Salt-tolerant disperse printing thickening agent and preparation method thereof

Abstract

The invention discloses a salt-resistant disperse printing thickening agent and a preparation method thereof, and belongs to the technical field of textile dyeing and printing auxiliaries. The raw materials comprise the following components: 3%-5% of polyethylene glycol-6000, 1%-3% of hexamethylene diisocyanate, 0.02%-0.05% of a catalyst organic bismuth, 0.5%-2% of hydroxyethyl acrylate, 10%-20% of an unsaturated acidic monomer, 15%-30% of a neutralizing agent, 1%-5% of octadecyl methacrylate, 3%-5% of methyl methacrylate, 3%-6% of Span-80 and 0.1%-0.6% of sodium hydrogen sulfite. The cleaning agent is prepared from the following components in percentage by weight: 0.1-0.6% of sodium persulfate, 8-15% of odorless kerosene, 2-5% of Tween-80 and the balance of deionized water. According to the salt-resistant disperse printing thickening agent and the preparation method thereof disclosed by the invention, a novel cross-linking agent is obtained through polycondensation reaction of polyethylene glycol-6000, hexamethylene diisocyanate and hydroxyethyl acrylate, and then the cross-linking agent is introduced into a polyacrylate main chain through the polycondensation reaction, so that the salt-resistant disperse printing thickening agent is obtained. Therefore, the thickening capacity and electrolyte resistance of the product are improved by utilizing the combined action of the polyurethane thickening agent and the acrylate thickening agent.

Description

Technical Field

[0001] The invention relates to the technical field of textile dyeing and printing auxiliaries, in particular to a salt-resistant disperse printing thickener and a preparation method thereof. Background Art

[0002] Disperse printing is a printing method that uses thickeners to transfer finely dispersed pigment particles onto fabrics. It has the characteristics of simple processing technology, no steaming and washing, and less "three wastes". In disperse printing, the disperse printing paste is composed of thickeners, water and paint. The printing machine scraper generates shear force on the printing paste, which greatly reduces its viscosity in an instant, and then prints it on the fabric after passing through the screen. When the shear force disappears, it returns to its original high viscosity, making the fabric printing outline clear. This viscosity change that occurs with the change in the size of the shear force is mainly achieved by the thickener.

[0003] The existing disperse printing thickeners are mainly acrylic synthetic thickeners, which have the characteristics of rapid thickening, low dosage, and easy use. The cross-linking agent N,N-methylenebisacrylamide used in the synthesis of traditional disperse thickeners has poor water solubility and high cross-linking reaction activity. Therefore, the synthesis reaction temperature is low, the reaction controllability is poor, the product molecular weight is low and the molecular weight distribution is large, resulting in poor thickening ability of the disperse thickener and low electrolyte resistance. When encountering electrolytes, the carboxylate stabilization system is destroyed, resulting in a significant decrease in the viscosity of the printing paste and instability of the paste system. Summary of the invention

[0004] The purpose of the present invention is to provide a salt-resistant disperse printing thickener and a preparation method thereof, and a disperse printing thickener with excellent thickening ability and electrolyte resistance is obtained by combining the combined effects of a polyurethane thickener and an acrylic thickener. Firstly, polyethylene glycol-6000, hexamethylene diisocyanate and hydroxyethyl acrylate are selected to synthesize a new cross-linking agent, which has excellent water solubility and also has a certain phase thickening ability; then the new cross-linking agent, unsaturated acidic monomers, octadecyl methacrylate, methyl methacrylate, etc. are subjected to inverse emulsion polymerization to obtain the salt-resistant disperse printing thickener.

[0005] To achieve the above purpose, the present invention provides a salt-resistant disperse printing thickener, which comprises the following components in weight percentage: 3-5% of polyethylene glycol-6000, 1-3% of hexamethylene diisocyanate, 0.02-0.05% of catalyst organic bismuth, 0.5-2% of hydroxyethyl acrylate, 10-20% of unsaturated acid monomer, 15-30% of neutralizer, 1-5% of octadecyl methacrylate, 3-5% of methyl methacrylate, 3-6% of Span-80, 0.1-0.6% of sodium bisulfite, 0.1-0.6% of sodium persulfate, 8-15% of odorless kerosene, 2-5% of Tween-80, and the balance is deionized water.

[0006] Preferably, the unsaturated acidic monomer includes one or more of acrylic acid, methacrylic acid and itaconic acid.

[0007] Preferably, the neutralizing agent is liquid alkali with a mass fraction of 32%.

[0008] The present invention also provides a method for preparing a salt-resistant disperse printing thickener, comprising the following steps:

[0009] Step 1, preparing a new cross-linking agent;

[0010] Step 2, preparing a neutralization solution;

[0011] Step 3, preparing an aqueous phase liquid;

[0012] Step 4, preparing an emulsion;

[0013] Step 5: preparing a salt-resistant disperse printing thickener.

[0014] Preferably, the specific operation of step one is: adding weighed polyethylene glycol-6000 to a reactor, gradually heating to 50-100° C., adding weighed hexamethylene diisocyanate and catalyst organic bismuth to the reactor, keeping the temperature for reaction for 1-2 hours, adding weighed hydroxyethyl acrylate, and continuing to keep the temperature for reaction for 2-4 hours to obtain a new cross-linking agent.

[0015] Preferably, the specific operation of step 2 is: adding weighed unsaturated acidic monomer and deionized water into a neutralization tank, slowly adding weighed neutralizing agent under stirring at 20-25 Hz, and controlling the neutralization temperature to be less than 35°C.

[0016] Preferably, the specific operation of step three is: when the neutralized solution in step two is cooled to 25° C., the novel cross-linking agent and sodium persulfate are added and stirred evenly to obtain an aqueous phase liquid.

[0017] Preferably, the specific operation of step 4 is: adding weighed odorless kerosene, Span-80, octadecyl methacrylate and methyl methacrylate into an emulsification tank, adding the aqueous phase liquid under rapid stirring, emulsifying for 20-40 minutes, and the emulsification temperature is less than 35°C.

[0018] Preferably, the specific operation of step five is: adding the emulsion into a reaction kettle, slowly adding a 3% sodium bisulfite aqueous solution under stirring at 10-15 Hz until no obvious heat is released, controlling the reaction temperature at 65-75° C., reacting for 2-3 hours, heating to 80-100° C., and reacting for 1-2 hours;

[0019] After the reaction is completed, the temperature is lowered to 60°C-65°C, Tween-80 is added, and stirring is continued for 10-20 minutes. Stirring is stopped, and the material is filtered to obtain a salt-resistant disperse printing thickener.

[0020] Therefore, the present invention adopts the above-mentioned salt-tolerant disperse printing thickener and its preparation method, which has the following beneficial effects:

[0021] 1. The present invention improves the thickening ability and electrolyte resistance of the product by combining the polyurethane thickener and the acrylic thickener;

[0022] 2. The present invention synthesizes a novel crosslinking agent from polyethylene glycol-6000, hexamethylene diisocyanate and hydroxyethyl acrylate. The crosslinking agent has excellent water solubility and a certain phase thickening ability. Therefore, it has a certain protective effect during the synthesis of the inverse emulsion, thereby making the polymerization reaction control more stable.

[0023] 3. By introducing long polyethylene glycol chains into the main chain of acrylic polymer, the product has both associative thickening and chain entanglement thickening capabilities;

[0024] 4. By introducing non-ionic polyethylene glycol through polymer chain segments, the printing paste has excellent water retention properties, and the printed pattern is clearer and does not bleed.

[0025] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The invention discloses a synthetic flow chart of a salt-tolerant disperse printing thickener and a preparation method thereof. DETAILED DESCRIPTION

[0027] The technical solution of the present invention is further described below through the accompanying drawings and embodiments.

[0028] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0029] The invention provides a salt-resistant disperse printing thickener, which comprises the following components in percentage by weight: 3-5% of polyethylene glycol-6000, 1-3% of hexamethylene diisocyanate, 0.02-0.05% of catalyst organic bismuth, 0.5-2% of hydroxyethyl acrylate, 10-20% of unsaturated acid monomer, 15-30% of neutralizer, 1-5% of octadecyl methacrylate, 3-5% of methyl methacrylate, 3-6% of Span-80, 0.1-0.6% of sodium bisulfite, 0.1-0.6% of sodium persulfate, 8-15% of odorless kerosene, 2-5% of Tween-80, and the balance is deionized water.

[0030] The unsaturated acidic monomer includes one or more of acrylic acid, methacrylic acid and itaconic acid, and the neutralizing agent is liquid alkali with a mass fraction of 32%.

[0031] like Figure 1 As shown, the present invention also provides a method for preparing a salt-resistant disperse printing thickener, comprising the following steps:

[0032] Step 1, prepare a new cross-linking agent; add weighed polyethylene glycol-6000 to a reactor, gradually increase the temperature to 50-100°C, add weighed hexamethylene diisocyanate and catalyst organic bismuth to the reactor, keep the temperature for 1-2 hours, add weighed hydroxyethyl acrylate, and continue to keep the temperature for 2-4 hours to obtain a new cross-linking agent.

[0033] Step 2, prepare neutralization solution; add weighed unsaturated acidic monomer and deionized water into the neutralization tank, slowly add weighed neutralizer under stirring at 20-25Hz, and control the neutralization temperature to be less than 35°C.

[0034] Step 3, preparing an aqueous phase liquid; when the neutralized liquid in step 2 is cooled to 25° C., the novel cross-linking agent and sodium persulfate are added and stirred evenly to obtain an aqueous phase liquid.

[0035] Step 4, prepare emulsion: add weighed odorless kerosene, Span-80, octadecyl methacrylate and methyl methacrylate into an emulsification tank, add aqueous phase liquid under rapid stirring, emulsify for 20-40 minutes, and the emulsification temperature is less than 35°C.

[0036] By introducing the long carbon chain in the structure of octadecyl methacrylate, the hydrophobic effect of the long carbon chain can be compounded with the hydrophilic structure of polyethylene glycol-6000, thereby improving the thickening ability of the product; at the same time, the long carbon chain of the side group has a certain protective effect, protecting the carboxyl group from the influence of electrolytes, thereby improving the electrolyte resistance of the product.

[0037] Since most of the raw materials of the product are hydrophilic, their reactivity is not much different, and the raw materials are more inclined to homopolymerization, resulting in a lower relative molecular mass of the product. By introducing water-insoluble methyl methacrylate to adjust the reactivity of different raw materials, the raw materials are more likely to copolymerize, thereby increasing the relative molecular mass of the product and further improving the thickening ability of the product.

[0038] Step 5, preparing a salt-resistant disperse printing thickener: adding the emulsion into a reaction kettle, slowly adding a 3% sodium bisulfite aqueous solution under stirring at 10-15 Hz until no obvious heat is released, controlling the reaction temperature at 65-75°C, reacting for 2-3 hours, heating to 80-100°C, and reacting for 1-2 hours;

[0039] After the reaction is completed, the temperature is lowered to 60°C-65°C, Tween-80 is added, and stirring is continued for 10-20 minutes. Stirring is stopped, and the material is filtered to obtain a salt-resistant disperse printing thickener.

[0040] Example 1

[0041] A method for preparing a salt-resistant disperse printing thickener comprises the following steps:

[0042] Preparation of a novel crosslinking agent: 3 g of polyethylene glycol-6000 was added to a reaction kettle, the temperature was gradually raised to 75°C, 1 g of hexamethylene diisocyanate and 0.02 g of catalyst organic bismuth were added to the reaction kettle, the reaction was kept warm for 1 hour, 2 g of hydroxyethyl acrylate was added, and the reaction was continued for 2 hours to obtain a novel crosslinking agent;

[0043] Preparation of neutralization solution: Add 10g acrylic acid and deionized water into a neutralization tank, slowly add 15g neutralizer while stirring at 20Hz, and control the neutralization temperature to be less than 35℃;

[0044] Preparation of aqueous phase liquid: Add the above-mentioned novel cross-linking agent and 0.1 g of sodium persulfate to the above-mentioned neutralized liquid cooled to 25° C. and stir evenly to obtain an aqueous phase liquid;

[0045] Preparation of emulsion: Add 8g of odorless kerosene, 3g of Span-80, 1g of octadecyl methacrylate and 3g of methyl methacrylate into an emulsifying tank, add the aqueous phase liquid under rapid stirring, emulsify for 20 minutes, and the emulsification temperature is less than 35°C;

[0046] Preparation of salt-tolerant disperse printing thickener: add the emulsion into the reactor, slowly add 3% sodium bisulfite aqueous solution with stirring at 10Hz until no obvious heat is released, control the reaction temperature at 65℃, react for 2h, raise the temperature to 85℃, and react for 1h;

[0047] After the reaction was completed, the temperature was lowered to 60°C, 2 g of Tween-80 was added, and stirring was continued for 10 min. Stirring was stopped, and the material was filtered to obtain a salt-tolerant disperse printing thickener.

[0048] Example 2

[0049] A method for preparing a salt-resistant disperse printing thickener comprises the following steps:

[0050] Preparation of a novel crosslinking agent: Add 5 g of polyethylene glycol-6000 to a reaction kettle, gradually raise the temperature to 75°C, add 5 g of hexamethylene diisocyanate and 0.05 g of catalyst organic bismuth to the reaction kettle, keep the temperature for reaction for 1 hour, add 0.5 g of hydroxyethyl acrylate, and continue to keep the temperature for reaction for 4 hours to obtain a novel crosslinking agent;

[0051] Preparation of neutralization solution: Add 15g methacrylic acid, 5g itaconic acid and deionized water into a neutralization tank, slowly add 30g neutralizer while stirring at 25Hz, and control the neutralization temperature to be less than 35℃;

[0052] Preparation of aqueous phase liquid: Add the above-mentioned novel cross-linking agent and 0.6 g of sodium persulfate to the above-mentioned neutralized liquid cooled to 25° C. and stir evenly to obtain an aqueous phase liquid;

[0053] Preparation of emulsion: Add 15g of odorless kerosene, 6g of Span-80, 5g of octadecyl methacrylate and 5g of methyl methacrylate into an emulsifying tank, add the aqueous phase liquid under rapid stirring, emulsify for 40 minutes, and the emulsification temperature is less than 35°C;

[0054] Preparation of salt-tolerant disperse printing thickener: add the emulsion into the reactor, slowly add 3% sodium bisulfite aqueous solution with stirring at 15Hz until no obvious heat is released, control the reaction temperature at 75℃, react for 3h, raise the temperature to 85℃, and react for 2h;

[0055] After the reaction was completed, the temperature was lowered to 65°C, 5 g of Tween-80 was added, and stirring was continued for 20 min. Stirring was stopped, and the material was filtered to obtain a salt-resistant disperse printing thickener.

[0056] Example 3

[0057] A method for preparing a salt-resistant disperse printing thickener comprises the following steps:

[0058] Preparation of a novel cross-linking agent: 4 g of polyethylene glycol-6000 was added to a reaction kettle, the temperature was gradually raised to 75°C, 2 g of hexamethylene diisocyanate and 0.04 g of catalyst organic bismuth were added to the reaction kettle, the reaction was kept warm for 1.5 h, 1 g of hydroxyethyl acrylate was added, and the reaction was continued for 3 h to obtain a novel cross-linking agent;

[0059] Preparation of neutralization solution: Add 13g acrylic acid, 2g itaconic acid and deionized water into a neutralization tank, slowly add 20g neutralizer while stirring at 20Hz, and control the neutralization temperature to be less than 35℃;

[0060] Preparation of aqueous phase liquid: Add the above-mentioned novel cross-linking agent and 0.4 g of sodium persulfate to the above-mentioned neutralized liquid cooled to 25° C. and stir evenly to obtain an aqueous phase liquid;

[0061] Preparation of emulsion: Add 12g of odorless kerosene, 4g of Span-80, 3g of octadecyl methacrylate and 4g of methyl methacrylate into an emulsifying tank, add the aqueous phase liquid under rapid stirring, emulsify for 30 minutes, and the emulsification temperature is less than 35°C;

[0062] Preparation of salt-tolerant disperse printing thickener: add the emulsion into the reactor, slowly add 3% sodium bisulfite aqueous solution with stirring at 12Hz until no obvious heat is released, control the reaction temperature at 70℃, react for 2.5h, raise the temperature to 85℃, and react for 1.5h;

[0063] After the reaction was completed, the temperature was lowered to 62°C, 4 g of Tween-80 was added, and stirring was continued for 15 min. Stirring was stopped, and the material was filtered to obtain a salt-tolerant disperse printing thickener.

[0064] The products obtained in the above embodiments were subjected to performance tests:

[0065] 1. Dispersed printing test

[0066] Fabric Used: Polyester Woven;

[0067] Color paste formula: 5% disperse dye, X% thickener, the balance is water;

[0068] Color paste viscosity: 25000mPa·S;

[0069] Printing process: prepare color paste → printing → drying (100℃×1min) → washing → baking (180℃×150s) → performance evaluation;

[0070] 2. White slurry viscosity test

[0071] Deionized water was used to prepare a 2% thickener paste, and the white paste viscosity was measured at a constant speed of 6 rpm at room temperature.

[0072] 3. Electrolyte resistance test

[0073] Electrolyte resistance is expressed as viscosity retention rate. Add 1g of 0.5% sodium chloride aqueous solution to the above thickener white paste and measure the viscosity of the white paste after adding electrolyte. Viscosity retention rate = η 加氯化钠后 / η 加氯化钠前 , the higher the viscosity retention rate, the better the electrolyte resistance.

[0074] 4. Color yield test

[0075] The above disperse printed fabric samples were used as test samples and tested on a Datacolor colorimeter. K / S is used to represent the apparent color yield of the fabric. The larger the K / S value, the darker the color yield.

[0076] Table 1 Application performance of disperse printing thickener

[0077]

[0078] It can be seen from the above table that the disperse printing thickener of the present invention has excellent thickening ability, electrolyte resistance and high color yield.

[0079] Therefore, the present invention adopts the above-mentioned salt-resistant disperse printing thickener and its preparation method, obtains a new cross-linking agent by polycondensation reaction of polyethylene glycol-6000, hexamethylene diisocyanate and hydroxyethyl acrylate, and then introduces the cross-linking agent into the polyacrylate main chain through polymerization reaction, thereby utilizing the combined effect of the polyurethane thickener and the acrylate thickener to improve the thickening ability and electrolyte resistance of the product.

[0080] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A salt-tolerant disperse printing thickener, characterized in that: The invention comprises the following components in percentage by weight: 3-5% of polyethylene glycol-6000, 1-3% of hexamethylene diisocyanate, 0.02-0.05% of catalyst organic bismuth, 0.5-2% of hydroxyethyl acrylate, 10-20% of unsaturated acidic monomer, 15-30% of neutralizing agent, 1-5% of octadecyl methacrylate, 3-5% of methyl methacrylate, 3-6% of Span-80, 0.1-0.6% of sodium bisulfite, 0.1-0.6% of sodium persulfate, 8-15% of odorless kerosene, 2-5% of Tween-80, and the balance is deionized water.

2. A salt-tolerant disperse printing thickener according to claim 1, characterized in that: The unsaturated acidic monomer includes one or more of acrylic acid, methacrylic acid and itaconic acid.

3. A salt-tolerant disperse printing thickener according to claim 2, characterized in that: The neutralizing agent is liquid alkali with a mass fraction of 32%.

4. A method for preparing a salt-tolerant disperse printing thickener as claimed in claim 3, characterized in that: The following steps are involved: Step 1, preparing a new cross-linking agent; Step 2, preparing a neutralization solution; Step 3, preparing an aqueous phase liquid; Step 4: preparing an emulsion; Step 5: preparing a salt-resistant disperse printing thickener.

5. The method for preparing a salt-tolerant disperse printing thickener according to claim 4, characterized in that: The specific operation of step one is: add weighed polyethylene glycol-6000 to the reactor, gradually increase the temperature to 50-100°C, add weighed hexamethylene diisocyanate and catalyst organic bismuth to the reactor, keep the temperature for 1-2 hours, add weighed hydroxyethyl acrylate, and continue to keep the temperature for 2-4 hours to obtain a new cross-linking agent.

6. The method for preparing a salt-tolerant disperse printing thickener according to claim 4, characterized in that: The specific operation of step 2 is: add the weighed unsaturated acidic monomer and deionized water into the neutralization tank, slowly add the weighed neutralizer under stirring at 20-25 Hz, and control the neutralization temperature to be less than 35°C.

7. The method for preparing a salt-tolerant disperse printing thickener according to claim 4, characterized in that: The specific operation of step three is: when the neutralized solution in step two is cooled to 25° C., the novel cross-linking agent and sodium persulfate are added and stirred evenly to obtain an aqueous phase liquid.

8. The method for preparing a salt-tolerant disperse printing thickener according to claim 4, characterized in that: The specific operation of step four is: add weighed odorless kerosene, Span-80, octadecyl methacrylate and methyl methacrylate into the emulsification tank, add the aqueous phase liquid under rapid stirring, emulsify for 20-40 minutes, and the emulsification temperature is less than 35°C.

9. The method for preparing a salt-tolerant disperse printing thickener according to claim 4, characterized in that: The specific operation of step five is: add the emulsion into the reactor, slowly add 3% sodium bisulfite aqueous solution under stirring at 10-15Hz until no obvious heat is released, control the reaction temperature at 65-75°C, react for 2-3h, raise the temperature to 80-100°C, and react for 1-2h; After the reaction is completed, the temperature is lowered to 60°C-65°C, Tween-80 is added, and stirring is continued for 10-20 minutes. Stirring is stopped, and the material is filtered to obtain a salt-resistant disperse printing thickener.

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