CN114133633A - Preparation process of water-based vulcanized rubber for shoes - Google Patents
Preparation process of water-based vulcanized rubber for shoes Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention relates to a preparation process of water-based vulcanized rubber for shoes, which belongs to the technical field of shoe rubber and comprises the following steps: sieving the water-based natural latex with a 60-mesh sieve, putting the water-based natural latex into a stirring kettle, adding an emulsifier under stirring, slowly adding the water-based polyurethane resin filtered by the 60-mesh sieve into the stirring kettle, stirring for 15min, adding a vulcanization assistant, continuously stirring for 30min, adding a defoaming agent, stirring for 10min, adding a rheological assistant and a tackifier, and stirring for 30min to obtain the water-based vulcanized rubber for shoes; wherein, the tackifier is prepared by the following steps: mixing a macromolecular stabilizer, ethylene glycol dimethyl ether and chloroplatinic acid to obtain a modified solution; the preparation method comprises the steps of mixing hydrogen-containing silicone oil, p-hydroxyanisole and ethylene glycol dimethyl ether, stirring, heating to 80 ℃, adding the modified solution, and reacting for 2 hours under heat preservation to obtain the tackifier.
Description
Technical Field
The invention belongs to the technical field of shoe rubber, and particularly relates to a preparation process of water-based vulcanized rubber for shoes.
Background
At present, two kinds of glue, namely oil-based adhesive and natural latex, are commonly used for vulcanized shoes in the shoe making market. The adhesive force intensity of the natural latex is not ideal enough and sometimes can not reach the standard, the natural latex contains ammonia water as a preservative, the natural latex has pungent smell, most of the vulcanizing aids added into the natural latex are solid particles, and the vulcanizing aids can be added into the latex after being ball-milled and emulsified for 48 hours by using a ball mill or a stirrer, so that the period is long, the service time is short, and the performance is unstable. The oily vulcanized rubber is used, oily adhesives have high TVOC (total volatile organic compounds), the emission of organic solvents can cause resource waste, environmental pollution and harm to the health of direct contact persons, the molecular chain structure of natural latex contains double bonds with high activity, and the natural latex is easy to react with ozone in the air and the like, so that the natural latex has poor thermal oxidation aging resistance and ozone resistance, and the bonding strength of the existing oily adhesives and natural latex and vamp materials is low, so that the water-based vulcanized rubber for shoes, which is resistant to aging, environment-friendly and high in bonding strength, is provided.
Disclosure of Invention
In order to solve the technical problems mentioned in the background technology, the invention provides a preparation process of water-based vulcanized rubber for shoes.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of water-based vulcanized rubber for shoes comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 40-60 parts of water-based natural latex, 40-60 parts of water-based polyurethane resin, 1-3 parts of vulcanization auxiliary agent, 1-3 parts of emulsifier, 0.01-0.1 part of defoaming agent, 0.1-1 part of rheological auxiliary agent and 0.5-1 part of tackifier;
and secondly, filtering the water-based natural latex by using a 60-mesh filter screen, putting the filtered water-based natural latex into a stirring kettle, starting stirring, adding an emulsifier at the rotation speed of 100-mesh filter screen and 200r/min, stirring for 15min, slowly adding the water-based polyurethane resin filtered by using the 60-mesh filter screen into the stirring kettle while stirring, stirring for 15min at the rotation speed of 200-mesh filter screen and 400r/min, then adding a vulcanization aid, continuously stirring for 30min, then slowly adding an antifoaming agent, stirring for 10min at the rotation speed of 100-mesh filter screen and 200r/min, adding a rheological aid and a tackifier, and stirring for 30min to obtain the water-based vulcanized rubber for shoes.
Further, the tackifier is prepared by the following steps:
step S11, 2200 × 10 mass fractions of macromolecular stabilizer, glycol dimethyl ether and platinum-6% chloroplatinic acid was added to the round bottom flask,stirring for 30min at room temperature to obtain a modified solution;
wherein the mass fractions of the macromolecular stabilizer, the glycol dimethyl ether and the platinum are 2200 multiplied by 10-6% of chloroplatinic acid is 10: 10: 0.01;
step S12, mixing hydrogen-containing silicone oil, p-hydroxyanisole and ethylene glycol dimethyl ether, stirring at the rotation speed of 200r/min, heating to 80 ℃, adding a modified solution, carrying out heat preservation reaction for 2 hours, cooling to 40 ℃, adding activated carbon to adsorb a chloroplatinic acid catalyst for 1 hour, carrying out suction filtration, and carrying out rotary evaporation on a filtrate to remove the ethylene glycol dimethyl ether to obtain a tackifier;
wherein the mass of active hydrogen in the hydrogen-containing silicone oil is 1.6%, the viscosity is 20mPa & s, and the dosage ratio of the hydrogen-containing silicone oil, the p-hydroxyanisole, the glycol dimethyl ether and the modified solution is 11.5-12.0 g: 0.1 g: 100-120 mL: 40g, and obtaining the tackifier through hydrosilylation reaction under the catalytic action of chloroplatinic acid.
Further, the macromolecular stabilizer is prepared by the following steps:
step S21, mixing cyanuric chloride and acetone, adding an acetonitrile solution of 7-amino-4-methylcoumarin and an acetonitrile solution of 2, 4-dihydroxybenzophenone, stirring for 5-10min, adding diethylenetriamine and potassium carbonate, carrying out light-shielding reflux reaction for 48h, concentrating a reaction product to 1/4 of the original volume after the reaction is finished, transferring the reaction product to distilled water, standing for 12h, carrying out suction filtration, washing a filter cake with distilled water for 3-5 times, and drying at 60 ℃ to constant weight to obtain a light-stabilized compound;
wherein the dosage ratio of the cyanuric chloride, the acetone, the acetonitrile solution of the 7-amino-4-methylcoumarin, the acetonitrile solution of the 2, 4-dihydroxy benzophenone, the diethylenetriamine and the potassium carbonate is 0.03 mol: 40mL of: 40mL of: 40mL of: 0.01 mol: 0.02-0.03mol of acetonitrile solution of 7-amino-4-methylcoumarin from 7-amino-4-methylcoumarin and acetonitrile in the amount of 0.01 mol: 40mL of a mixture of 2, 4-dihydroxybenzophenone and acetonitrile, wherein the acetonitrile solution of 2, 4-dihydroxybenzophenone is prepared by mixing 2, 4-dihydroxybenzophenone and acetonitrile according to a molar ratio of 0.01 mol: 40mL of the mixture is mixed, under the alkaline condition, cyanuric chloride, 7-amino-4-methylcoumarin, 2, 4-dihydroxy benzophenone and diethylenetriamine are subjected to HCl elimination reaction to obtain a light-stabilized compound;
step S22, adding hydroxyl polybutadiene and THF into a three-neck flask, stirring for 10min, heating to 70-80 ℃, adding a THF solution of thioglycolic acid and AIBN, stirring for reaction for 3h, adding a THF solution of 2, 6-di-tert-butyl-4-methylphenol, stopping heating and stirring, performing rotary evaporation on a reaction product to 1/4 of the original volume, then transferring the reaction product into ice methanol, oscillating for 3-5min, standing for 2h, performing suction filtration, and performing vacuum drying on a filter cake at 60 ℃ for 12h to obtain polycarboxy polybutadiene;
wherein the hydroxyl value of the hydroxyl-terminated polybutadiene is 0.91mmol/g, the dosage ratio of the hydroxyl-terminated polybutadiene, THF solution of THF, thioglycolic acid and AIBN and the THF solution of 2, 6-di-tert-butyl-4-methylphenol is 10 g: 50mL of: 20-25 mL: 3mL of a THF solution of thioglycolic acid and AIBN was prepared from thioglycolic acid, AIBN and THF in a ratio of 1-3 g: 0.1 g: 20 to 25mL of a mixture of 2, 6-di-tert-butyl-4-methylphenol in THF was prepared from 2, 6-di-tert-butyl-4-methylphenol and THF in an amount of 0.05 to 0.2 g: 3mL of the modified polybutadiene is mixed, AIBN is used as an initiator, thioglycolic acid is used as a functional modifier, and the multi-carboxyl polybutadiene is obtained by utilizing a mercapto-alkene click reaction;
step S23, mixing polycarboxy polybutadiene and ethylene glycol dimethyl ether, then adding a light-stable compound, NHS and EDC, magnetically stirring and reacting for 6h at room temperature in a dark place, and after the reaction is finished, removing the ethylene glycol dimethyl ether by rotary evaporation to obtain a macromolecular stabilizer;
wherein, the dosage ratio of the polycarboxy polybutadiene, the glycol dimethyl ether, the light stabilizing compound, the NHS and the EDC is 5 g: 50-60 mL: 0.4-0.6 g: 0.2 g: 0.4g, under the catalytic action of NHS and EDC, the carboxyl of the polycarboxy polybutadiene and the amino of the light-stabilizing compound are subjected to amidation reaction to obtain the macromolecular stabilizer.
Furthermore, the solid content of the water-based natural latex is 55-65%, the viscosity is 30-300cps, the pH value is 9-11, and the content of the organic solvent is 0-1%.
Furthermore, the solid content of the waterborne polyurethane resin is 40-60%, the viscosity is 30-300cps, the pH value is 5-9, and the content of the organic solvent is 0-3%.
Further, the emulsifier is a non-ionic emulsifier.
Further, the defoaming agent is a silicone defoaming agent.
Further, the rheological additive is LT aqueous rheological additive and WT-204 aqueous rheological additive according to the mass ratio of 1: 1 are mixed.
The invention has the beneficial effects that:
1. the product mainly comprises water-based natural latex and water-based polyurethane resin, the main medium is water, the discharge of TVOC (total volatile organic compound) is zero, the pollution to the atmospheric environment is avoided, the harm to the health of direct contact persons is small, the product can be produced only by stirring at normal temperature without heating and dissolving reaction, the energy consumption is low, the production efficiency is high, the explosion risk is avoided, the product can be used after being sealed and stored for 6 months at the temperature of 5-40 ℃, the cover is opened, no pungent smell exists, the environment is protected, no pollution is caused, and the operation is easy.
2. In order to overcome the problems of poor aging resistance and low bonding strength of the existing vulcanized rubber, the invention adds the tackifier into the vulcanized rubber, the tackifier is modified polysiloxane, groups such as phenyl, hindered phenol, coumarin and the like are introduced into a polysiloxane molecular chain, and strong hydrogen bond action or chemical bond connection is formed between the genes and an adherend, so that the vulcanized rubber is endowed with strong bonding performance and the aging resistance is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides a tackifier made by the steps of:
step S11, mixing 20g of macromolecular stabilizer, 20g of glycol dimethyl ether and 0.02g of platinum with the mass fraction of 2200 × 10-6% chloroplatinic acid is added into a round-bottom flask, and the mixture is stirred for 30min at room temperature to obtain a modified solution;
step S12, mixing 11g of hydrogen-containing silicone oil, 0.1g of p-hydroxyanisole and 100mL of ethylene glycol dimethyl ether, stirring at a rotation speed of 200r/min, heating to 80 ℃, adding 40g of modified solution, carrying out heat preservation reaction for 2 hours, cooling to 40 ℃, adding activated carbon to adsorb a chloroplatinic acid catalyst for 1 hour, carrying out suction filtration, and carrying out rotary evaporation on filtrate to remove the ethylene glycol dimethyl ether to obtain the tackifier, wherein the mass of active hydrogen in the hydrogen-containing silicone oil is 1.6%, and the viscosity is 20mPa · S.
The macromolecular stabilizer is prepared by the following steps:
step S21, mixing 0.03mol of cyanuric chloride with 40mL of acetone, then adding 40mL of acetonitrile solution of 7-amino-4-methylcoumarin and 40mL of acetonitrile solution of 2, 4-dihydroxybenzophenone, stirring for 5min, then adding 0.01mol of diethylenetriamine and 0.02mol of potassium carbonate, carrying out light-shielding reflux reaction for 48h, after the reaction is finished, concentrating the reaction product to 1/4 of the original volume, then transferring the reaction product to distilled water, standing for 12h, carrying out suction filtration, washing the filter cake with distilled water for 3 times, and then drying at 60 ℃ to constant weight to obtain a photostabilized compound, wherein the acetonitrile solution of 7-amino-4-methylcoumarin is prepared from 7-amino-4-methylcoumarin and acetonitrile according to 0.01 mol: 40mL of a mixture of 2, 4-dihydroxybenzophenone and acetonitrile, wherein the acetonitrile solution of 2, 4-dihydroxybenzophenone is prepared by mixing 2, 4-dihydroxybenzophenone and acetonitrile according to a molar ratio of 0.01 mol: 40mL of the mixture is mixed;
step S22, adding 10g of hydroxyl-terminated polybutadiene and 50mL of THF into a three-neck flask, stirring for 10min, heating to 70 ℃, adding 20mL of THF solution of thioglycolic acid and AIBN, stirring for reaction for 3h, adding 3mL of THF solution of 2, 6-di-tert-butyl-4-methylphenol, stopping heating and stirring, carrying out rotary evaporation on a reaction product to 1/4 of the original volume, then transferring the reaction product into ice methanol, oscillating for 3min, standing for 2h, carrying out suction filtration, placing a filter cake at 60 ℃ and carrying out vacuum drying for 12h to obtain polycarboxy polybutadiene, wherein the THF solution of thioglycolic acid and AIBN is prepared from thioglycolic acid, AIBN and THF according to the dosage ratio of 1 g: 0.1 g: 20mL of a THF solution of 2, 6-di-tert-butyl-4-methylphenol was prepared by mixing 2, 6-di-tert-butyl-4-methylphenol and THF in an amount of 0.05 g: 3mL of the mixture is mixed;
and step S23, mixing 5g of polycarboxy polybutadiene and 50mL of ethylene glycol dimethyl ether, then adding 0.4g of light-stable compound, 0.2g of NHS and 0.4g of EDC, magnetically stirring and reacting for 6h at room temperature in a dark place, and after the reaction is finished, removing the ethylene glycol dimethyl ether through rotary evaporation to obtain the macromolecular stabilizer.
Example 2
This example provides a tackifier made by the steps of:
step S11, mixing 20g of macromolecular stabilizer, 20g of glycol dimethyl ether and 0.02g of platinum with the mass fraction of 2200 × 10-6% chloroplatinic acid is added into a round-bottom flask, and the mixture is stirred for 30min at room temperature to obtain a modified solution;
step S12, mixing 12.0g of hydrogen-containing silicone oil, 0.1g of p-hydroxyanisole and 120mL of ethylene glycol dimethyl ether, stirring at a rotation speed of 200r/min, heating to 80 ℃, adding 40g of modified solution, carrying out heat preservation reaction for 2 hours, cooling to 40 ℃, adding activated carbon to adsorb chloroplatinic acid catalyst for 1 hour, carrying out suction filtration, and carrying out rotary evaporation on filtrate to remove the ethylene glycol dimethyl ether to obtain the tackifier, wherein the mass of active hydrogen in the hydrogen-containing silicone oil is 1.6%, and the viscosity is 20mPa · S.
The macromolecular stabilizer is prepared by the following steps:
step S21, mixing 0.03mol of cyanuric chloride with 40mL of acetone, then adding 40mL of acetonitrile solution of 7-amino-4-methylcoumarin and 40mL of acetonitrile solution of 2, 4-dihydroxybenzophenone, stirring for 10min, adding 0.01mol of diethylenetriamine and 0.03mol of potassium carbonate, carrying out light-shielding reflux reaction for 48h, after the reaction is finished, concentrating the reaction product to 1/4 of the original volume, then transferring the reaction product to distilled water, standing for 12h, carrying out suction filtration, washing the filter cake for 5 times with distilled water, and drying at 60 ℃ to constant weight to obtain a light-stabilized compound, wherein the acetonitrile solution of 7-amino-4-methylcoumarin is prepared from 7-amino-4-methylcoumarin and acetonitrile according to 0.01 mol: 40mL of a mixture of 2, 4-dihydroxybenzophenone and acetonitrile, wherein the acetonitrile solution of 2, 4-dihydroxybenzophenone is prepared by mixing 2, 4-dihydroxybenzophenone and acetonitrile according to a molar ratio of 0.01 mol: 40mL of the mixture is mixed;
step S22, adding 10g of hydroxyl-terminated polybutadiene and 50mL of THF into a three-neck flask, stirring for 10min, heating to 80 ℃, adding 25mL of THF solution of thioglycolic acid and AIBN, stirring for reaction for 3h, adding 3mL of THF solution of 2, 6-di-tert-butyl-4-methylphenol, stopping heating and stirring, performing rotary evaporation on the reaction product to 1/4 of the original volume, then transferring the reaction product into ice methanol, oscillating for 5min, standing for 2h, performing suction filtration, placing the filter cake at 60 ℃ and performing vacuum drying for 12h to obtain polycarboxy polybutadiene, wherein the THF solution of thioglycolic acid and AIBN is prepared from thioglycolic acid, AIBN and THF according to the dosage ratio of 3 g: 0.1 g: 25mL of a THF solution of 2, 6-di-tert-butyl-4-methylphenol was prepared by mixing 2, 6-di-tert-butyl-4-methylphenol and THF in an amount of 0.2 g: 3mL of the mixture is mixed;
and step S23, mixing 5g of polycarboxy polybutadiene and 60mL of ethylene glycol dimethyl ether, then adding 0.6g of light-stable compound, 0.2g of NHS and 0.4g of EDC, magnetically stirring and reacting for 6h at room temperature in a dark place, and after the reaction is finished, removing the ethylene glycol dimethyl ether through rotary evaporation to obtain the macromolecular stabilizer.
Example 3
A preparation process of water-based vulcanized rubber for shoes comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 40 parts of water-based natural latex, 60 parts of water-based polyurethane resin, 1 part of vulcanization auxiliary agent, 1 part of emulsifier, 0.01 part of defoaming agent, 0.1 part of rheological auxiliary agent and 0.5 part of tackifier in example 1;
and secondly, filtering the water-based natural latex by using a 60-mesh filter screen, putting the filtered water-based natural latex into a stirring kettle, starting stirring, adding an emulsifier at the rotation speed of 100r/min, stirring for 15min, slowly adding the water-based polyurethane resin filtered by using the 60-mesh filter screen into the stirring kettle while stirring, stirring for 15min at the rotation speed of 200r/min, then adding a vulcanization auxiliary agent, continuously stirring for 30min, then slowly adding an antifoaming agent, stirring for 10min at the rotation speed of 100r/min, adding a rheological auxiliary agent and a tackifier for shoes, and stirring for 30min to obtain the water-based vulcanized rubber.
The water-based natural latex comprises 55% of solid content, 30cps of viscosity, 9 of pH value, 40% of solid content of water-based polyurethane resin, 30cps of viscosity, 5 of pH value, 3% of organic solvent, alkylphenol ethoxylate as an emulsifier, SN-154 as a defoaming agent, LT water-based rheological additive and WT-204 water-based rheological additive according to a mass ratio of 1: 1 and the tackifier is the product obtained in example 1.
Example 4
A preparation process of water-based vulcanized rubber for shoes comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 50 parts of water-based natural latex, 50 parts of water-based polyurethane resin, 2 parts of vulcanization auxiliary agent, 2 parts of emulsifier, 0.06 part of defoaming agent, 0.5 part of rheological auxiliary agent and 0.8 part of tackifier in example 2;
and secondly, filtering the water-based natural latex by using a 60-mesh filter screen, putting the filtered water-based natural latex into a stirring kettle, starting stirring, adding an emulsifier at the rotation speed of 150r/min, stirring for 15min, slowly adding the water-based polyurethane resin filtered by using the 60-mesh filter screen into the stirring kettle while stirring, stirring for 15min at the rotation speed of 300r/min, then adding a vulcanization auxiliary agent, continuously stirring for 30min, then slowly adding an antifoaming agent, stirring for 10min at the rotation speed of 150r/min, adding a rheological auxiliary agent and a tackifier for shoes, and stirring for 30min to obtain the water-based vulcanized rubber.
The water-based natural latex comprises 60% of solid content, 100cps of viscosity, 10 of pH value, 2% of organic solvent, 50% of water-based polyurethane resin, 100cps of viscosity, 7 of pH value, 1% of organic solvent, alkylphenol ethoxylates as an emulsifier, SN-154 as an antifoaming agent, LT water-based rheological additive and WT-204 water-based rheological additive according to a mass ratio of 1: 1 and the tackifier is the product obtained in example 2.
Example 5
A preparation process of water-based vulcanized rubber for shoes comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 60 parts of water-based natural latex, 40 parts of water-based polyurethane resin, 3 parts of vulcanization auxiliary agent, 3 parts of emulsifier, 0.1 part of defoaming agent, 1 part of rheological auxiliary agent and 1 part of tackifier in example 1;
and secondly, filtering the water-based natural latex by using a 60-mesh filter screen, putting the filtered water-based natural latex into a stirring kettle, starting stirring, adding an emulsifier at the rotation speed of 200r/min, stirring for 15min, slowly adding the water-based polyurethane resin filtered by using the 60-mesh filter screen into the stirring kettle while stirring, stirring for 15min at the rotation speed of 400r/min, then adding a vulcanization auxiliary agent, continuously stirring for 30min, then slowly adding an antifoaming agent, stirring for 10min at the rotation speed of 200r/min, adding a rheological auxiliary agent and a tackifier for shoes, and stirring for 30min to obtain the water-based vulcanized rubber.
The water-based natural latex comprises 65% of solid content, 300cps of viscosity, 11 of pH value, 1% of organic solvent, 60% of water-based polyurethane resin, 300cps of viscosity, 9 of pH value, 3% of organic solvent, alkylphenol ethoxylates as an emulsifier, SN-154 as an antifoaming agent, LT water-based rheological additive and WT-204 water-based rheological additive according to a mass ratio of 1: 1 and the tackifier was the product obtained in example 3.
Comparative example 1
The tackifier in example 3 was removed, and the remaining raw materials and preparation process were unchanged.
Comparative example 2
The tackifier in example 5 was replaced with the macromolecular stabilizer prepared in example 2, and the rest of the raw materials and the preparation process were unchanged.
The vulcanizates of examples 3-5 and comparative examples 1-2 were tested as follows:
adhesive strength: coating the prepared adhesive on the cloth to be bonded by using a gluing brush, drying the adhesive at 45 ℃ for 5 minutes, bonding the adhesive with the rubber shoe foxing strip, vulcanizing the adhesive at the rubber shoe vulcanizing temperature once after bonding, and finally testing the bonding strength of the foxing strip and the cloth according to the standard GB/T7760 plus 2003.
Ozone crack resistance time: coating the prepared adhesive on cloth to be bonded by a gluing brush, drying the adhesive at 45 ℃ for 5 minutes, bonding the adhesive with rubber shoe surrounding strips, vulcanizing the adhesive at the vulcanization temperature of the rubber shoes once after bonding, and testing the cracking time of the adhesive at the temperature of 40 ℃ under the ozone concentration of 50pphm and the humidity of 50%;
the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the vulcanizates for shoes prepared in examples 3-5 have high adhesive strength and long ozone crack resistance.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. A preparation process of water-based vulcanized rubber for shoes is characterized by comprising the following steps:
firstly, preparing the following raw materials in parts by weight: 40-60 parts of water-based natural latex, 40-60 parts of water-based polyurethane resin, 1-3 parts of vulcanization auxiliary agent, 1-3 parts of emulsifier, 0.01-0.1 part of defoaming agent, 0.1-1 part of rheological auxiliary agent and 0.5-1 part of tackifier;
secondly, mixing a macromolecular stabilizer, ethylene glycol dimethyl ether and chloroplatinic acid to obtain a modified solution; mixing hydrogen-containing silicone oil, p-hydroxyanisole and ethylene glycol dimethyl ether, stirring, heating to 80 ℃, adding a modified solution, carrying out heat preservation reaction for 2 hours, then cooling to 40 ℃, adding activated carbon to adsorb a chloroplatinic acid catalyst for 1 hour, carrying out suction filtration, and carrying out rotary evaporation on a filtrate to obtain a tackifier;
and thirdly, screening the water-based natural latex by a 60-mesh sieve, then putting the water-based natural latex into a stirring kettle, starting stirring, adding an emulsifier under stirring, slowly adding the water-based polyurethane resin filtered by the 60-mesh sieve into the stirring kettle while stirring, stirring for 15min, then adding the vulcanization assistant, continuously stirring for 30min, then adding the defoaming agent, stirring for 10min, then adding the rheological assistant and the tackifier, and stirring for 30min to obtain the water-based vulcanized rubber for shoes.
2. The preparation process of the water-based vulcanized rubber for shoes as claimed in claim 1, wherein the mass of active hydrogen in the hydrogen-containing silicone oil is 1.6%, the viscosity is 20mPa · s, and the dosage ratio of the hydrogen-containing silicone oil, the p-hydroxyanisole, the ethylene glycol dimethyl ether and the modified solution is 11.5-12.0 g: 0.1 g: 100-120 mL: 40 g.
3. The process for preparing the water-based vulcanized rubber for shoes according to claim 1, wherein the macromolecular stabilizer is prepared by the following steps:
mixing polycarboxy polybutadiene and ethylene glycol dimethyl ether, adding a light-stable compound, NHS and EDC, magnetically stirring and reacting for 6h at room temperature in a dark place, and performing rotary evaporation to obtain the macromolecular stabilizer.
4. The process for preparing the water-based vulcanized rubber for shoes according to claim 3, wherein the polycarboxy polybutadiene is prepared by the following steps:
mixing hydroxyl polybutadiene and THF, heating to 70-80 ℃, adding a THF solution of thioglycolic acid and AIBN, stirring for reaction for 3h, adding a THF solution of 2, 6-di-tert-butyl-4-methylphenol, stopping heating and stirring, performing rotary evaporation on a reaction product to 1/4 of the original volume, then transferring the reaction product to ice methanol, oscillating for 3-5min, standing for 2h, performing suction filtration, and placing a filter cake at 60 ℃ for vacuum drying for 12h to obtain the polycarboxy polybutadiene.
5. The process of claim 3, wherein the light-stabilizing compound is prepared by the following steps:
mixing cyanuric chloride and acetone, adding acetonitrile solution of 7-amino-4-methylcoumarin and acetonitrile solution of 2, 4-dihydroxy benzophenone, stirring for 5-10min, adding diethylenetriamine and potassium carbonate, carrying out light-resistant reflux reaction for 48h, and carrying out post-treatment to obtain the light-stabilized compound.
6. The process for preparing the water-based vulcanizate for shoes according to claim 5, wherein the acetonitrile solution of 7-amino-4-methylcoumarin is prepared from 7-amino-4-methylcoumarin and acetonitrile according to 0.01 mol: 40mL of the mixture was mixed.
7. The process of claim 5, wherein the acetonitrile solution of 2, 4-dihydroxybenzophenone is prepared from 2, 4-dihydroxybenzophenone and acetonitrile according to 0.01 mol: 40mL of the mixture was mixed.
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| CN202111655136.2A Active CN114133633B (en) | 2021-12-30 | 2021-12-30 | Preparation process of water-based vulcanized rubber for shoes |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5450590A (en) * | 1977-09-29 | 1979-04-20 | Hirono Kagaku Kogyo | Preparation of modified 1*22polybutadiene |
| US20040063597A1 (en) * | 2002-09-27 | 2004-04-01 | Adair Matha J. | Fabric care compositions |
| CN104530475A (en) * | 2014-12-15 | 2015-04-22 | 绍兴瑞康生物科技有限公司 | Preparation method of multifunctional synergistic antioxidative stabilizer |
| CN108250833A (en) * | 2018-03-21 | 2018-07-06 | 湖北中烟工业有限责任公司 | A kind of color inhibition UV ink for screen printing |
| CN110358475A (en) * | 2019-08-15 | 2019-10-22 | 广州泽远实业股份有限公司 | A kind of method of the aqueous vulcanizate of shoes |
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2021
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5450590A (en) * | 1977-09-29 | 1979-04-20 | Hirono Kagaku Kogyo | Preparation of modified 1*22polybutadiene |
| US20040063597A1 (en) * | 2002-09-27 | 2004-04-01 | Adair Matha J. | Fabric care compositions |
| CN104530475A (en) * | 2014-12-15 | 2015-04-22 | 绍兴瑞康生物科技有限公司 | Preparation method of multifunctional synergistic antioxidative stabilizer |
| CN108250833A (en) * | 2018-03-21 | 2018-07-06 | 湖北中烟工业有限责任公司 | A kind of color inhibition UV ink for screen printing |
| CN110358475A (en) * | 2019-08-15 | 2019-10-22 | 广州泽远实业股份有限公司 | A kind of method of the aqueous vulcanizate of shoes |
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| CN114133633B (en) | 2023-05-02 |
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