CN115434169A

CN115434169A - Formaldehyde-free color fixing agent and preparation method thereof

Info

Publication number: CN115434169A
Application number: CN202210996272.6A
Authority: CN
Inventors: 刘汉茂; 孙锋; 刘海平; 吕学海
Original assignee: Jiangxi Desheng Fine Chemicals Co ltd
Current assignee: Jiangxi Desheng Fine Chemicals Co ltd
Priority date: 2022-08-19
Filing date: 2022-08-19
Publication date: 2022-12-06

Abstract

The invention discloses an aldehyde-free color fixing agent, which comprises epichlorohydrin, methyl ethyl ketone, aluminate, ethylene acetonitrile, sodium phenolate, acrylamide, 4-methyl-1-hexene, an initiator and water. The color fixing agent prepared by the reaction of the invention does not contain formaldehyde, so that no formaldehyde is released, and the color fixing agent is safer and more environment-friendly to use.

Description

Formaldehyde-free color fixing agent and preparation method thereof

Technical Field

The invention relates to the technical field of dye fixation, in particular to an aldehyde-free fixing agent and a preparation method thereof.

Background

The color fixing agent is one of important assistants in printing and dyeing industry [1] in recent years, along with the development of scientific technology, dyeing and finishing technology is also obviously improved, and as international textile trade is expanded and living level and environmental protection consciousness of people are improved, textile is required to be comfortable, clean and safe, since the 70 th 20 th century, after the ' blue angel ' plan is firstly launched in Germany, some developed countries (Japan, america and the like) in the world pass and implement relevant laws and regulations successively, various indexes of textile are regulated, and the green textile requires that carcinogenicity, teratogenicity and biodegradability which are regulated in the regulations are forbidden to use dyes produced by certain aromatic amine intermediates in printing and dyeing processing, and simultaneously requires that the used assistants do not contain heavy metal ions and do not produce free formaldehyde [2-4], namely, the ' green assistants are used, and the development and application of aldehyde-free color fixing agent KS are in accordance with the requirements

Because the color fixing effect of the color fixing agent is poor, the dyeing needs to be repeatedly carried out, the stability is poor, especially the chlorine fastness is poor, the use of people is not facilitated, and more color fixing agents contain formaldehyde and can cause harm to human bodies, so the stability is high, the chlorine fastness is good, and the color fixing agent containing no formaldehyde can better meet the production requirements of enterprises.

Disclosure of Invention

The invention provides an aldehyde-free color fixing agent and a preparation method thereof to overcome the defects in the prior art.

In order to solve the technical problems, the invention adopts the following technical scheme: an aldehyde-free color fixing agent comprises epichlorohydrin, methyl ethyl ketone, aluminate, ethylene acetonitrile, sodium phenolate, acrylamide, 4-methyl-1-hexene, an initiator and water.

The sodium phenolate has a relatively stable structure, does not react violently, can reduce the generation of impurities by matching with the reaction of an allyl polymer and epichlorohydrin in the reaction, is alkaline, can adjust the alkalinity in the reaction process, enables the epichlorohydrin to react more completely in an alkaline environment, can reduce the impurities after the addition reaction of the epichlorohydrin, improves the reaction efficiency of the polymer, ensures the quality of a color fixing agent, and reduces the process difficulty caused by excessive impurities;

methyl ethyl ketone has carbonyl and active hydrogen adjacent to the carbonyl, so that various reactions are easy to occur, and the ethylene acetonitrile is matched to increase reactive groups in molecules, contains lone electron pairs and can be used as a Hydrogen Bond Acceptor (HBA) to form a hydrogen bond effect, finally can form strong molecular attraction on cloth, can well form close ion combination with cloth fibers, has larger attraction with cellulose molecules, and especially can form hydrogen bonds with the fiber molecules, thereby improving the color fixing effect;

the aluminate contains groups which can react with active hydrogen, so that the aluminate can generate bonding action with inorganic filler containing hydroxyl, carboxyl or surface adsorbed water, and the affinity and the bonding force with organic polymers are improved, so that an anti-settling effect is generated, the bonding strength can be improved, and the stability is strong;

preferably, the preparation method of the aldehyde-free color fixing agent comprises the following steps:

(1) Under normal temperature and normal pressure, sequentially putting acrylamide, 4-methyl-1-hexene, an initiator and ionized water into a reaction kettle, mixing and stirring the acrylamide, the 4-methyl-1-hexene, the initiator and the ionized water according to a mass ratio of 1.2;

(2) Under low temperature and normal pressure, placing epoxy chloropropane and sodium phenolate into a reaction kettle according to the mass ratio of 0.5;

(3) At normal temperature and normal pressure, firstly, dripping 300-450 parts of the polymerization solution obtained in the step (1) into the mixed solution obtained in the step (2), dripping for 1-1.5h, then dripping ethylene acetonitrile into the reaction kettle, and standing to obtain an organic solution after dripping is finished;

(4) 4-8 parts of aluminate are added into the reaction liquid in the step (3) and stirred for 0.5-0.8h to obtain reaction liquid;

(5) And regulating the pH value of the reaction solution to 6-8, and cooling to 18-23 ℃ to obtain the color fixing agent.

Preferably, step (3) further comprises: after obtaining the organic solution, reducing the temperature to 18-20 ℃, adding 9-14 parts of methyl ethyl ketone into the organic solution, stirring, and stirring for 0.4-0.7h to obtain the organic solution, wherein the organic solution is a final product.

Preferably, in the step (2), after the mixed solution is obtained, the epichlorohydrin is slowly dripped into the mixed solution at the dripping speed of 19-27/min for 1-1.5h, and after the dripping is finished, the mixed solution is slowly stirred for 30-45min to obtain the mixed solution, wherein the mixed solution is a final product.

The method comprises the steps of adding epoxy chloropropane after obtaining a mixed solution, wherein epoxy chloropropane is added, the characteristic of epoxy chloropropane is firstly that if the consumption of epoxy chloropropane is excessive, a three-dimensional condensation compound is formed, reactive groups in molecules are increased, the color fixing effect is improved, but the effect is opposite to the actual situation, the color fixing agent is of a three-dimensional structure rather than a planar structure, the hydrogen bond attraction between the color fixing agent and fibers is weakened, and the color fixing effect is reduced.

Preferably, in the step (2), when the epichlorohydrin is dripped into the mixed solution, the dripping speed is 27/min when the initial temperature is 18-21 ℃, the dripping speed is 23/min when the epichlorohydrin is dripped into the mixed solution for 0.25h, the temperature is increased to 26-30 ℃, and the dripping speed is 19/min when the epichlorohydrin is dripped into the mixed solution for 0.45h, and the temperature is increased to 34-39 ℃ until the dripping speed is finished.

Preferably, in the step (3), the dropping speed of the dropwise adding mixed solution is 40-55/min, the dropping speed of the dropwise adding ethylene acetonitrile is 40-55/min, and the time of the dropwise adding ethylene acetonitrile is 0.5-0.7h.

7. The method of claim 1, wherein the initiator is a free radical initiator.

Compared with the prior art, the invention has the following effects:

1. the epichlorohydrin is matched with the sodium phenolate, and the epichlorohydrin is added in matching by times. The generation of impurities can be greatly reduced.

2. The color fixing agent prepared by the reaction does not contain formaldehyde, so that no formaldehyde is released, and the color fixing agent is safer and more environment-friendly to use.

3. Methyl ethyl ketone cooperates with vinyl acetonitrile, so that the hydrogen bond effect is enhanced, the reaction is more complete while the reaction rate is accelerated, the generation of impurities is reduced, the intermolecular combination is increased, and the color fixing agent is softer.

Detailed Description

The present invention will be described in detail with reference to examples.

Example 1

The invention relates to an aldehyde-free color fixing agent which comprises 110 parts of epoxy chloropropane, 13 parts of methyl ethyl ketone, 6 parts of aluminate, 64 parts of ethylene acetonitrile, 94 parts of sodium phenolate, 90 parts of acrylamide, 18 parts of 4-methyl-1-hexene, 90 parts of an initiator and 360 parts of water.

Example 2

An aldehyde-free color fixing agent comprises 100 parts of epoxy chloropropane, 9 parts of methyl ethyl ketone, 4 parts of aluminate, 56 parts of ethylene acetonitrile, 91 parts of sodium phenolate, 86 parts of acrylamide, 16 parts of 4-methyl-1-hexene, 86 parts of an initiator and 338 parts of water.

Comparative example 1

Comparative example 1 compared to example 1, without the addition of aluminate, is otherwise the same as example 1.

Comparative example 2

Comparative example 2 compared to example 1, no ethylene acetonitrile was added, and the rest was the same as example 1.

Comparative example 3

Comparative example 3, compared to example 1, did not add methyl ethyl ketone and vinyl acetonitrile, and the rest was the same as example 1.

Comparative example 4

Comparative example 4 is different from example 1 in that sodium phenolate was replaced with diethylenetriamine, and the rest is the same as example 1, compared with example 1.

The color fixing agents are prepared in the examples 1-2 and the comparative examples 1-4 through the same preparation method, the prepared color fixing agents are subjected to experimental comparison, and the specific data are shown in the table 1;

the same preparation method comprises the following steps: mixing and stirring acrylamide, 4-methyl-1-hexene, an initiator and water to obtain an organic mixed solution, mixing epoxy chloropropane and sodium phenolate (or diethylenetriamine) to obtain a mixed solution, dropwise adding the mixed solution into the organic mixed solution at a dropping speed of 40-55/min until the dropwise adding is finished to obtain a reaction solution, sequentially adding ethylene acetonitrile, methyl ethyl ketone and aluminate into the reaction solution, mixing and stirring, and regulating the pH value to be 7 after the stirring is finished and cooling to obtain the color fixing agent.

The detection method of the experiment comprises the following steps:

and (3) color spot precipitation observation: observing the color spot precipitation condition on the microfiber leather by naked eyes, and grading the sample quality according to the size of the color spot area: no color spots are recorded as level 1; marking the area of the color spot less than 4 percent as 2 grade, the area of the color spot more than or equal to 4 percent and less than 8 percent as 3 grade, the area of the color spot more than or equal to 8 percent and less than 12 percent as 4 grade, and the area of the color spot more than or equal to 12 percent as 5 grade; the results are reported in table 1.

And (3) rubbing fastness detection test: testing the sample according to the GB3920-1997 standard, and recording the testing result in the table 1;

method for testing color fastness to washing: covering half of the cloth to be tested by using an opaque black card, then horizontally placing the cloth under an ultraviolet lamp at a position 60cm below the ultraviolet lamp, starting a light source to irradiate for 10 hours, and testing the light fastness, wherein the cloth is divided into 8 grades, and the best grade of 8 is 1 grade and the worst grade;

TABLE 1

As can be seen from table 1, example 1 is the most preferred embodiment.

The comparative example 1 does not add aluminate, but the aluminate can increase the binding force of the color fixing agent, can be better and tightly combined with the fiber, and forms a film on the surface of the fiber, and the aluminate also improves the bonding strength, so that the formed film is not easy to fall off and the color falling phenomenon is reduced, while the comparative example 1 does not add aluminate, so that the color spot precipitation and the color fastness to washing are slightly inferior to those of the example 1.

Comparative example 2 no ethyleneacetonitrile was added, hydrogen bonding was formed, strong molecular attraction was formed on the cloth, and the bonding with the example of cloth fiber was strengthened, thereby improving the fixing effect, and thus the color fastness to washing was slightly inferior to that of example 1.

Comparative example 3 does not add methyl ethyl ketone and vinyl acetonitrile, methyl ethyl ketone cooperates with vinyl acetonitrile, strengthen the hydrogen bond effect, make the reaction more complete while accelerating the reaction rate, reduce the impurity and produce, increase the intermolecular association, make the color fixing agent softer, therefore the fastness to rubbing and color fastness to washing are inferior to example 1 slightly.

Comparative example 4 sodium phenate was replaced with diethylenetriamine, sodium phenate was structurally stable, was fundamentally reduced in the generation of impurities, and was basic to allow more complete reaction, and thus was slightly inferior to example 1 in terms of mottling precipitation, rubbing fastness, and color fastness to washing.

Example 3

The preparation method of the aldehyde-free color fixing agent comprises the following steps:

(2) Under low temperature and normal pressure, placing epoxy chloropropane and sodium phenolate into a reaction kettle according to the mass ratio of 0.5, stirring for 0.6-1h, then slowly dripping epoxy chloropropane into the mixed solution, wherein when the initial temperature is 18 ℃, the dripping speed is 27/min, when the dripping speed is 0.25h, the temperature is increased to 26 ℃, the dripping speed is 23/min, when the dripping speed is 0.45h, the temperature is increased to 34 ℃, the dripping speed is 19/min until the dripping is finished, the dripping time is 1h, and after the dripping is finished, slowly stirring for 30min to obtain mixed solution;

(3) Dropping the mixed solution obtained in the step (2) into 300 parts of the polymerization solution obtained in the step (1) in a reaction kettle at normal temperature and normal pressure, wherein the dropping speed of the dropped mixed solution is 40/min, the dropping time is 1-1.5h, then dropping ethylene acetonitrile into the reaction kettle, the dropping speed is 40/min, the dropping time of ethylene acetonitrile is 0.5h, after the dropping is finished, reducing the temperature to 18 ℃, then adding 9-14 parts of methyl ethyl ketone into the organic solution, stirring for 0.4h, and standing to obtain an organic solution;

(4) Adding 4 parts of aluminate into the reaction liquid obtained in the step (3), and stirring for 0.5h to obtain a reaction liquid;

(5) And regulating the pH value of the reaction solution to 6, and cooling to 18 ℃ to obtain the color fixing agent.

Example 4

(2) Under low temperature and normal pressure, placing epoxy chloropropane and sodium phenolate into a reaction kettle according to the mass ratio of 0.5, stirring for 0.8h, then slowly dripping epoxy chloropropane into the mixed solution, wherein when the initial temperature is 19 ℃ and the dripping speed is 27/min, when the dripping speed is 0.25h, the temperature is increased to 28 ℃, the dripping speed is 23/min, when the dripping speed is 0.45h, the temperature is increased to 37 ℃, the dripping speed is 19/min until the dripping is finished, the dripping time is 1.2h, and after the dripping is finished, slowly stirring for 37min to obtain a mixed solution;

(3) Under normal temperature and normal pressure, firstly, dripping 420 parts of the polymerization solution obtained in the step (1) into the mixed solution obtained in the step (2), wherein the dripping speed of the dripped mixed solution is 46/min, dripping for 1.3h, then dripping ethylene acetonitrile into the reaction kettle at the dripping speed of 48/min for 0.65h, after the dripping is finished, reducing the temperature to 19 ℃, adding 11 parts of methyl ethyl ketone into the organic solution, stirring for 0.5h, and standing to obtain an organic solution;

(4) 4-8 parts of aluminate are added into the reaction liquid obtained in the step (3) and stirred for 0.75h to obtain reaction liquid;

(5) And adjusting the pH value of the reaction solution to 7, and cooling to 20 ℃ to obtain the color fixing agent.

Example 5

The preparation method of the formaldehyde-free color fixing agent comprises the following steps:

(2) Under low temperature and normal pressure, placing epoxy chloropropane and sodium phenolate into a reaction kettle according to the mass ratio of 0.5, stirring for 1h, then slowly dripping epoxy chloropropane into the mixed solution, wherein when the initial temperature is 21 ℃, the dripping speed is 27/min, when the dripping speed is 0.25h, when the temperature is increased to 30 ℃, the dripping speed is 23/min, when the dripping speed is 0.45h, the temperature is increased to 39 ℃, the dripping speed is 19/min until the dripping is finished, the dripping time is 1.5h, and after the dripping is finished, slowly stirring for 45min to obtain a mixed solution;

(3) At normal temperature and normal pressure, firstly, dripping 450 parts of the polymerization solution obtained in the step (1) into the mixed solution obtained in the step (2), wherein the dripping speed of the dripped mixed solution is 55/min, the dripping time is 1.5h, then, dripping ethylene acetonitrile into the reaction kettle, the dripping speed is 55/min, the dripping time of the ethylene acetonitrile is 0.7h, after the dripping is finished, reducing the temperature to 20 ℃, then, adding 14 parts of methyl ethyl ketone into the organic solution, stirring for 0.7h, and standing to obtain the organic solution;

(4) Adding 8 parts of aluminate into the reaction liquid obtained in the step (3), and stirring for 0.8h to obtain a reaction liquid;

(5) And (3) adjusting the pH value of the reaction solution to 8, and then cooling to 23 ℃ to obtain the color fixing agent.

Comparative example 5

Compared with the example 3, in the step (2), in the comparative example 6, the epichlorohydrin is not slowly dripped after the epichlorohydrin and the sodium phenolate are mixed, but the epichlorohydrin is directly mixed two by two to obtain a mixed solution to be subjected to the next process, and the rest is the same as the example 3.

Comparative example 6

Compared with the example 3, the ethylene acetonitrile is not added in a mode of slowly dripping, but is directly added and stirred, and the rest is the same as the example 3.

Comparative example 7

The difference from example 3 is that, in step (2), epichlorohydrin was slowly dropped into the mixed solution at a temperature of 35 ℃ without gradually raising the temperature in 3 stages, and the rest is the same as example 3.

Comparative example 8

In contrast to example 3, comparative example 8 does not employ step (4), but the laking reagent is obtained directly after obtaining the organic solution, otherwise it is identical to example 3.

The color fixing agents prepared in examples 3-5 and comparative examples 5-8 are compared in experiments, and specific data are shown in Table 2;

the detection method of the experiment comprises the following steps:

color spot precipitation observation: and (3) observing the color spot precipitation condition on the microfiber leather by naked eyes, and grading the sample quality according to the area of the color spot: no color spots are recorded as level 1; marking the color spot area of less than 4 percent as 2 grade, marking the color spot area of more than 4 percent and less than 8 percent as 3 grade, marking the color spot area of more than 8 percent and less than 12 percent as 4 grade, and marking the color spot area of more than 12 percent and less than 5 grade; the results are reported in table 2.

Rub fastness detection test: testing the sample according to the GB3920-1997 standard, and recording the testing result in the table 2;

TABLE 2

	Color spot deposition rating	Crocking fastness rating	Color fastness to washing grade
				Example 3	1	5	7
Example 4	1	5	6
				Example 5	1	5	6
Comparative example 6	2	4	4
				Comparative example 7	2	4	6
Comparative example 8	4	4	5

As can be seen from table 2, example 3 is the optimum formulation.

Comparative example 5 does not use the slow addition of epichlorohydrin after mixing epichlorohydrin and sodium phenolate to reduce the formation of three-dimensional condensates and therefore the crock, mottle and wash fastness were less than in example 1.

Comparative example 6 does not adopt the way of slowly adding dropwise to add ethylene acetonitrile, make the reaction more complete, increase the molecular attraction gradually, if add ethylene acetonitrile once only, will accelerate the reaction, make the reaction aggravate, the reaction process can be uncontrollable and will produce unnecessary impurity, will also make the reaction incomplete.

Comparative example 7 does not use 3 stages of gradual temperature rise and with the temperature rise gradually reduced dropping amount, thus producing more impurities than example 3, and therefore in the mottle precipitation and color fastness to washing is slightly inferior to example 1.

Comparative example 8 does not include step (4), and does not include aluminate, which increases the binding force of the fixing agent, and can be well combined with the fiber, and a thin film is formed on the surface of the fiber, and the aluminate also increases the binding strength, so that the formed thin film is not easy to fall off, and the color fall-off phenomenon is reduced, whereas comparative example 8 does not include aluminate, and thus the color fastness of the color patch to precipitation and washing is less than that of example 3.

The above examples only show several embodiments of the present invention, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the patent and protection scope of the present invention shall be subject to the appended claims.

Claims

1. An aldehyde-free color fixing agent is characterized in that: epichlorohydrin, methyl ethyl ketone, aluminate, ethylene acetonitrile, sodium phenolate, acrylamide, 4-methyl-1-hexene, an initiator and water.

2. The method of claim 1, comprising the steps of:

3. The method for preparing the aldehyde-free color fixing agent according to claim 2, wherein the step (3) further comprises: after obtaining the organic solution, reducing the temperature to 12-15 ℃, adding 9-14 parts of methyl ethyl ketone into the organic solution, stirring for 0.4-0.7h, and obtaining the organic solution which is the final product.

4. The method for preparing the aldehyde-free color fixing agent according to claim 2, wherein in the step (2), after the mixed solution is obtained, the epichlorohydrin is slowly dropped into the mixed solution at a dropping speed of 19-27/min for 1-1.5h, and after the dropping is finished, the mixed solution is slowly stirred for 30-45min to obtain the final product.

5. The method for preparing the aldehyde-free color fixing agent according to claim 4, wherein in the step (2), the initial temperature of the epichlorohydrin is 18-21 ℃ and the dropping speed is 27/min, the temperature is increased to 26-30 ℃ and the dropping speed is 23/min when the epichlorohydrin is added to the mixed solution for 0.25h, and the temperature is increased to 34-39 ℃ and the dropping speed is 19/min when the epichlorohydrin is added to 0.45h until the end of the addition.

6. The method for preparing the formaldehyde-free color fixing agent as claimed in claim 3, wherein in the step (3), the dropping speed of the dropwise adding mixed solution is 40-55/min, the dropping speed of the dropwise adding ethylene acetonitrile is 40-55/min, and the time of the dropwise adding ethylene acetonitrile is 0.5-0.7h.

7. The method of claim 1, wherein the initiator is a free radical initiator.