in dyeing machine and carries out high-temperature pressure dyeing.Wherein dyeing accelerant is that cyclohexanol and methyl isobutyl carbinol are mixed to get by a certain percentage, and mixed solubility parameter is 20.8 (J/cm ³) ^1/2left and right.

Dyeing is: room temperature enters dye, is incubated 30min after being warming up to 130 DEG C with 3 DEG C/min, then takes out after being down to 80 DEG C with 4 DEG C/min, washing, reduction cleaning, and washing is dried.Reduction cleaning technique is: sodium hydrosulfite 2g/L, sodium carbonate 2g/L, bath raio 1:50, temperature 80 DEG C, time 10min.

Embodiment 4:

Under bath raio 1:20, disperse yellow dye consumption is 3.5%o.w.f, dyeing accelerant consumption is 75g/L, bleeding agent consumption is 2mL/L, acetic acid consumption is 0.5g/L (pH=5-6), pour into after dye liquor is prepared in dye cup, add through the wetting polyimide fiber of deionized water, the dye cup of good seal is placed in dyeing machine and carries out high-temperature pressure dyeing.Wherein dyeing accelerant is that methyl isobutyl carbinol and DMF (DMF) are mixed to get by a certain percentage, and mixed solubility parameter is about 23.4 (J/cm ³) ^1/2.

Dyeing is: room temperature enters dye, is incubated 30min after being warming up to 130 DEG C with 3 DEG C/min, then takes out after being down to 80 DEG C with 4 DEG C/min, washing, reduction cleaning, and washing is dried.Reduction cleaning technique is: sodium hydrosulfite 2g/L, sodium carbonate 2g/L, bath raio 1:50, temperature 80 DEG C, time 10min.

The Color of embodiment 2-4, respectively as shown in Fig. 1-3 and table 3.

Table 3 adds polyimide fiber Color after dyeing accelerant

Use method of the present invention, need not carry out surface modification or alkali treatment before dyeing to fiber, can contaminate to obtain comparatively dark colour, every fastness is better, meets national standard, remains the brute force of fiber to greatest extent.

Embodiment 5:

Under bath raio 1:50, dispersed blue dye consumption is 5%o.w.f, dyeing accelerant consumption is 100g/L, bleeding agent consumption is 2mL/L, acetic acid consumption is 0.5g/L, pour into after dye liquor is prepared in dye cup, add through the wetting polyimide fiber of deionized water, the dye cup of good seal is placed in dyeing machine and carries out high-temperature pressure dyeing.Wherein dyeing accelerant is n-octyl alcohol, methyl isobutyl carbinol, cyclohexanol be mixed to get by a certain percentage, and mixed solubility parameter is 22 (J/cm ³) ^1/2left and right.

Dyeing is: room temperature enters dye, is incubated 45min after being warming up to 135 DEG C with 2 DEG C/min, then takes out after being down to 80 DEG C with 3 DEG C/min, washing.To record dye uptake be 81.41%, K/S value is 22.3 in experiment, strength loss rate only 2%.

Embodiment 6:

Under bath raio 1:35, disperse yellow dye consumption is 5%o.w.f, and (methyl isobutyl carbinol and n-octyl alcohol composition, solubility parameter is about 20.2 (J/cm to dyeing accelerant ³) ^1/2) consumption is 100g/L, bleeding agent consumption is 2mL/L, and acetic acid consumption is 0.5g/L (pH=4-6), pours in dye cup after being prepared by dye liquor, add through the wetting polyimide fiber of deionized water, the dye cup of good seal is placed in dyeing machine and carries out high-temperature pressure dyeing.Dyeing is: room temperature enters dye, is incubated 60min after being warming up to 125 DEG C with 2.5 DEG C/min, then takes out after being down to 75 DEG C with 4 DEG C/min, washing, reduction cleaning, and washing is dried.To record dye uptake be 76.73%, K/S value is 21.9 in experiment, strength loss rate only 2.00%.

Embodiment 7:

Under bath raio 1:20, dispersive red dye consumption is 2%o.w.f, dyeing accelerant consumption is 50g/L, bleeding agent consumption is 2mL/L, acetic acid consumption is 0.5g/L (pH=5-6), pour into after being prepared by dye liquor in dye cup, the dye cup adding the yarn good seal containing polyimide fiber soaked through deionized water is placed in dyeing machine and carries out high-temperature pressure dyeing.Wherein dyeing accelerant is mixed by n-octyl alcohol, 2-ethyl butanol, DMF (DMF), cyclohexanol, methyl isobutyl carbinol these 5 kinds, and mixed solubility parameter is at 21.4 (J/cm ³) ^1/2left and right.

Dyeing is: room temperature enters dye, is incubated 60min after being warming up to 130 DEG C with 3 DEG C/min, then takes out after being down to 80 DEG C with 4 DEG C/min, washing, reduction cleaning, and washing is dried.Reduction cleaning technique is: sodium hydrosulfite 2g/L, sodium carbonate 2g/L, bath raio 1:50, temperature 80 DEG C, time 10min.To record dye uptake be 86.93%, K/S value is 22.4 in experiment, strength loss rate only 1.99%.

Embodiment 8:

Under bath raio 1:20, dispersive red dye consumption is 2%o.w.f, dyeing accelerant consumption is 50g/L, bleeding agent consumption is 2mL/L, acetic acid consumption is 0.5g/L (pH=5-6), pour into after dye liquor is prepared in dye cup, add through the wetting polyimides knitted fabric of deionized water, the dye cup of good seal is placed in dyeing machine and carries out high-temperature pressure dyeing.Wherein the solubility parameter of dyeing accelerant is at 21.0 (J/cm ³) ^1/2left and right.

Dyeing is: room temperature enters dye, is incubated 60min after being warming up to 130 DEG C with 3 DEG C/min, then takes out after being down to 80 DEG C with 4 DEG C/min, washing, reduction cleaning, and washing is dried.Reduction cleaning technique is: sodium hydrosulfite 2g/L, sodium carbonate 2g/L, bath raio 1:50, temperature 80 DEG C, time 10min.To record dye uptake be 82.83%, K/S value is 22.6 in experiment, strength loss rate only 2.02%.

Embodiment 9:

Under bath raio 1:20, dispersive red dye consumption is 2%o.w.f, dyeing accelerant consumption is 50g/L, bleeding agent consumption is 2mL/L, acetic acid consumption is 0.5g/L (pH=5-6), pour into after dye liquor is prepared in dye cup, add through the wetting polyimides woven fabric of deionized water, the dye cup of good seal is placed in dyeing machine and carries out high-temperature pressure dyeing.Wherein the solubility parameter of dyeing accelerant is at 20.8 (J/cm ³) ^1/2left and right.

Dyeing is: room temperature enters dye, is incubated 60min after being warming up to 130 DEG C with 3 DEG C/min, then takes out after being down to 80 DEG C with 4 DEG C/min, washing, reduction cleaning, and washing is dried.Reduction cleaning technique is: sodium hydrosulfite 2g/L, sodium carbonate 2g/L, bath raio 1:50, temperature 80 DEG C, time 10min.To record dye uptake be 80.06%, K/S value is 22.3 in experiment, strength loss rate only 2.04%.

Although the present invention with preferred embodiment openly as above; but it is also not used to limit the present invention, any person skilled in the art, without departing from the spirit and scope of the present invention; all can do various changes and modification, what therefore protection scope of the present invention should define with claims is as the criterion.

Claims (10)

1. a polyimide fiber goods dyeing accelerant, it is characterized in that, described dyeing accelerant is by any two kinds or to be two or morely mixed to get in n-octyl alcohol, 2-ethyl butanol, DMF (DMF), cyclohexanol, methyl isobutyl carbinol.

2. dyeing accelerant according to claim 1, is characterized in that, described dyeing accelerant is for promoting DISPERSE DYES contaminates polyimide fiber, and the solubility parameter of dyeing accelerant is 0.9-1.1 times of the solubility parameter of polyimides.

3. dyeing accelerant according to claim 2, is characterized in that, described solubility parameter is according to formula:

δ _t=Σ Φ _iδ _icalculate, wherein Φ _ithe volume fraction of=each component, δ _ithe solubility parameter of=each component; The solubility parameter δ of each component _iobtain according to Group Contribution Method.

4. dyeing accelerant according to claim 1, is characterized in that, described dyeing accelerant is made up of n-octyl alcohol and 2-ethyl butanol.

5. the application of the arbitrary described dyeing accelerant of claim 1-4 in dyeing.

6. application according to claim 5, is characterized in that, described application is dyeed for polyimide fiber; Described polyimide fiber refers to the bulk fibre containing polyimides, or yarn, knitted fabric or the woven fabric containing polyimides.

7. promote method DISPERSE DYES contaminating polyimide fiber, it is characterized in that, described method is the dyeing accelerant using claim 1, adopts high-temperature and high pressure dyeing process to carry out disperse dyeing to polyimide fiber.

8. method according to claim 7, is characterized in that, described method does not need to carry out pre-treatment to polyimide fiber, and directly the working solution of configuration containing dyeing accelerant, then adds polyimide fiber, directly carry out high-temperature pressure dyeing.

9. method according to claim 8, is characterized in that, the dyeing prescription of described disperse dyeing: DISPERSE DYES 2-5%o.w.f, dyeing accelerant 50-100g/L, acetic acid 0.5g/L (pH4-6), bleeding agent 2mL/L, bath raio 1:20-50; Dyeing is: room temperature enters dye, and 2-3 DEG C/min is warming up to 125-135 DEG C, and constant temperature 0.5h-1h, 3-4 DEG C/min is cooled to 75-85 DEG C, and dyeing terminates; Take out fiber, washing.

10. method according to claim 9, is characterized in that, described bleeding agent is fatty alcohol-polyoxyethylene ether.