阅读说明：本技术 一种活性染料印花用低温皂洗剂及其制备方法 (Low-temperature soaping agent for printing of reactive dye and preparation method thereof ) 是由 郭素明 李正雄 于 2020-12-28 设计创作，主要内容包括：本发明提供一种活性染料印花用低温皂洗剂及其制备方法。本发明的皂洗剂包括如下组分：65-92重量％功能性化合物、3-28重量％聚有机酸盐、0.1-2重量％高效分散剂、0.5-5重量％乳化剂、0.5-5重量％其他添加剂,所述功能性化合物含有硫代酰胺基团。本发明产品不仅具有去浮色、防沾色的性能,而且稳定性好,具有优异的干、湿摩擦牢度和皂洗牢度。(The invention provides a low-temperature soaping agent for printing of reactive dyes and a preparation method thereof. The soaping agent comprises the following components: 65-92 wt% of functional compound, 3-28 wt% of poly organic acid salt, 0.1-2 wt% of high-efficiency dispersant, 0.5-5 wt% of emulsifier and 0.5-5 wt% of other additives, wherein the functional compound contains thioamide group. The product of the invention not only has the performances of removing floating color and preventing staining, but also has good stability and excellent dry and wet rubbing fastness and soaping fastness.)

1. The low-temperature soaping agent for printing the reactive dye comprises the following components:

the functional compound contains a thioamide group,

the poly organic acid salt is polyhexamethylene guanidine hydrochloride, sodium poly alcohol ether sulfonate, sodium poly stearate, polylysine hydrochloride or the mixture thereof,

the high-efficiency dispersing agent is sodium polycarboxylate, sodium polyphosphate, ammonium polyacrylate, sodium lignosulfonate or a mixture of the sodium polycarboxylate, the sodium polyphosphate and the sodium lignosulfonate.

2. The low-temperature soaping agent for reactive dye printing according to claim 1, wherein the functional compound is formed by reacting a compound containing a thioamide group with a compound containing both an alkenyl group and a ketone group.

3. The low-temperature soaping agent for reactive dye printing according to claim 2, wherein the compound containing a thioamide group is dithiooxamide, N-dibenzyldithiooxamide, benzene-1, 4-dithiobenzamide, didodecyldiaminooxalamide or a compound of formula (I):

R¹is H, (CH)₂)_n1CH₃Or a phenyl group,

n1 is an integer from 0 to 17,

the compound shown in the formula (I) is preferably selected from thiocarboxamide, thioacetamide, thionicotinamide, thiobenzamide and 3, 4-dimethylthiobenzamide.

4. The low-temperature soaping agent for reactive dye printing according to claim 2, wherein the compound containing both alkenyl and ketone groups is a compound represented by formula (II):

R²is H, CH₃、C₂H₅、C₃H₇Or a phenyl group,

R³is H or CH₃，

R⁴Is (CH)₂)_n2CH₃A phenyl group or a cyclopropyl group,

n2 is an integer from 0 to 12,

the compound containing both alkenyl and ketone groups is preferably selected from the group consisting of phenylbutenone, 1-cyclopropyl-2-propenone, 3-penten-2-one, 1-penten-3-one, 4-hexen-3-one, 3-methyl-3-hexen-2-one, 3-hepten-2-one, 1-hepten-3-one, 1-octen-3-one, 3-methyl-3-buten-2-one, and phenylpropenone.

5. The low-temperature soaping agent for printing reactive dyes according to claim 2, wherein the functional compound is a compound represented by formula (III):

R¹is H, (CH)₂)_n1CH₃Or a phenyl group,

n1 is an integer from 0 to 17,

R²is H, CH₃、C₂H₅、C₃H₇Or a phenyl group,

R³is H or CH₃，

R⁴Is (CH)₂)_n2CH₃A phenyl group or a cyclopropyl group,

n2 is an integer from 0 to 12.

6. The low-temperature soaping agent for printing of reactive dyes according to claim 5, wherein the molecular weight of the compound of formula (III) is 200-1000.

7. The low-temperature soaping agent for reactive dye printing according to claim 2, wherein the compound containing thioamide group and the compound containing both alkenyl and ketone groups are reacted in a weight ratio of 1: 1.0-2.2.

8. The low-temperature soaping agent for reactive dye printing according to claim 1, wherein the emulsifier is a nonionic surfactant, preferably an isomeric fatty alcohol polyoxyethylene ether, a sorbitan fatty acid ester or a mixture thereof,

the other additives are fatty alcohol ether ammonium sulfate, coco diethanol amide, coco propyl amide betaine or a mixture thereof,

in the low-temperature soaping agent for printing reactive dyes, the functional compound is more preferably 70-90 wt%, particularly preferably 74-80 wt%, the poly organic acid salt is more preferably 5-25 wt%, particularly preferably 15-20 wt%, the other additives are more preferably 1-5 wt%, particularly preferably 3-5 wt%, and the high-efficiency dispersant is more preferably 0.4-1 wt%, particularly preferably 0.5-0.8 wt%.

9. A preparation method of a low-temperature soaping agent for printing of reactive dyes comprises the following steps:

a) preparation of functional compounds: adding thioamide group-containing compound, alkenyl and keto-containing compound and anhydrous ethanol into a reactor, dissolving completely, heating and refluxing at 70-85 deg.C for 8-12 hr, cooling the reaction solution to room temperature, distilling under low pressure to remove ethanol,

b) in the presence of an emulsifier, uniformly mixing a high-efficiency dispersant, other additives, a poly organic acid salt and a functional compound in a weight ratio of 1:5-50:20-200:65-300, more preferably in a weight ratio of 1:5-10:22-40:80-180, particularly preferably in a weight ratio of 1:6-9:23-35:90-150,

the poly organic acid salt is polyhexamethylene guanidine hydrochloride, sodium poly alcohol ether sulfonate, sodium poly stearate, polylysine hydrochloride or the mixture thereof,

the high-efficiency dispersing agent is sodium polycarboxylate, sodium polyphosphate, ammonium polyacrylate, sodium lignosulfonate or a mixture of the sodium polycarboxylate, the sodium polyphosphate and the sodium lignosulfonate.

10. The method for preparing the low-temperature soaping agent for printing reactive dyes according to claim 9, wherein the functional compound is a compound represented by formula (III):

R¹is H, (CH)₂)_n1CH₃Or a phenyl group,

n1 is an integer from 0 to 17,

R²is H, CH₃、C₂H₅、C₃H₇Or a phenyl group,

R³is H or CH₃，

R⁴Is (CH)₂)_n2CH₃A phenyl group or a cyclopropyl group,

n2 is an integer from 0 to 12.

Technical Field

The invention belongs to the technical field of textile auxiliary agents, and particularly relates to a low-temperature soaping agent for reactive dye printing and a preparation method thereof.

Background

After the reactive dye is printed, a sufficiently strict washing or soaping process is carried out to remove cloth cover residual slurry, but a large amount of natural or synthetic polymer slurry washed and removed in the bath is easily combined with unfixed dye, printing auxiliary agents and the like to be back-stained on printed fabrics, so that a series of problems of white bottom non-whiteness, pattern color change, fastness reduction and the like are caused, and the quality of the printed fabrics is influenced.

With the increasing environmental protection problem and the increasing environmental awareness of people, the exploration of low-energy, energy-saving and high-efficiency products becomes the trend of future development. Many researchers have done a lot of work, for example, chinese patent publication No. CN108252131A discloses a soaping agent containing laccase, which is added with various enzyme preparations to improve the specific performance with high efficiency, but the anti-sticky property is weak and the color change is easy to occur. For example, chinese patent publication No. CN102876516A discloses a method for preparing a novel soaping agent for deep color plucking printing, which is a copolymer prepared by reacting hydroxymethyl acrylic acid, maleic anhydride and N-vinyl pyrrolidone, wherein the soaping temperature is 85-100 ℃, but the preparation process is complicated and the energy-saving effect is poor. For another example, chinese patent publication No. CN108457105A discloses a method for preparing an environment-friendly low-temperature soaping agent and an application thereof, wherein a copolymer is prepared by reacting maleic anhydride, N-vinyl pyrrolidone, and polyethylene glycol, and the soaping temperature is 40-50 ℃, but the preparation process is complicated, and the reaction conditions are harsh and difficult to control.

Disclosure of Invention

The invention aims to provide the low-temperature soaping agent for printing the reactive dye, which has stable performance, energy conservation and high efficiency.

The invention adopts the monomer containing thioamide group and combines the monomer with multiple reaction groups to synthesize the functional compound, so that the functional compound has excellent dispersion performance, stronger chelating capacity for adsorbing metal ions and effectively prevents the contamination of fiber by the dirt combination in the processing process. Then, under the action of the synergistic effect of the poly organic acid salt, the high-efficiency dispersant and other additives, the slurry is easy to disperse and remove under the condition that the temperature is 55-65 ℃.

Specifically, according to one aspect of the invention, the low-temperature soaping agent for printing the reactive dye comprises the following components:

the functional compound contains a thioamide group,

the poly organic acid salt is polyhexamethylene guanidine hydrochloride, sodium poly alcohol ether sulfonate, sodium poly stearate, polylysine hydrochloride or the mixture thereof,

the high-efficiency dispersing agent is sodium polycarboxylate, sodium polyphosphate, ammonium polyacrylate, sodium lignosulfonate or a mixture of the sodium polycarboxylate, the sodium polyphosphate and the sodium lignosulfonate.

The functional compound is formed by reacting a thioamide group-containing compound with a compound having both an alkenyl group and a ketone group.

The compound containing the thioamide group is dithiooxamide, N-dibenzyldithiooxamide, benzene-1, 4-dithiobenzamide, didodecyldiaminooxalamide or a compound shown as a formula (I):

R¹is H, (CH)₂)_n1CH₃Or a phenyl group,

n1 is an integer from 0 to 17,

the compound shown in the formula (I) is preferably selected from thiocarboxamide, thioacetamide, thionicotinamide, thiobenzamide and 3, 4-dimethylthiobenzamide.

The compound containing both alkenyl and keto is a compound shown as a formula (II):

R²is H, CH₃、C₂H₅、C₃H₇Or a phenyl group,

R³is H or CH₃，

R⁴Is (CH)₂)_n2CH₃A phenyl group or a cyclopropyl group,

n2 is an integer from 0 to 12,

the compound containing both alkenyl and ketone groups is preferably selected from the group consisting of phenylbutenone, 1-cyclopropyl-2-propenone, 3-penten-2-one, 1-penten-3-one, 4-hexen-3-one, 3-methyl-3-hexen-2-one, 3-hepten-2-one, 1-hepten-3-one, 1-octen-3-one, 3-methyl-3-buten-2-one, and phenylpropenone.

The functional compound is a compound shown as a formula (III):

R¹is H, (CH)₂)_n1CH₃Or a phenyl group,

n1 is an integer from 0 to 17,

R²is H, CH₃、C₂H₅、C₃H₇Or a phenyl group,

R³is H or CH₃，

R⁴Is (CH)₂)_n2CH₃A phenyl group or a cyclopropyl group,

n2 is an integer from 0 to 12.

According to another aspect of the invention, a preparation method of a low-temperature soaping agent for printing reactive dyes is provided, which comprises the following steps:

a) preparation of functional compounds: adding thioamide group-containing compound, alkenyl and keto-containing compound and anhydrous ethanol into a reactor, dissolving completely, heating and refluxing at 70-85 deg.C for 8-12 hr, cooling the reaction solution to room temperature, distilling under low pressure to remove ethanol,

b) in the presence of an emulsifier, uniformly mixing a high-efficiency dispersant, other additives, a poly organic acid salt and a functional compound in a weight ratio of 1:5-50:20-200:65-300, more preferably in a weight ratio of 1:5-10:22-40:80-180, particularly preferably in a weight ratio of 1:6-9:23-35:90-150,

the poly organic acid salt is polyhexamethylene guanidine hydrochloride, sodium poly alcohol ether sulfonate, sodium poly stearate, polylysine hydrochloride or the mixture thereof,

the high-efficiency dispersing agent is sodium polycarboxylate, sodium polyphosphate, ammonium polyacrylate, sodium lignosulfonate or a mixture of the sodium polycarboxylate, the sodium polyphosphate and the sodium lignosulfonate.

The functional compound is preferably a compound represented by formula (III):

R¹is H, (CH)₂)_n1CH₃Or a phenyl group,

n1 is an integer from 0 to 17,

R²is H, CH₃、C₂H₅、C₃H₇Or a phenyl group,

R³is H or CH₃，

R⁴Is (CH)₂)_n2CH₃A phenyl group or a cyclopropyl group,

n2 is an integer from 0 to 12.

According to the technical scheme of the invention, the low-temperature soaping agent with excellent stain resistance, cleaning performance and dispersion performance can be obtained.

Detailed Description

In one embodiment of the invention, the low-temperature soaping agent for printing the reactive dye comprises the following components:

the functional compound contains a thioamide group,

the poly organic acid salt is polyhexamethylene guanidine hydrochloride, sodium poly alcohol ether sulfonate, sodium poly stearate, polylysine hydrochloride or the mixture thereof,

the high-efficiency dispersing agent is sodium polycarboxylate, sodium polyphosphate, ammonium polyacrylate, sodium lignosulfonate or a mixture of the sodium polycarboxylate, the sodium polyphosphate and the sodium lignosulfonate.

In the low-temperature soaping agent for printing reactive dyes, the functional compound is more preferably 70-90 wt%, particularly preferably 74-80 wt%, the poly organic acid salt is more preferably 5-25 wt%, particularly preferably 15-20 wt%, the other additives are more preferably 1-5 wt%, particularly preferably 3-5 wt%, and the high-efficiency dispersant is more preferably 0.4-1 wt%, particularly preferably 0.5-0.8 wt%.

In a preferred embodiment of the present invention, the functional compound is formed by reacting a thioamide group-containing compound with a compound containing both an alkenyl group and a ketone group.

In a preferred embodiment of the invention, the compound containing a thioamide group is dithiooxamide, N-dibenzyldithiooxamide, benzene-1, 4-dithiobenzamide, didodecyldiaminooxalamide or a compound of formula (I):

R¹is H, (CH)₂)_n1CH₃Or a phenyl group,

n1 is an integer from 0 to 17,

the compound shown in the formula (I) is preferably selected from thiocarboxamide, thioacetamide, thionicotinamide, thiobenzamide and 3, 4-dimethylthiobenzamide. The thioamide group-containing compound has a function of chelating metal ions.

In a preferred embodiment of the present invention, the compound having both an alkenyl group and a ketone group is a compound represented by formula (II):

R²is H, CH₃、C₂H₅、C₃H₇，

R³Is H or CH₃，

R⁴Is (CH)₂)_n2CH₃A phenyl group or a cyclopropyl group,

n2 is an integer from 0 to 12,

the compound containing both alkenyl and ketone groups is preferably selected from the group consisting of phenylbutenone, 1-cyclopropyl-2-propenone, 3-penten-2-one, 1-penten-3-one, 4-hexen-3-one, 3-methyl-3-hexen-2-one, 3-hepten-2-one, 1-hepten-3-one, 1-octen-3-one, 3-methyl-3-buten-2-one, and phenylpropenone.

In a preferred embodiment of the present invention, the functional compound is a compound represented by formula (III):

R¹is H, (CH)₂)_n1CH₃Or a phenyl group,

n1 is an integer from 0 to 17,

R²is H, CH₃、C₂H₅、C₃H₇Or a phenyl group,

R³is H or CH₃，

R⁴Is (CH)₂)_n2CH₃A phenyl group or a cyclopropyl group,

n2 is an integer from 0 to 12.

In a more preferred embodiment of the invention, the compound of formula (III) has a molecular weight of 200-1000.

In a more preferred embodiment of the invention, the compound containing a thioamide group is reacted with the compound containing both an alkenyl group and a keto group in a weight ratio of 1:1.0 to 2.2.

In a more preferred embodiment of the invention, the emulsifier is a non-ionic surfactant, preferably an isomeric fatty alcohol polyoxyethylene ether, a sorbitan fatty acid ester or a mixture thereof,

the other additives are ammonium fatty alcohol ether sulfate, cocodiethanolamide, cocopropylamidobetaine or their mixture.

In a preferred embodiment of the invention, the preparation method of the low-temperature soaping agent for printing the reactive dye is provided, and comprises the following steps:

a) preparation of functional compounds: adding thioamide group-containing compound, alkenyl and keto-containing compound and anhydrous ethanol into a reactor, dissolving completely, heating and refluxing at 70-85 deg.C for 8-12 hr, cooling the reaction solution to room temperature, distilling under low pressure to remove ethanol,

b) in the presence of an emulsifier, uniformly mixing a high-efficiency dispersant, other additives, a poly organic acid salt and a functional compound in a weight ratio of 1:5-50:20-200:65-300, more preferably in a weight ratio of 1:5-10:22-40:80-180, particularly preferably in a weight ratio of 1:6-9:23-35:90-150,

the poly organic acid salt is polyhexamethylene guanidine hydrochloride, sodium poly alcohol ether sulfonate, sodium poly stearate, polylysine hydrochloride or the mixture thereof,

the high-efficiency dispersing agent is sodium polycarboxylate, sodium polyphosphate, ammonium polyacrylate, sodium lignosulfonate or a mixture of the sodium polycarboxylate, the sodium polyphosphate and the sodium lignosulfonate.

The functional compound is a compound shown as a formula (III):

R¹is H, (CH)₂)_n1CH₃Or a phenyl group,

n1 is an integer from 0 to 17,

R²is H, CH₃、C₂H₅、C₃H₇Or a phenyl group,

R³is H or CH₃，

R⁴Is (CH)₂)_n2CH₃A phenyl group or a cyclopropyl group,

n2 is an integer from 0 to 12.

For example, in one embodiment, the preparation method of the low-temperature soaping agent for printing reactive dyes comprises the following preferred steps:

1) enabling thiocarboxamide, absolute ethyl alcohol and phenyl acrylketone to perform reflux reaction for 10 hours in a three-neck flask at the temperature of 70-85 ℃ according to the weight ratio of 1 (60-200) to 1.0-2.2, cooling to the room temperature of 25-30 ℃ after complete reaction, and distilling at low pressure to remove the ethyl alcohol for later use;

2) under the action of an emulsifier, uniformly mixing a high-efficiency dispersant, other additives, a poly organic acid salt and a formula (III) according to a weight ratio of 1 (5-50) to 20-200 to 65-300 to obtain the low-temperature soaping agent for reactive dye printing.

The invention can control the performance index of the mixture by adjusting the weight ratio, the product is not easy to hydrolyze, and the appearance and the structural stability are improved.

Examples

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.

The performance of the low-temperature soaping agent for printing of the reactive dye prepared in each example of the invention is verified by the following test.

Low temperature soaping agent performance test for reactive dye printing

1. Fabric: printing woven cloth

2. Process for the preparation of a coating

Conventional process

Printed fabric → cold water washing → hot water washing → 90-100 ℃ soaping (1-2g/L of commercially available soaping agent) → warm water washing → cold water washing → drying

Low temperature process

Printed fabric → cold water washing → warm water washing → 55-65 ℃ soaping (1-2g/L soaping agent) → warm water washing → cold water washing → drying

3. Performance testing

3.1 stability

And (3) placing the product in a closed sample bottle, placing for 6 months at 25 ℃, and observing whether the product is layered or not and whether a precipitate appears or not.

3.2 Friction fastness

Dry and wet rub fastness: according to GB/T3920-.

3.3 soaping fastness

Referring to GB/T3921-.

3.4 stain resistance

(1) Preparation of hydrolytic reactive dyes: 0.1g of reactive red dye is weighed and dissolved in 1L of water, and the pH value is adjusted to 6-7.

(2) And (3) testing the stain resistance: white pure cotton fabric, bath ratio of 1:20, sample soaping agent of 2g/L, the hydrolyzed dye as a solvent, heating to 60 ℃/95 ℃ at a heating rate of 2 ℃/min for processing for 20min, simultaneously performing a blank solution test, and after drying, evaluating the color difference of the two samples by using a gray sample card, wherein the higher the numerical value is, the better the soaping fastness is.

3.5 foaming Properties

The foaming performance of the soaping agent solution of the sample under different temperature conditions (30/60/90 ℃) is tested by adopting a Roche foamer method, and the lower the foaming (the lower the foam breaking height value), the faster the defoaming (the lower the foam breaking height value after 5min or the shorter the foam breaking time within 5 min), the better the defoaming performance.

3.6 Depasting Properties

Weighing a piece of printing fabric to obtain the weight W of the printing fabric;

scraping, drying, steaming, keeping constant weight, and weighing_A；

Cleaning, drying, weighingW_B。

Percent of paste removal%_A-W_B)/(W_A-W)×100％

The higher the number of the paste removal rate, the better the paste removal effect.

Example 1

1) Enabling 0.136 weight part of thiocarbamide, 20 weight parts of absolute ethyl alcohol and 0.168 weight part of phenyl acrylketone to react for 12 hours in a three-neck flask at the temperature of 80 ℃, cooling to room temperature after the reaction is completed, and distilling under low pressure to remove the ethyl alcohol for later use.

2) Under the action of 4 parts by weight of emulsifier sorbitan fatty acid ester, 1 part by weight of sodium lignosulfonate, 6 parts by weight of fatty alcohol ether ammonium sulfate, 25 parts by weight of polylysine hydrochloride and 100 parts by weight of the polymer are uniformly mixed to obtain the low-temperature soaping agent for reactive dye printing.

Example 2

1) 0.106 weight part of dithiooxamide, 20 weight parts of absolute ethyl alcohol and 0.232 weight part of benzyl ketone are reacted in a three-neck flask at the temperature of 80 ℃ for 12 hours, after the reaction is completed, the reaction product is cooled to the room temperature, and the ethyl alcohol is removed by low-pressure distillation for later use.

2) Under the action of 3 parts by weight of sorbitol fatty acid ester serving as an emulsifier, 1 part by weight of ammonium polyacrylate, 6 parts by weight of ammonium fatty alcohol ether sulfate, 28 parts by weight of polylysine hydrochloride and 106 parts by weight of the polymer are uniformly mixed to obtain the low-temperature soaping agent for printing the reactive dye.

Example 3

1) 0.096 part by weight of benzene-1, 4-dithiobenzamide, 18 parts by weight of absolute ethyl alcohol and 0.210 part by weight of 3-penten-2-ketone are reacted in a three-neck flask at the temperature of 80 ℃ for 12 hours, after the reaction is completed, the mixture is cooled to room temperature, and the ethyl alcohol is removed through low-pressure distillation for later use.

2) Under the action of 6 parts by weight of emulsifier heterogeneous fatty alcohol-polyoxyethylene ether, uniformly mixing 1 part by weight of sodium polyphosphate, 8 parts by weight of coconut oil-based diethanolamide, 30 parts by weight of sodium polyolethersulfonate and 128 parts by weight of the polymer to obtain the low-temperature soaping agent for reactive dye printing.

Example 4

1) Reacting 0.136 weight part of thioacetamide, 25 weight parts of absolute ethyl alcohol and 0.148 weight part of phenyl propenyl ketone in a three-neck flask at the temperature of 80 ℃ for 12 hours, cooling to room temperature after complete reaction, and distilling under low pressure to remove the ethyl alcohol for later use.

2) Under the action of 5 parts by weight of emulsifier heterogeneous fatty alcohol-polyoxyethylene ether, 1 part by weight of sodium polycarboxylate, 6 parts by weight of coco propyl amide betaine, 32 parts by weight of polylysine hydrochloride and 140 parts by weight of the polymer are uniformly mixed to obtain the low-temperature soaping agent for reactive dye printing.

The application effects of the examples are compared as shown in table 1.

TABLE 1 comparison of the application effects of different printing soaping agents

From table 1, the application effects of the low-temperature soaping agent for printing of reactive dyes prepared in examples 1 to 4 can be obtained, and the low-temperature soaping agent has the advantages of good stability, low foam, good dry and wet rubbing fastness, prominent anti-sticking effect, small color change, excellent soaping fastness, good paste removal performance and good hand feeling.

Although the present invention has been described with reference to the above embodiments, it should be understood that the scope of the present invention is not limited thereto, and that various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention.