Polymeric polymer printing oil and preparation method thereof

Abstract

The invention belongs to the technical field of printing and dyeing auxiliaries, and particularly discloses polymeric high-molecular printing oil and a preparation method thereof.The polymeric high-molecular printing oil is prepared from, by weight, 75-85 parts of oil-phase synthetic solvent, 0.3-0.8 part of initiator, 0.3-0.6 part of nucleophilic addition catalyst, 10-15 parts of solvent, 0.1-0.4 part of neutralization regulating acid, 8-14 parts of fatty acid and 25-40 parts of polymeric monomer, 12 to 16 parts of acryloylethylenediamine and 28 to 45 parts of pure water. According to the polymeric high-molecular printing oil and the preparation method thereof, the synthesized high-molecular printing oil is a comb-shaped polymer, the apparent viscosity of slurry is effectively improved, the rheological property of the slurry is changed, meanwhile, entanglement between thickeners can be reduced, washing in the soaping process is facilitated, the hand feeling after soaping is improved through adsorption of the polymeric high-molecular printing oil, and the printing quality is improved. And a good promotion effect can be achieved on reactive printing and disperse printing.

Description

Technical Field

[0001] The invention relates to the technical field of printing and dyeing auxiliaries, in particular to a polymerized high molecular printing oil and a preparation method thereof. Background Art

[0002] Reactive printing thickeners can provide good rheological properties, transfer the glue or color paste on the printing screen or printing plate to the fabric, and gradually penetrate the dye into the surface of the fiber, ensuring that the printed pattern has clear outlines, distinct patterns, bright colors, and uniformity. The color is developed under specific humidity and temperature conditions. After the dye is fixed, the reaction products and residues are easy to remove in the downstream process to avoid affecting the feel of the fabric. Reactive printing thickeners usually include starch, carboxymethyl cellulose, and polymers of high molecular weight acrylic acid and acrylic esters. During the post-soap washing process of printing, due to the entanglement of its larger molecular chains, or the cross-linking of the hydroxyl groups contained in it with the multi-active group dyes, it remains on the fabric, resulting in a poor feel.

[0003] In order to solve the problem of the hand feel of printed fabrics after washing, we usually need to use carboxymethyl cellulose with lower viscosity and higher degree of substitution, but the cost increase and color yield reduction caused by this have always been the core problem that plagues the hand feel of thickeners after washing. Such problems exist not only on pure cotton fabrics, but are more prominent on viscose and modal fabrics. The residual active thickener not only affects the hand feel, but the anionic structure brought by its structure will also cause problems such as sticking to the roller and additive spots in the subsequent processing of adding cationic finishing agents.

[0004] Solving such problems is the key to improving the processing quality of fabrics. Usually, printing oil and other substances are added to the color paste to further improve the rheological properties of the paste and effectively reduce the cross-adhesion phenomenon of the polymer during the washing process, thereby improving the removal efficiency of the thickener, and the fabric will feel better after washing. However, the amount of conventional printing oil added is relatively large, and the improvement in the feel is not obvious. At the same time, there is almost no charge neutralization effect on the anionic thickener. Therefore, the present invention takes the above shortcomings as the starting point and designs a new polymerized polymer printing oil to solve the above problems. Summary of the invention

[0005] The purpose of the present invention is to provide a polymerized high molecular printing oil and a preparation method thereof. The synthesized high molecular printing oil is a comb-type polymer. The high surface activity and molecular weight can effectively improve the apparent viscosity of the slurry, change the rheological property of the slurry, and make the printed pattern clearer and fuller. At the same time, the entanglement between thickeners can be reduced, which is convenient for washing in the soaping process. The weak cationic property carried by the polymerized high molecular printing oil can effectively adsorb fabrics, reduce the negative impact of the anionic charge brought by the thickener on the finishing after the fabric is adsorbed, and can also improve the hand feel after soaping through its own adsorption, and can play a good role in promoting both active printing and disperse printing.

[0006] To achieve the above purpose, the present invention provides a polymerized high molecular printing oil, comprising the following raw materials in parts by weight: 75-85 parts of an oil phase synthetic solvent, 0.3-0.8 parts of an initiator, 0.3-0.6 parts of a nucleophilic addition catalyst, 10-15 parts of a solvent, 0.1-0.4 parts of a neutralizing regulating acid, 8-14 parts of a fatty acid, 25-40 parts of a polymerized monomer, 12-16 parts of acrylamide, and 28-45 parts of pure water.

[0007] Preferably, the initiator is azobisisobutylcyanide.

[0008] Preferably, the oil phase synthesis solvent is cyclohexanone.

[0009] Preferably, the nucleophilic addition catalyst is 4-dimethylaminopyridine.

[0010] Preferably, the solvent is ethylene glycol or glycerol.

[0011] Preferably, the neutralizing regulating acid is citric acid.

[0012] Preferably, the fatty acid is oleic acid, erucic acid or stearic acid.

[0013] Preferably, the structural formula of the polymerizable monomer is:

[0014]

[0015] Among them, R1 is oleic acid, R2 is cardanol, R3 is oleic acid, erucic acid or stearic acid; m and n are 3-50; a, b, c are all greater than or equal to 2.

[0016] The present invention also provides a method for preparing a polymerized high molecular weight printing oil, comprising the following steps:

[0017] Step 1: Add the polymerization monomer and the oil phase synthesis solvent to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a condenser reflux device, respectively, and stir them evenly at room temperature;

[0018] Step 2: Add initiator and ethylenediamine to the reaction kettle, heat to 110-115°C, start dripping initiator and ethylenediamine, dripping time is 2h, after dripping is completed, keep warm at 115°C for 2-3h;

[0019] Step 3: After the heat preservation is completed, the temperature is lowered to 75-80°C, a nucleophilic addition catalyst and a fatty acid are added, the mixture is fully stirred and heated to 125-130°C, and the mixture is kept warm for 4-6 hours, and the condensation reflux device is turned on;

[0020] Step 4, after the insulation is completed, the solution is cooled to below 50°C and transferred to a rotary evaporator to remove the oil phase synthetic solvent. After the oil phase synthetic solvent is evaporated, the solvent and pure water are added to the reactor and the temperature is raised to 105-110°C for pressure emulsification. The emulsification time is 1-1.5h. After completion, the temperature is lowered to below 50°C, and a neutralizing adjusting acid is added to adjust the pH value to 6.5-7.5.

[0021] The advantages and beneficial effects of the present invention using the above-mentioned polymerized polymer printing oil and its preparation method are:

[0022] 1. The polymer printing oil synthesized by the present invention is a comb-type polymer. The higher surface activity and molecular weight can effectively increase the apparent viscosity of the slurry, change the rheological properties of the slurry, and make the printed pattern clearer and fuller. At the same time, it can reduce the entanglement between thickeners, which is convenient for washing in the soaping process. The weak cationic properties it carries can effectively adsorb fabrics, reduce the negative impact of the anionic charge brought by the thickener adsorption on the fabric on the post-finishing, and can also improve the feel after soaping through its own adsorption, which can play a good role in promoting both reactive printing and disperse printing.

[0023] 2. The present invention adopts solvent polymerization and is prepared by high-pressure emulsification. No additional emulsifier is needed, and the solvent is recycled in the process. The produced high molecular polymer has a better degree of polymerization and better copolymerization uniformity. The use effect of the product has great promotion value.

[0024] The technical solution of the present invention is further described in detail below through embodiments. DETAILED DESCRIPTION

[0025] The technical solution of the present invention is further illustrated by the following examples.

[0026] 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.

[0027] Unless otherwise defined, the instruments, equipment and reagents used in the present invention are all commercially available.

[0028] A polymerized high molecular printing oil comprises the following raw materials in parts by weight: 75-85 parts of an oil phase synthetic solvent, 0.3-0.8 parts of an initiator, 0.3-0.6 parts of a nucleophilic addition catalyst, 10-15 parts of a solvent, 0.1-0.4 parts of a neutralizing regulating acid, 8-14 parts of a fatty acid, 25-40 parts of a polymerized monomer, 12-16 parts of acrylamide and 28-45 parts of pure water.

[0029] The initiator is azobisisobutyl cyanide.

[0030] The oil phase synthesis solvent is cyclohexanone.

[0031] The nucleophilic addition catalyst is 4-dimethylaminopyridine.

[0032] The solvents are ethylene glycol and glycerol.

[0033] The neutralizing adjusting acid is citric acid.

[0034] The fatty acid is oleic acid, erucic acid or stearic acid.

[0035] The structural formula of the polymerized monomer is:

[0036]

[0037] Among them, R1 is oleic acid, R2 is cardanol, R3 is oleic acid, erucic acid or stearic acid; m and n are 3-50; a, b, c are all greater than or equal to 2.

[0038] A method for preparing a polymerized high molecular weight printing oil comprises the following steps:

[0039] Step 1: Add the polymerization monomer and the oil phase synthesis solvent to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a condenser reflux device, respectively, and stir them evenly at room temperature;

[0040] Step 2: Add initiator and ethylenediamine to the reaction kettle, heat to 110-115°C, start dripping initiator and ethylenediamine, and control the temperature at about 115°C for 2 hours. After the dripping is completed, keep the temperature at 115°C for 2-3 hours.

[0041] Step 3: After the heat preservation is completed, the temperature is lowered to 75-80°C, a nucleophilic addition catalyst and a fatty acid are added, the mixture is fully stirred and heated to 125-130°C, and the mixture is kept warm for 4-6 hours, and the condensation reflux device is turned on;

[0042] Step 4, after the insulation is completed, the solution is cooled to below 50°C and transferred to a rotary evaporator to remove the oil phase synthetic solvent. After the oil phase synthetic solvent is evaporated, the solvent and pure water are added to the reactor and the temperature is raised to 105-110°C for pressure emulsification. The emulsification time is 1-1.5h. After completion, the temperature is lowered to below 50°C, and a neutralizing adjusting acid is added to adjust the pH value to 6.5-7.5.

[0043] Example 1

[0044] A polymerized high molecular printing oil comprises the following raw materials in parts by weight: 80 parts of cyclohexanone as an oil phase synthetic solvent, 0.5 parts of azobisisobutylcyanide as an initiator, 0.5 parts of 4-dimethylaminopyridine as a nucleophilic addition catalyst, 10 parts of glycerol as a solvent, 0.2 parts of citric acid as a neutralizing regulating acid, 8 parts of erucic acid as a fatty acid, 18 parts of acrylic acid polyoxyethylene ether oleate (n=10) and 20 parts of acrylic acid cardanol polyoxyethylene ester (m=5) as polymerization monomers, 15 parts of acrylamide and 40 parts of pure water.

[0045] A method for preparing a polymerized high molecular weight printing oil comprises the following steps:

[0046] Step 1: Add polyoxyethylene acrylate oleate, polyoxyethylene acrylate cardanol ester and cyclohexanone to a four-necked flask equipped with a thermometer, a constant pressure dropper and a condenser reflux device, respectively, and stir them evenly at room temperature;

[0047] Step 2: Add azobisisobutyl cyanide and acrylamide to the reaction kettle, heat to 110-115°C, start to drop azobisisobutyl cyanide and acrylamide, and control the temperature at about 115°C for 2 hours. After the dropwise addition is completed, keep the temperature at 115°C for 2-3 hours.

[0048] Step 3: After the heat preservation is completed, the temperature is lowered to 75-80°C, 4-dimethylaminopyridine and erucic acid are added, the mixture is fully stirred and the temperature is raised to 125-130°C, and the mixture is kept warm for 4-6 hours, and the condensation reflux device is turned on;

[0049] Step 4: After the insulation is completed, the solution is cooled to below 50°C and transferred to a rotary evaporator to remove cyclohexanone. After the cyclohexanone is evaporated, glycerol and pure water are added to the reactor and the temperature is raised to 105-110°C for pressure emulsification. The emulsification time is 1-1.5 hours. After completion, the temperature is lowered to below 50°C, and citric acid is added to adjust the pH value to 6.5-7.5.

[0050] Example 2

[0051] A polymerized high molecular printing oil comprises the following raw materials in parts by weight: 75 parts of cyclohexanone as an oil phase synthetic solvent, 0.4 parts of azobisisobutylcyanide as an initiator, 0.4 parts of 4-dimethylaminopyridine as a nucleophilic addition catalyst, 12 parts of ethylene glycol as a solvent, 0.3 parts of citric acid as a neutralizing regulating acid, 10 parts of stearic acid as a fatty acid, 12 parts of acrylic acid polyoxyethylene ether oleate (n=8) and 16 parts of acrylic acid cardanol polyoxyethylene ester (m=12) as polymerization monomers, 12 parts of acrylamide and 32 parts of pure water.

[0052] A method for preparing a polymerized high molecular weight printing oil comprises the following steps:

[0053] Step 1: Add polyoxyethylene acrylate oleate, polyoxyethylene acrylate cardanol ester and cyclohexanone to a four-necked flask equipped with a thermometer, a constant pressure dropper and a condenser reflux device, respectively, and stir them evenly at room temperature;

[0054] Step 2: Add azobisisobutyl cyanide and acrylamide to the reaction kettle, heat to 110-115°C, start to drop azobisisobutyl cyanide and acrylamide, and control the temperature at about 115°C for 2 hours. After the dropwise addition is completed, keep the temperature at 115°C for 2-3 hours.

[0055] Step 3: After the heat preservation is completed, the temperature is lowered to 75-80°C, 4-dimethylaminopyridine and stearic acid are added, the mixture is fully stirred and the temperature is raised to 125-130°C, and the mixture is kept warm for 4-6 hours, and the condensation reflux device is turned on;

[0056] Step 4, after the insulation is completed, the solution is cooled to below 50°C and transferred to a rotary evaporator to remove cyclohexanone. After the cyclohexanone is evaporated, ethylene glycol and pure water are added to the reactor and the temperature is raised to 105-110°C for pressure emulsification. The emulsification time is 1-1.5 hours. After completion, the temperature is lowered to below 50°C, and citric acid is added to adjust the pH value to 6.5-7.5.

[0057] The polymerized polymer printing oil sample PT synthesized in Example 1 was compared with the conventional printing oil sample A on the market for hand feel after washing, slurry viscosity and PVI value change test. The hand feel was evaluated from three perspectives: fluffy, smooth and soft using a 9-person group evaluation method. Table 1 shows the configuration components, and the test results are shown in Tables 2 and 3.

[0058] Table 1 Configuration components (total configuration 100g)

[0059] Component (g) PT group Conventional sample group A Blank group Synthetic thickener 3 3 3 Resistant salt 1 1 1 baking soda 4 4 4 Active Turquoise 4 4 4 Urea 6 6 6 PT 3 / / Conventional sample A / 3 / Hydration 79 79 82

[0060] Table 2 Slurry viscosity and PVI value results

[0061]

[0062]

[0063] Table 3 Fluffy, smooth and soft performance test results

[0064] fluffy soft smooth PT group 9 8 7 Conventional sample group A 4 3 2 Blank group 1 2 1

[0065] It can be seen from the data in Table 1, Table 2 and Table 3 that the polymerized high molecular printing oil synthesized by the present invention has an excellent hand feeling effect compared with conventional products on the market.

[0066] Therefore, the present invention adopts the above-mentioned polymerized high molecular printing oil and the preparation method thereof. The synthesized high molecular printing oil is a comb-type polymer. The higher surface activity and molecular weight can effectively improve the apparent viscosity of the slurry, change the rheological property of the slurry, and make the printed pattern clearer and fuller. At the same time, it can reduce the entanglement between thickeners, and is convenient for washing in the soaping process. The weak cationic property carried by it can effectively adsorb the fabric, reduce the negative impact of the anionic charge brought by the thickener adsorbed on the fabric on the post-finishing, and can also improve the feel after soaping through its own adsorption, and can play a good role in promoting both active printing and disperse printing.

[0067] 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 polymerized high molecular printing oil, characterized in that: The invention comprises the following raw materials in parts by weight: 75-85 parts of oil phase synthetic solvent, 0.3-0.8 parts of initiator, 0.3-0.6 parts of nucleophilic addition catalyst, 10-15 parts of solvent, 0.1-0.4 parts of neutralizing adjustment acid, 8-14 parts of fatty acid, 25-40 parts of polymerization monomer, 12-16 parts of acrylamide and 28-45 parts of pure water.

2. The polymerized high molecular printing oil according to claim 1, characterized in that: The initiator is azobisisobutyl cyanide.

3. The polymerized high molecular printing oil according to claim 1, characterized in that: The oil phase synthetic solvent is cyclohexanone.

4. The polymerized high molecular printing oil according to claim 1, characterized in that: The nucleophilic addition catalyst is 4-dimethylaminopyridine.

5. The polymerized high molecular printing oil according to claim 1, characterized in that: The solvent is ethylene glycol or glycerol.

6. The polymerized high molecular printing oil according to claim 1, characterized in that: The neutralizing adjusting acid is citric acid.

7. The polymerized high molecular printing oil according to claim 1, characterized in that: The fatty acid is oleic acid, erucic acid or stearic acid.

8. The polymerized high molecular printing oil according to claim 1, characterized in that: The structural formula of the polymerizable monomer is: Among them, R1 is oleic acid, R2 is cardanol, R3 is oleic acid, erucic acid or stearic acid; m and n are 3-50; a, b, c are all greater than or equal to 2.

9. A method for preparing a polymerized high molecular printing oil according to any one of claims 1 to 6, characterized in that: The steps include: Step 1: Add the polymerization monomer and the oil phase synthesis solvent to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a condenser reflux device, respectively, and stir them evenly at room temperature; Step 2: Add initiator and ethylenediamine to the reaction kettle, heat to 110-115°C, start dripping initiator and ethylenediamine, dripping time is 2h, after dripping is completed, keep warm at 115°C for 2-3h; Step 3: After the heat preservation is completed, the temperature is lowered to 75-80°C, a nucleophilic addition catalyst and a fatty acid are added, the mixture is fully stirred and heated to 125-130°C, and the mixture is kept warm for 4-6 hours, and the condensation reflux device is turned on; Step 4, after the insulation is completed, the solution is cooled to below 50°C and transferred to a rotary evaporator to remove the oil phase synthetic solvent. After the oil phase synthetic solvent is evaporated, the solvent and pure water are added to the reactor and the temperature is raised to 105-110°C for pressure emulsification. The emulsification time is 1-1.5h. After completion, the temperature is lowered to below 50°C, and a neutralizing adjusting acid is added to adjust the pH value to 6.5-7.5.

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