Polyacrylate for acid dye printing instead of urea and synthesis method

Abstract

The invention discloses a polyacrylate compound for acid dye printing replacing urea and a synthesis method, belonging to the technical field of polymer material synthesis. The polyacrylate compound for acid dye printing replacing urea comprises a polymerization monomer, a cross-linking monomer, a composite emulsifier and an initiator, the polymerization monomer comprises at least an acrylic acid monomer, an acrylic ester and sodium styrene sulfonate, and also comprises itaconic acid or maleic anhydride, the cross-linking monomer comprises diallyl phthalate, the composite emulsifier comprises a reactive emulsifier, a nonionic emulsifier and / or an anionic emulsifier, the above raw materials are subjected to emulsion polymerization in a redox system to obtain the polyacrylate compound for acid dye printing replacing urea, the polyacrylate compound forms a network structure in an extended state, and the ability to bind water molecules and the network coating and holding water can be greatly improved in combination with the multiple anionic groups possessed by the polyacrylate compound, the polyacrylate compound has excellent moisture absorption, moisture retention, osmotic solubilization, dispersion and other properties, and has excellent environmental protection.

Description

Technical Field

[0001] The invention relates to the technical field of polymer material synthesis, in particular to polyacrylate for acid dye printing replacing urea and a synthesis method thereof. Background Art

[0002] In the processing of nylon fabrics, printing on them with acid dyes is a relatively mainstream processing method. However, urea is used as an auxiliary agent in the processing process. The ammonia nitrogen content in urea is relatively high, which will cause ammonia nitrogen emissions to exceed the standard.

[0003] Combined with the structural characteristics of acid dyes, they are generally aromatic sodium sulfonates, containing sulfonic acid groups, hydroxyl groups and other groups. A few are sodium carboxylates that ionize into pigment acid anions in water and can combine with amino or amide groups on the fiber. Nylon contains a large number of amino and carboxyl groups, which are cationic in acidic media. Due to the effect of Coulomb attraction, they can positionally adsorb anionic dyes and bond with nylon under high-temperature steaming conditions. However, weak acid dyes for nylon have the problem of low dye solubility. When preparing the color paste, it is necessary to add appropriate urea, which has the effects of hygroscopicity, swelling, solubilization, etc., to help acid dyes dissolve and improve the color brightness. If urea is not added to the printing paste to help dissolve, the dye is difficult to dissolve, and condensation will occur after cooling. The addition of urea can not only improve the solubility stability of the dye, but also accelerate the bonding of the dye to the nylon fiber.

[0004] In the prior art, researchers have done a lot of work to reduce ammonia nitrogen emissions, such as the synthesis method of polyalkyl polysaccharide compounds as active printing urea substitutes with application number 202311465003.8, which replaces urea with synthesized polyalkyl polysaccharide compounds to improve the three functions of water locking, moisture absorption, dispersion and volume expansion, and fiber expansion of active dyes in the slurry, but it only has excellent effects on active dye printing; another example is an acidic digital printing ammonia nitrogen-free urea substitute with application number 202410119082.5, its preparation method and use, which is used as a raw material for the preparation of acidic digital printing sizing agents and is not suitable for acidic dye printing processes.

[0005] Based on various public information, there is a need for an ammonia nitrogen-free urea alternative compound for acid dye printing of nylon and its blended fabrics, so as to effectively reduce ammonia nitrogen emissions while ensuring the treatment effect of nylon fabrics. Summary of the invention

[0006] The object of the present invention is to provide polyacrylate for acid dye printing instead of urea and a synthesis method thereof, so as to solve the problems in the background technology.

[0007] To achieve the above object, the technical scheme adopted by the present invention is: a polyacrylate for replacing urea for acid dye printing, wherein the urea replacement compound comprises a polymerizable monomer, a cross-linking monomer, a composite emulsifier and an initiator, wherein the polymerizable monomer comprises at least an acrylic acid monomer, an acrylic ester and sodium styrene sulfonate, and also comprises itaconic acid and / or maleic anhydride, wherein the cross-linking monomer comprises diallyl phthalate, and the composite emulsifier comprises a reactive emulsifier, a nonionic emulsifier and / or an anionic emulsifier, wherein the reactive emulsifier is 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate;

[0008] The urea replacement compound has the following structural formula:

[0009] ,

[0010] Among them, R1 is one or more of -H, -CH3, -CH2COOH or -COOH; R2 is one or more of -CH3, -CH2CH3, -C4H9; R3 is -H and / or -CH3.

[0011] As a further optimization, the acrylate is one or more of methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate.

[0012] As a further optimization, in the polymerized monomers, the mass ratio of the acrylic ester to other polymerized monomers is (1-1.5):1.

[0013] As a further optimization, the acrylic acid monomer is acrylic acid and / or methacrylic acid.

[0014] As a further optimization, the mass of diallyl phthalate is 0.01-0.3% of the total mass.

[0015] As a further optimization, the anionic emulsifier is sodium dodecyl sulfate and / or sodium dodecylbenzene sulfonate, and the nonionic emulsifier is one or more of Peregal O-25, AEO-9, OP-9 or OP-21.

[0016] As a further optimization, the mass of the 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate is 1.5-5% of the total mass.

[0017] As a further optimization, the initiator includes an oxidant and a reductant, the oxidant is ammonium persulfate and / or potassium persulfate, and the reductant is sodium bisulfite.

[0018] As a further optimization, the mass ratio of the oxidant to the reductant is 1:1, and the mass of the initiator is 0.1-1% of the total mass.

[0019] The present invention also provides a method for synthesizing polyacrylate for acid dye printing instead of urea, comprising the following steps:

[0020] S1) dissolving deionized water and part of the composite emulsifier at 40° C., and slowly dropping the polymerization monomer and the cross-linking monomer at 60-65° C., and emulsifying for 30-60 minutes after the dropping is completed, to obtain a pre-emulsion;

[0021] S2) dissolving the deionized water and the remaining composite emulsifier at 70-80 ° C, adding part of the pre-emulsion as the base liquid, and adding the reducing agent, and continuing emulsification for 10 min;

[0022] S3) continuing to add part of the oxidant aqueous solution to initiate polymerization, while dripping the remaining pre-emulsion and the remaining oxidant aqueous solution, the dripping time is 1.5-2.5 h;

[0023] S4) After the addition is completed, the reaction is continued at 80-88° C. for 2-4 hours. After the reaction is completed, the temperature is lowered to below 40° C., alkali is added to adjust the pH to 6-7, and the mixture is filtered to obtain polyacrylate for acid dye printing instead of urea.

[0024] As a further optimization, the mass of the pre-emulsion added in S2 is 1 / 9-1 / 4 of the total mass of the pre-emulsion; the mass of the oxidant aqueous solution added for the first time in S3 is 1 / 4-1 / 5 of the total mass of the oxidant aqueous solution.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] 1. The polyacrylate for acid dye printing replacing urea of ​​the present invention contains almost no nitrogen (the ultra-trace nitrogen element contained in the reactive emulsifier can be ignored). When it is applied to acid dye printing, it can effectively reduce the ammonia nitrogen index content in sewage and has excellent environmental protection characteristics;

[0027] 2. The polyacrylate for acid dye printing replacing urea of ​​the present invention has the functions of moisture absorption, moisturizing, penetrating solubility, and dispersion stability. When it is applied to acid dye printing, the prepared color paste has good stability. When it is used for acid dye printing of nylon and its blended fabrics, it can completely replace urea. The printed fabric has excellent apparent color depth, bright color, and little color light influence;

[0028] 3. The polyacrylate used in acid dye printing to replace urea has a large molecular weight, and a large amount of -COO- and a small amount of SO3 are introduced into the main chain of the macromolecule. -Anionic groups generate negative charges on the polymer molecular chain. The opposite charges in the system repel each other, which promotes the extension of the polymer molecular chain. In the steaming process after acid dye printing, it can better bind a large number of water molecules through hydrogen bonding to improve moisture absorption and moisturizing effects.

[0029] 4. The polyacrylate for acid dye printing replacing urea of ​​the present invention uses diallyl phthalate as a crosslinking monomer, the addition of which enables the system to have a certain three-dimensional crosslinking of the molecular framework. A large number of anionic groups on the side chains in the system combine with water molecules to form hydrogen bonds. The force of the hydrogen bonds causes the curled polymer molecular chains to unwind in the aqueous solution and form a network structure in an extended state, which greatly improves the ability to bind water molecules and the network's ability to wrap and hold water, and can effectively enhance the moisture absorption and moisturizing effects;

[0030] 5. A reactive emulsifier is introduced into the polyacrylate for replacing urea for acid dye printing of the present invention, and a long-chain nonionic hydrophilic segment is introduced into the macromolecular chain, so that the system has good wetting and penetration ability, increases the electrolyte resistance and dispersion stability of the system, avoids the re-aggregation of the dye after dissolution, and ensures the water holding capacity and color paste stability in the subsequent color paste; and in the molecular structure, the reactive emulsifier is the benzene ring in the side chain formed by 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate, and the benzene ring in the side chain formed by the cross-linking monomer diallyl phthalate, which can make the two side chains more effectively form and maintain a synchronous extended structure and network structure through the interaction force between adjacent benzene rings (such as van der Waals force), and further maintain the moisture absorption and moisturizing effect. DETAILED DESCRIPTION

[0031] The following are specific embodiments of the present invention, which further describe the technical solutions of the present invention, but the present invention is not limited to these embodiments.

[0032] Example 1: A method for synthesizing polyacrylate for acid dye printing instead of urea, comprising the following steps:

[0033] S1) dissolving 163 g of deionized water, 4 g of Peregal O-25, 2 g of sodium dodecyl sulfate, and 0.5 g of 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate at 40° C., and slowly adding dropwise polymerization monomers (30 g of methyl acrylate, 30 g of butyl acrylate, 5 g of sodium styrene sulfonate, 30 g of methacrylic acid, and 5 g of itaconic acid) and crosslinking monomers (0.1 g of diallyl phthalate) at 60-65° C., and emulsifying the mixture for 30 min after the addition is completed, to obtain a pre-emulsion;

[0034] S2) dissolving 50 g of deionized water, 4 g of Peregal O-25, 2 g of sodium dodecyl sulfate, and 0.5 g of 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate at 70-80° C., adding 1 / 8 of the pre-emulsion as a base liquid into a three-necked flask, heating to 75° C., adding 0.333 g of a reducing agent, sodium bisulfite, and continuing emulsification for 10 min;

[0035] S3) dissolving 0.333 g of ammonium persulfate in 20 g of deionized water to prepare an aqueous solution of ammonium persulfate, adding 1 / 4 of the aqueous solution of ammonium persulfate to the product of S2 to initiate polymerization, and simultaneously adding the remaining pre-emulsion and the remaining aqueous solution of ammonium persulfate dropwise for 1.5 h;

[0036] S4) After the addition is completed, the reaction is continued at 85°C for 3 h. After the reaction is completed, the temperature is lowered to below 40°C, and alkali is added to adjust the pH to 6-7 to obtain polyacrylate for acid dye printing instead of urea.

[0037] Embodiment 2: A method for synthesizing polyacrylate for acid dye printing instead of urea, comprising the following steps:

[0038] S1) 163 g of deionized water, 4 g of OP-9, 2 g of sodium dodecyl sulfate, and 0.5 g of 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate were dissolved at 40° C., and polymerization monomers (30 g of methyl acrylate, 30 g of butyl acrylate, 5 g of sodium styrene sulfonate, 30 g of methacrylic acid, and 5 g of itaconic acid) and crosslinking monomers (0.1 g of diallyl phthalate) were slowly added dropwise at 60-65° C. After the addition was completed, the mixture was kept warm and emulsified for 30 min to obtain a pre-emulsion;

[0039] S2) 50 g of deionized water and 4 g of OP-9, 2 g of sodium dodecyl sulfate, and 0.5 g of 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate were dissolved at 70-80 ° C, 1 / 8 of the pre-emulsion was added as the base liquid into a three-necked flask, the temperature was raised to 75 ° C, 0.333 g of reducing agent sodium bisulfite was added, and emulsification was continued for 10 min;

[0040] S3) dissolving 0.333 g of ammonium persulfate in 20 g of deionized water to prepare an aqueous solution of ammonium persulfate, adding 1 / 4 of the aqueous solution of ammonium persulfate to the product of S2 to initiate polymerization, and simultaneously adding the remaining pre-emulsion and the remaining aqueous solution of ammonium persulfate dropwise for 1.5 h;

[0041] S4) After the addition is completed, the reaction is continued at 85°C for 3 h. After the reaction is completed, the temperature is lowered to below 40°C, and alkali is added to adjust the pH to 6-7 to obtain polyacrylate for acid dye printing instead of urea.

[0042] Example 3: A method for synthesizing polyacrylate for acid dye printing instead of urea, comprising the following steps:

[0043] S1) 163 g of deionized water, 4 g of AEO-9, 2 g of sodium dodecylbenzene sulfonate, and 0.5 g of 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate are dissolved at 40° C., and polymerization monomers (60 g of ethyl acrylate, 5 g of sodium styrene sulfonate, 30 g of methacrylic acid, and 5 g of maleic anhydride) and crosslinking monomers (0.133 g of diallyl phthalate) are slowly added dropwise at 60-65° C. After the addition is completed, the mixture is kept warm and emulsified for 30 min to obtain a pre-emulsion;

[0044] S2) 50 g of deionized water, 4 g of AEO-9, 2 g of sodium dodecylbenzene sulfonate, and 0.5 g of 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate were dissolved at 70-80 ° C, 1 / 9 of the pre-emulsion was added as the base liquid into a three-necked flask, the temperature was raised to 75 ° C, 0.333 g of reducing agent sodium bisulfite was added, and emulsification was continued for 10 min;

[0045] S3) dissolving 0.333 g of potassium persulfate in 20 g of deionized water to prepare a potassium persulfate aqueous solution, adding 1 / 4 of the potassium persulfate aqueous solution to the product of S2 to initiate polymerization, and simultaneously adding the remaining pre-emulsion and the remaining potassium persulfate aqueous solution dropwise for 1.5 h;

[0046] S4) After the addition is completed, the reaction is continued at 85°C for 3 h. After the reaction is completed, the temperature is lowered to below 40°C, and alkali is added to adjust the pH to 6-7 to obtain polyacrylate for acid dye printing instead of urea.

[0047] Example 4: A method for synthesizing polyacrylate for acid dye printing instead of urea, comprising the following steps:

[0048] S1) dissolving 163 g of deionized water, 3 g of OP-21, and 6 g of 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate at 40° C., and slowly adding dropwise polymerization monomers (33 g of methyl acrylate, 22 g of butyl acrylate, 5 g of sodium styrene sulfonate, 30 g of methacrylic acid, 5 g of acrylic acid, and 5 g of maleic anhydride) and crosslinking monomers (0.20 g of diallyl phthalate) at 60-65° C., and emulsifying the mixture at room temperature for 30 min after the addition is completed, to obtain a pre-emulsion;

[0049] S2) Dissolve 50 g of deionized water, 3 g of OP-21, and 6 g of 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate at 70-80 ° C, add 1 / 7 of the pre-emulsion as a base liquid into a three-necked flask, heat to 75 ° C, add 0.500 g of reducing agent sodium bisulfite, and continue emulsification for 10 min;

[0050] S3) dissolving 0.5 g of ammonium persulfate in 20 g of deionized water to prepare an aqueous solution of ammonium persulfate, adding 1 / 4 of the aqueous solution of ammonium persulfate to the product of S2 to initiate polymerization, and simultaneously adding the remaining pre-emulsion and the remaining aqueous solution of ammonium persulfate dropwise for 1.5 h;

[0051] S4) After the addition is completed, the reaction is continued at 85°C for 3 h. After the reaction is completed, the temperature is lowered to below 40°C, and alkali is added to adjust the pH to 6-7 to obtain polyacrylate for acid dye printing instead of urea.

[0052] Application examples:

[0053] The acid dye printing prepared in Examples 1 to 4 is used in the acid dye printing process of nylon fabric instead of urea polyacrylate. The acid dye printing paste formula is shown in Table 1. For the convenience of application, the solid content of the product is converted to 30% as the basis and then used.

[0054] Table 1 Acid dye printing paste formula

[0055]

[0056] Acid dye printing process: acid dye printing paste → printing → drying (100℃) → steam fixation (102-105℃, 20-45 min) → soaping and washing → drying → printed fabric performance testing and evaluation; the acid dyes selected for printing are weak acid light yellow G, acid red XG, and weak acid dark blue 5R.

[0057] The SCT textile colorimetric system (US X-Rite) and its color difference evaluation system were used to test the K / S value, Integ value, color difference value ∆E, etc. of the printed fabric. The average value was taken from the 4 test points and used as a reference sample with urea printed fabric. The test results of the printed fabric performance are shown in Table 2.

[0058] Table 2 Comparison of nylon acid dye printing performance

[0059]

[0060] It can be seen from the data in Table 2 that for acid dye printing of nylon fabric, the acid dye printing prepared in Examples 1 to 4 of the present invention replaces urea with polyacrylate at a dosage of 5%, and the printing effect reaches the printing effect of 10% of urea. From the perspective of the color yield of the printed fabric, the present invention can reach or slightly exceed the traditional urea printing, the color light is less affected, and the product of the present invention basically does not contain ammonia nitrogen, so it can greatly reduce ammonia nitrogen emissions, improve the comprehensive performance of printed fabrics, and has good economic and social ecological benefits.

[0061] The specific embodiments described herein are merely examples of the spirit of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in similar ways, but they will not deviate from the spirit of the present invention or exceed the scope defined by the appended claims.

Claims

1. A polyacrylate for replacing urea for acid dye printing, characterized in that: The raw materials for preparing the polyacrylate for replacing urea include polymerized monomers, crosslinked monomers, composite emulsifiers and initiators. The polymerized monomers include at least acrylic acid monomers, acrylic acid esters and sodium styrene sulfonate, and also include itaconic acid and / or maleic anhydride. The crosslinked monomers include diallyl phthalate. The composite emulsifier includes reactive emulsifiers, nonionic emulsifiers and anionic emulsifiers, wherein the reactive emulsifier is 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate; the initiator includes an oxidant and a reducing agent, wherein the oxidant is ammonium persulfate and / or potassium persulfate, and the reducing agent is sodium bisulfite. The mass ratio of the oxidant to the reducing agent is 1:1, and the mass of the initiator is 0.1-1% of the total mass.

2. The polyacrylate for replacing urea for acid dye printing according to claim 1, characterized in that: The acrylic acid ester is one or more of methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate.

3. The polyacrylate for replacing urea for acid dye printing according to claim 2, characterized in that: In the polymerizable monomers, the mass ratio of the acrylic ester to other polymerizable monomers is (1-1.5):

1.

4. The polyacrylate for replacing urea for acid dye printing according to claim 1, characterized in that: The acrylic acid monomer is acrylic acid and / or methacrylic acid.

5. The polyacrylate for replacing urea for acid dye printing according to claim 1, characterized in that: The mass of the diallyl phthalate is 0.01-0.3% of the total mass.

6. The polyacrylate for replacing urea for acid dye printing according to claim 1, characterized in that: The anionic emulsifier is sodium dodecyl sulfate and / or sodium dodecylbenzene sulfonate, and the nonionic emulsifier is one or more of Peregal O-25, AEO-9, OP-9 or OP-21.

7. The polyacrylate for replacing urea for acid dye printing according to claim 6, characterized in that: The mass of the 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate is 1.5-5% of the total mass.

8. A method for synthesizing polyacrylate for acid dye printing as a substitute for urea according to any one of claims 1 to 7, characterized in that: The steps include: S1) dissolving deionized water and part of the composite emulsifier at 40° C., and slowly dropping the polymerization monomer and the cross-linking monomer at 60-65° C., and emulsifying for 30-60 minutes after the dropping is completed, to obtain a pre-emulsion; S2) dissolving the deionized water and the remaining composite emulsifier at 70-80 ° C, adding part of the pre-emulsion as the base liquid, and adding the reducing agent, and continuing emulsification for 10 min; S3) adding part of the oxidant aqueous solution to initiate polymerization, and simultaneously dripping the remaining pre-emulsion and the remaining oxidant aqueous solution, the dripping time being 1.5-2.5 h; S4) After the addition is completed, the reaction is continued at 80-88° C. for 2-4 hours. After the reaction is completed, the temperature is lowered to below 40° C., alkali is added to adjust the pH to 6-7, and the mixture is filtered to obtain polyacrylate for acid dye printing instead of urea.

9. The method for synthesizing polyacrylate for replacing urea for acid dye printing according to claim 8, characterized in that: The mass of the pre-emulsion added in S2 is 1 / 9-1 / 4 of the total mass of the pre-emulsion; the mass of the oxidant aqueous solution added for the first time in S3 is 1 / 4-1 / 5 of the total mass of the oxidant aqueous solution.

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