CN113004466B - Preparation method of butyronitrile latex for soft gloves - Google Patents
Preparation method of butyronitrile latex for soft gloves Download PDFInfo
- Publication number
- CN113004466B CN113004466B CN202110249894.8A CN202110249894A CN113004466B CN 113004466 B CN113004466 B CN 113004466B CN 202110249894 A CN202110249894 A CN 202110249894A CN 113004466 B CN113004466 B CN 113004466B
- Authority
- CN
- China
- Prior art keywords
- stirring
- hours
- oil phase
- parts
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Gloves (AREA)
Abstract
The invention belongs to the technical field of butyronitrile latex, and particularly relates to a preparation method of butyronitrile latex for soft gloves. The invention provides a preparation method of butyronitrile latex for soft gloves, aiming at solving the problems that the flexibility of the butyronitrile gloves can not be improved and the wearing comfort can not be improved in a mode of not reducing the content of acrylonitrile in the prior art. According to the invention, the long-chain unsaturated terminal polymer and the long-chain unsaturated diene are introduced into the polymer molecular chain, so that the flexibility of the molecular chain is improved, and the softness and the wearing comfort of the prepared nitrile latex gloves are improved on the premise of not reducing the content of acrylonitrile.
Description
Technical Field
The invention belongs to the technical field of butyronitrile latex, and particularly relates to a preparation method of butyronitrile latex for soft gloves.
Background
With the continuous improvement of the output of the butyronitrile latex for the butyronitrile gloves in China, the output of the butyronitrile latex gloves is also continuously increased, and the butyronitrile latex gloves can be widely applied to the fields of medical treatment, labor protection, scientific research and the like due to excellent physical and chemical properties. The butyronitrile latex gloves gradually increase along with the acrylonitrile content in the butyronitrile latex, the mechanical strength and the chemical oil resistance and corrosion resistance of the gloves gradually become better, but the hardness of the gloves gradually increases, the flexibility gradually becomes worse, the wearing comfort is reduced, and the experience of wearing the gloves for a long time becomes worse. There is a need for nitrile latex gloves that are more comfortable to wear without reducing the acrylonitrile content while providing flexibility.
For example, the chinese patent application discloses a method for preparing high solid content carboxylated nitrile latex [ application No.: 201910859449.6], the preparation method of the high-solid content carboxylic acrylonitrile butadiene latex is prepared by the following raw materials: 20-30% of carboxyl nitrile rubber, 15-25% of phenolic rubber, 10-20% of ethanedioic acid ethylene diester, 5-15% of dimethyl sebacate, 5-10% of organosilicon waterproofing agent, 15-25% of modified starch and 5-15% of deionized water.
The invention application has the advantages of being beneficial to improving the alkali resistance and the antioxidant effect, but the problem is not solved yet.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of butyronitrile latex for soft gloves with high wearing comfort.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of butyronitrile latex for soft gloves comprises the following steps:
the preparation method of the seed emulsion comprises the following steps: adding 5-20 parts of long-chain unsaturated hydroxyl-terminated monomer and 5-20 parts of long-chain unsaturated carboxyl-terminated monomer into a reaction kettle after vacuumizing and dewatering, heating to 30-60 ℃, adding 0.05-0.1 part of catalyst, stirring at a high speed for reaction for 1-2 hours, adding 1-3 parts of anionic emulsifier, 50-70 parts of water and 0.5-0.8 part of zwitterionic emulsifier, shearing at a high speed for emulsification for 2-4 hours, cooling to 20-30 ℃, and filtering to obtain seed emulsion;
a water phase preparation step: adding 50-70 parts of water, 1-2 parts of anionic emulsifier, 0.3-1 part of zwitterionic emulsifier, 0.05-0.1 part of pH value regulator and 0.05-0.1 part of chelating agent into a mixing tank with sealed belt stirring, and stirring and dispersing for 1.5-2 hours to obtain a water phase;
preparing an oil phase I: adding 20-40 parts of acrylonitrile, 0.3-0.8 part of molecular weight regulator and 3-5 parts of unsaturated carboxylic acid monomer into a mixing tank with sealed belt stirring, stirring and mixing for 1.5-2 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 10-20 parts of long-chain unsaturated diolefin and 50-70 parts of butadiene into a metering tank with a sealed belt for stirring, and circularly mixing and dispersing in the tank for 1-2 hours to obtain an oil phase II;
an initiator phase preparation step: adding 0.5-1.1 parts of initiator and 20-60 parts of water into a mixing tank with sealed stirring belt, and stirring and dispersing for 1-2 hours to obtain an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, the water phase, the oil phase I and the oil phase II into a reaction kettle, heating to 10-35 ℃, sampling and detecting, starting to dropwise add 1-3 parts of neutralizing agent when the conversion rate of a reaction system reaches more than 90%, and dropwise adding for reaction for 1-3 hours;
a discharging step: adding 0.5-1 part of terminator, heating to 30-60 ℃, vacuumizing and degassing, cooling to 20-30 ℃ after degassing, discharging, filtering and packaging to obtain the finished product.
In the preparation method of the butyronitrile latex for the soft glove, the long-chain unsaturated hydroxyl-terminated monomer in the seed emulsion preparation step comprises hydroxyl-terminated polybutadiene, and the molecular weight of the hydroxyl-terminated polybutadiene is 3000g/mol-5000 g/mol.
In the preparation method of the nitrile-butadiene latex for the soft glove, the long-chain unsaturated carboxyl-terminated monomer in the seed emulsion preparation step comprises carboxyl-terminated polybutadiene, and the molecular weight of the carboxyl-terminated polybutadiene is 2800g/mol-4500 g/mol.
In the above preparation method of the nitrile rubber latex for the soft glove, the long-chain unsaturated diene in the oil phase II preparation step includes one or more of 2, 6-octadiene, 1, 6-heptadiene and 1, 8-nonadiene.
In the above method for preparing the nitrile latex for the soft glove, the anionic emulsifier comprises butyl ricinoleate triethanolamine or sodium dodecyl benzene sulfonate.
In the above method for preparing butyronitrile latex for soft gloves, the zwitterionic emulsifier comprises one or more of sodium N-dodecyl- β -aminopropionate, sodium N-nonyl- β -aminopropionate, sodium N-cocamidoethyl-N-hydroxyethyl glycinate, cocamidosulfobetaine and N- (3-dimethylaminopropyl) -2- (1, 1, 2, 2-tetrahydroperfluorodecylthio) succinic acid.
In the above preparation method of the nitrile rubber latex for the soft glove, the unsaturated carboxylic acid monomer in the oil phase I preparation step includes one or more of nonadienoic acid, ethyl 2, 4-decadienoate and butyl pentenoate.
In the above method for preparing butyronitrile latex for soft gloves, the molecular weight regulator in the step of preparing the oil phase I comprises one or more of ethylene glycol dimethyl ether, hydrogen, sulfur dioxide, butyl mercaptan, 1-pentanethiol, tetraethylthiuram disulfide and tetrabutylthiuram disulfide.
In the above method for preparing butyronitrile latex for soft gloves, the catalyst in the step of preparing the seed emulsion comprises tert-butyl peroxypivalate.
In the above method for preparing the nitrile latex for the soft glove, the chelating agent in the step of preparing the aqueous phase comprises ethylenediaminetetraacetic acid.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the long-chain unsaturated terminal polymer and the long-chain unsaturated diene are introduced into the polymer molecular chain, so that the flexibility of the molecular chain is improved, and the softness and the wearing comfort of the prepared nitrile latex gloves are improved on the premise of not reducing the content of acrylonitrile.
2. According to the invention, the stability of a reaction system is improved by adopting a compounding mode of the anionic emulsifier and the zwitterionic emulsifier, and meanwhile, a neutralization reaction is adopted firstly, so that molecular chains are fully stretched, then a terminator is used for fully and completely terminating a polymerization reaction product, the structure of the product is improved, and finally, the particle size distribution is relatively in a narrow range.
3. The invention adopts unsaturated carboxylic acid monomer and sulfur-containing molecular weight regulator to carry out vulcanization crosslinking on polymer molecules, thereby improving the film-forming property and film-forming strength of the polymerization product.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1
This example provides a method for preparing a nitrile latex for soft gloves, comprising the following steps:
the preparation method of the seed emulsion comprises the following steps: adding 8kg of hydroxyl-terminated polybutadiene and 12kg of carboxyl-terminated polybutadiene into a reaction kettle after vacuumizing and dewatering, wherein the molecular weight of the hydroxyl-terminated polybutadiene is 4000g/mol, and the molecular weight of the carboxyl-terminated polybutadiene is 3500g/mol, heating to 50 ℃, adding 0.07kg of tert-butyl peroxypivalate, stirring at a high speed for reaction for 1.5 hours, adding 1.5kg of sodium dodecyl benzene sulfonate, 52kg of water and 0.7kg of sodium N-cocoamide ethyl-N-hydroxyethyl glycinate, shearing at a high speed for emulsification for 3 hours, cooling to 25 ℃, and filtering to obtain a seed emulsion;
a water phase preparation step: adding 60kg of water, 1.8kg of sodium dodecyl benzene sulfonate, 0.5kg of sodium N-cocoamidoethyl-N-hydroxyethyl glycinate, 0.08kg of baking soda and 0.08kg of ethylenediamine tetraacetic acid into a mixing tank with sealed stirring, and stirring and dispersing for 1.8 hours to obtain a water phase;
preparing an oil phase I: adding 25kg of acrylonitrile, 0.5kg of tetrabutylthiuram disulfide and 4kg of nonadienoic acid into a mixing tank with sealed belt stirring, stirring and mixing for 1.8 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 15kg of 2, 6-octadiene and 65kg of butadiene into a metering tank with a sealed belt for stirring, and circularly mixing and dispersing for 1.5 hours in the tank to obtain an oil phase II;
an initiator phase preparation step: adding 1kg of sodium persulfate and 40kg of water into a mixing tank with sealed stirring, and stirring and dispersing for 1.5 hours to prepare an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, the water phase, the oil phase I and the oil phase II into a reaction kettle, heating to 30 ℃, sampling and detecting, starting to dropwise add 2kg of cyclohexylamine when the conversion rate of a reaction system reaches over 90 percent, and dropwise adding for reaction for 2 hours;
a discharging step: adding 0.8kg of sodium nitrite, heating to 50 ℃, vacuumizing, degassing, cooling to 25 ℃ after degassing, discharging, filtering and packaging to obtain the finished product. The particle sizes of D10, D50, and D90 were measured using a laser particle sizer.
Example 2
This example provides a method for preparing a nitrile latex for soft gloves, comprising the following steps:
the preparation method of the seed emulsion comprises the following steps: adding 20kg of hydroxyl-terminated polybutadiene and 5kg of carboxyl-terminated polybutadiene into a reaction kettle after vacuumizing and dewatering, wherein the molecular weight of the hydroxyl-terminated polybutadiene is 5000g/mol, the molecular weight of the carboxyl-terminated polybutadiene is 4500g/mol, heating to 30 ℃, adding 0.05kg of tert-butyl peroxypivalate, stirring at a high speed for reaction for 1 hour, adding 1kg of sodium dodecyl benzene sulfonate, 50kg of water and 0.5kg of cocamide sulfonated betaine, shearing at a high speed for emulsification for 2 hours, cooling to 20 ℃, and filtering to obtain a seed emulsion;
a water phase preparation step: adding 50kg of water, 1kg of sodium dodecyl benzene sulfonate, 0.3kg of sodium N-cocoamidoethyl-N-hydroxyethyl glycinate, 0.05kg of sodium bicarbonate and 0.05kg of ethylene diamine tetraacetic acid into a mixing tank with sealed stirring, and stirring and dispersing for 1.5 hours to obtain a water phase;
preparing an oil phase I: adding 20kg of acrylonitrile, 0.3kg of ethylene glycol dimethyl ether and 3kg of ethyl 2, 4-decadienoate into a material mixing tank with sealed belt stirring, stirring and mixing for 1.5 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 10kg of 1, 6-heptadiene and 50kg of butadiene into a metering tank with stirring by a sealing belt, and circularly mixing and dispersing for 1 hour in the tank to obtain an oil phase II;
an initiator phase preparation step: adding 0.5kg of sodium persulfate and 20kg of water into a mixing tank with sealed stirring, and stirring and dispersing for 1 hour to prepare an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, a water phase, an oil phase I and an oil phase II into a reaction kettle, heating to 10 ℃, sampling and detecting, starting to dropwise add 1kg of cyclohexylamine when the conversion rate of a reaction system reaches more than 90%, and dropwise adding for reaction for 3 hours;
a discharging step: adding 0.5kg of sodium nitrite, heating to 30 ℃, vacuumizing, degassing, cooling to 20 ℃ after degassing, discharging, filtering and packaging to obtain the finished product. The particle sizes of D10, D50, and D90 were measured using a laser particle sizer.
Example 3
This example provides a method for preparing a nitrile latex for soft gloves, comprising the following steps:
the preparation method of the seed emulsion comprises the following steps: 5kg of hydroxyl-terminated polybutadiene and 20kg of carboxyl-terminated polybutadiene are added into a reaction kettle after vacuum pumping and water removal, wherein the molecular weight of hydroxyl-terminated polybutadiene is 3000g/mol, the molecular weight of carboxyl-terminated polybutadiene is 2800g/mol, the temperature is raised to 60 ℃, 0.1kg of tert-butyl peroxypivalate is added, the mixture is stirred at high speed for reaction for 2 hours, then adding 3kg of ricinoleic acid butyl ester sulfate triethanolamine, 70kg of water, 0.2kg of N-dodecyl-beta-aminopropionic acid sodium, 0.2kg of N-nonyl-beta-aminopropionic acid sodium, 0.2kg of cocamide sulfonated betaine and 0.2kg of N- (3-dimethylaminopropyl) -2- (1, 1, 2, 2-tetrahydroperfluorodecylthio) succinic acid, shearing and emulsifying for 4 hours at a high speed, cooling to 30 ℃, and filtering to prepare seed emulsion;
a water phase preparation step: adding 70kg of water, 2kg of ricinoleic acid butyl ester sulfate triethanolamine, 0.25kg of N-dodecyl-beta-aminopropionic acid sodium, 0.25kg of N-nonyl-beta-aminopropionic acid sodium, 0.25kg of cocamidosulfobetaine, 0.25kg of N- (3-dimethylaminopropyl) -2- (1, 1, 2, 2-tetrahydroperfluorodecylthio) succinic acid, 0.1kg of baking soda and 0.1kg of ethylenediamine tetraacetic acid into a dosing tank with sealed belt stirring, and stirring and dispersing for 2 hours to prepare a water phase;
preparing an oil phase I: adding 40kg of acrylonitrile, 0.8kg of butyl mercaptan, 2.5kg of butyl pentenoate and 2.5kg of nonadienoic acid into a mixing tank with stirring by a sealing belt, stirring and mixing for 2 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 10kg of 1, 8-nonadiene, 10kg of 2, 6-octadiene and 70kg of butadiene into a metering tank with a sealed belt for stirring, and circularly mixing and dispersing in the tank for 2 hours to obtain an oil phase II;
an initiator phase preparation step: adding 1.1kg of sodium persulfate and 60kg of water into a mixing tank with sealed stirring, and stirring and dispersing for 2 hours to prepare an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, a water phase, an oil phase I and an oil phase II into a reaction kettle, heating to 35 ℃, sampling and detecting, starting to dropwise add 3kg of cyclohexylamine when the conversion rate of a reaction system reaches over 90 percent, and dropwise adding for reaction for 1 hour;
a discharging step: adding 1kg of sodium polysulfide, heating to 60 deg.C, vacuum degassing, cooling to 30 deg.C, discharging, filtering, and packaging to obtain the final product. The particle sizes of D10, D50, and D90 were measured using a laser particle sizer.
Comparative example 1
The comparative example provides a method of preparing a nitrile latex for gloves, comprising the steps of:
the preparation method of the seed emulsion comprises the following steps: adding 8kg of hydroxyl-terminated polybutadiene and 12kg of carboxyl-terminated polybutadiene into a reaction kettle after vacuumizing and dewatering, wherein the molecular weight of the hydroxyl-terminated polybutadiene is 4000g/mol, and the molecular weight of the carboxyl-terminated polybutadiene is 3500g/mol, heating to 50 ℃, adding 0.07kg of tert-butyl peroxypivalate, stirring at a high speed for reaction for 1.5 hours, adding 52kg of water and 0.7kg of sodium N-cocamidoethyl-N-hydroxyethyl glycinate, shearing at a high speed for emulsification for 3 hours, cooling to 25 ℃, and filtering to obtain a seed emulsion;
a water phase preparation step: adding 60kg of water, 0.5kg of sodium N-cocamidoethyl-N-hydroxyethyl glycinate, 0.08kg of baking soda and 0.08kg of ethylenediamine tetraacetic acid into a mixing tank with sealed stirring, and stirring and dispersing for 1.8 hours to obtain a water phase;
preparing an oil phase I: adding 25kg of acrylonitrile, 0.5kg of tetrabutylthiuram disulfide and 4kg of nonadienoic acid into a mixing tank with sealed belt stirring, stirring and mixing for 1.8 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 15kg of 2, 6-octadiene and 65kg of butadiene into a metering tank with a sealed belt for stirring, and circularly mixing and dispersing for 1.5 hours in the tank to obtain an oil phase II;
an initiator phase preparation step: adding 1kg of sodium persulfate and 40kg of water into a mixing tank with sealed stirring, and stirring and dispersing for 1.5 hours to prepare an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, the water phase, the oil phase I and the oil phase II into a reaction kettle, heating to 30 ℃, sampling and detecting, starting to dropwise add 2kg of cyclohexylamine when the conversion rate of a reaction system reaches over 90 percent, and dropwise adding for reaction for 2 hours;
a discharging step: adding 0.8kg of sodium nitrite, heating to 50 ℃, vacuumizing, degassing, cooling to 25 ℃ after degassing, discharging, filtering and packaging to obtain the finished product. The particle sizes of D10, D50, and D90 were measured using a laser particle sizer.
Comparative example 2
The comparative example provides a method of preparing a nitrile latex for gloves, comprising the steps of:
the preparation method of the seed emulsion comprises the following steps: adding 8kg of hydroxyl-terminated polybutadiene and 12kg of carboxyl-terminated polybutadiene into a reaction kettle after vacuumizing and dewatering, wherein the molecular weight of the hydroxyl-terminated polybutadiene is 4000g/mol, and the molecular weight of the carboxyl-terminated polybutadiene is 3500g/mol, heating to 50 ℃, adding 0.07kg of tert-butyl peroxypivalate, stirring at a high speed for reaction for 1.5 hours, adding 1.5kg of sodium dodecyl benzene sulfonate and 52kg of water, shearing at a high speed for emulsification for 3 hours, cooling to 25 ℃, and filtering to obtain a seed emulsion;
a water phase preparation step: adding 60kg of water, 1.8kg of sodium dodecyl benzene sulfonate, 0.08kg of baking soda and 0.08kg of ethylenediamine tetraacetic acid into a mixing tank with sealed stirring, and stirring and dispersing for 1.8 hours to obtain a water phase;
preparing an oil phase I: adding 25kg of acrylonitrile, 0.5kg of tetrabutylthiuram disulfide and 4kg of nonadienoic acid into a mixing tank with sealed belt stirring, stirring and mixing for 1.8 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 15kg of 2, 6-octadiene and 65kg of butadiene into a metering tank with a sealed belt for stirring, and circularly mixing and dispersing for 1.5 hours in the tank to obtain an oil phase II;
an initiator phase preparation step: adding 1kg of sodium persulfate and 40kg of water into a mixing tank with sealed stirring, and stirring and dispersing for 1.5 hours to prepare an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, the water phase, the oil phase I and the oil phase II into a reaction kettle, heating to 30 ℃, sampling and detecting, starting to dropwise add 2kg of cyclohexylamine when the conversion rate of a reaction system reaches over 90 percent, and dropwise adding for reaction for 2 hours;
a discharging step: adding 0.8kg of sodium nitrite, heating to 50 ℃, vacuumizing, degassing, cooling to 25 ℃ after degassing, discharging, filtering and packaging to obtain the finished product. The particle sizes of D10, D50, and D90 were measured using a laser particle sizer.
Comparative example 3
The comparative example provides a method of preparing a nitrile latex for gloves, comprising the steps of:
the preparation method of the seed emulsion comprises the following steps: adding 8kg of hydroxyl-terminated polybutadiene and 12kg of carboxyl-terminated polybutadiene into a reaction kettle after vacuumizing and dewatering, wherein the molecular weight of the hydroxyl-terminated polybutadiene is 4000g/mol, and the molecular weight of the carboxyl-terminated polybutadiene is 3500g/mol, heating to 50 ℃, adding 0.07kg of tert-butyl peroxypivalate, stirring at a high speed for reaction for 1.5 hours, adding 1.5kg of sodium dodecyl benzene sulfonate, 52kg of water and 0.7kg of sodium N-cocoamide ethyl-N-hydroxyethyl glycinate, shearing at a high speed for emulsification for 3 hours, cooling to 25 ℃, and filtering to obtain a seed emulsion;
a water phase preparation step: adding 60kg of water, 1.8kg of sodium dodecyl benzene sulfonate, 0.5kg of sodium N-cocoamidoethyl-N-hydroxyethyl glycinate, 0.08kg of baking soda and 0.08kg of ethylenediamine tetraacetic acid into a mixing tank with sealed stirring, and stirring and dispersing for 1.8 hours to obtain a water phase;
preparing an oil phase I: adding 25kg of acrylonitrile, 0.5kg of tetrabutylthiuram disulfide and 4kg of nonadienoic acid into a mixing tank with sealed belt stirring, stirring and mixing for 1.8 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 15kg of 2, 6-octadiene and 65kg of butadiene into a metering tank with a sealed belt for stirring, and circularly mixing and dispersing for 1.5 hours in the tank to obtain an oil phase II;
an initiator phase preparation step: adding 1kg of sodium persulfate and 40kg of water into a mixing tank with sealed stirring, and stirring and dispersing for 1.5 hours to prepare an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, the water phase, the oil phase I and the oil phase II into a reaction kettle, heating to 30 ℃, sampling and detecting, and waiting until the conversion rate of a reaction system reaches more than 90%;
a discharging step: adding 0.8kg of sodium nitrite, heating to 50 ℃, vacuumizing, degassing, cooling to 25 ℃ after degassing, discharging, filtering and packaging to obtain the finished product. The particle sizes of D10, D50, and D90 were measured using a laser particle sizer.
Comparative example 4
The comparative example provides a method of preparing a nitrile latex for gloves, comprising the steps of:
the preparation method of the seed emulsion comprises the following steps: adding 8kg of hydroxyl-terminated polybutadiene into a reaction kettle after vacuumizing and dewatering, wherein the molecular weight of the hydroxyl-terminated polybutadiene is 4000g/mol, heating to 50 ℃, adding 0.07kg of tert-butyl peroxypivalate, stirring at a high speed for reaction for 1.5 hours, adding 1.5kg of sodium dodecyl benzene sulfonate, 52kg of water and 0.7kg of sodium N-cocoamidoethyl-N-hydroxyethyl glycinate, shearing at a high speed for emulsification for 3 hours, cooling to 25 ℃, and filtering to obtain a seed emulsion;
a water phase preparation step: adding 60kg of water, 1.8kg of sodium dodecyl benzene sulfonate, 0.5kg of sodium N-cocoamidoethyl-N-hydroxyethyl glycinate, 0.08kg of baking soda and 0.08kg of ethylenediamine tetraacetic acid into a mixing tank with sealed stirring, and stirring and dispersing for 1.8 hours to obtain a water phase;
preparing an oil phase I: adding 25kg of acrylonitrile, 0.5kg of tetrabutylthiuram disulfide and 4kg of nonadienoic acid into a mixing tank with sealed belt stirring, stirring and mixing for 1.8 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 15kg of 2, 6-octadiene and 65kg of butadiene into a metering tank with a sealed belt for stirring, and circularly mixing and dispersing for 1.5 hours in the tank to obtain an oil phase II;
an initiator phase preparation step: adding 1kg of sodium persulfate and 40kg of water into a mixing tank with sealed stirring, and stirring and dispersing for 1.5 hours to prepare an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, the water phase, the oil phase I and the oil phase II into a reaction kettle, heating to 30 ℃, sampling and detecting, starting to dropwise add 2kg of cyclohexylamine when the conversion rate of a reaction system reaches over 90 percent, and dropwise adding for reaction for 2 hours;
a discharging step: adding 0.8kg of sodium nitrite, heating to 50 ℃, vacuumizing, degassing, cooling to 25 ℃ after degassing, discharging, filtering and packaging to obtain the finished product.
Comparative example 5
The comparative example provides a method of preparing a nitrile latex for gloves, comprising the steps of:
the preparation method of the seed emulsion comprises the following steps: adding 12kg of carboxyl-terminated polybutadiene into a reaction kettle after vacuumizing and dewatering, wherein the molecular weight of the carboxyl-terminated polybutadiene is 3500g/mol, heating to 50 ℃, adding 0.07kg of tert-butyl peroxypivalate, stirring at a high speed for reaction for 1.5 hours, adding 1.5kg of sodium dodecyl benzene sulfonate, 52kg of water and 0.7kg of N-cocoamidoethyl-N-hydroxyethyl sodium glycinate, shearing at a high speed for emulsification for 3 hours, cooling to 25 ℃, and filtering to obtain a seed emulsion;
a water phase preparation step: adding 60kg of water, 1.8kg of sodium dodecyl benzene sulfonate, 0.5kg of sodium N-cocoamidoethyl-N-hydroxyethyl glycinate, 0.08kg of baking soda and 0.08kg of ethylenediamine tetraacetic acid into a mixing tank with sealed stirring, and stirring and dispersing for 1.8 hours to obtain a water phase;
preparing an oil phase I: adding 25kg of acrylonitrile, 0.5kg of tetrabutylthiuram disulfide and 4kg of nonadienoic acid into a mixing tank with sealed belt stirring, stirring and mixing for 1.8 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 15kg of 2, 6-octadiene and 65kg of butadiene into a metering tank with a sealed belt for stirring, and circularly mixing and dispersing for 1.5 hours in the tank to obtain an oil phase II;
an initiator phase preparation step: adding 1kg of sodium persulfate and 40kg of water into a mixing tank with sealed stirring, and stirring and dispersing for 1.5 hours to prepare an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, the water phase, the oil phase I and the oil phase II into a reaction kettle, heating to 30 ℃, sampling and detecting, starting to dropwise add 2kg of cyclohexylamine when the conversion rate of a reaction system reaches over 90 percent, and dropwise adding for reaction for 2 hours;
a discharging step: adding 0.8kg of sodium nitrite, heating to 50 ℃, vacuumizing, degassing, cooling to 25 ℃ after degassing, discharging, filtering and packaging to obtain the finished product.
Comparative example 6
The comparative example provides a method of preparing a nitrile latex for gloves, comprising the steps of:
the preparation method of the seed emulsion comprises the following steps: adding 8kg of hydroxyl-terminated polybutadiene and 12kg of carboxyl-terminated polybutadiene into a reaction kettle after vacuumizing and dewatering, wherein the molecular weight of the hydroxyl-terminated polybutadiene is 4000g/mol, and the molecular weight of the carboxyl-terminated polybutadiene is 3500g/mol, heating to 50 ℃, adding 0.07kg of tert-butyl peroxypivalate, stirring at a high speed for reaction for 1.5 hours, adding 1.5kg of sodium dodecyl benzene sulfonate, 52kg of water and 0.7kg of sodium N-cocoamide ethyl-N-hydroxyethyl glycinate, shearing at a high speed for emulsification for 3 hours, cooling to 25 ℃, and filtering to obtain a seed emulsion;
a water phase preparation step: adding 60kg of water, 1.8kg of sodium dodecyl benzene sulfonate, 0.5kg of sodium N-cocoamidoethyl-N-hydroxyethyl glycinate, 0.08kg of baking soda and 0.08kg of ethylenediamine tetraacetic acid into a mixing tank with sealed stirring, and stirring and dispersing for 1.8 hours to obtain a water phase;
preparing an oil phase I: adding 25kg of acrylonitrile, 0.5kg of tetrabutylthiuram disulfide and 4kg of nonadienoic acid into a mixing tank with sealed belt stirring, stirring and mixing for 1.8 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 65kg of butadiene into a metering tank with a sealed stirring belt, and circularly mixing and dispersing for 1.5 hours in the tank to obtain an oil phase II;
an initiator phase preparation step: adding 1kg of sodium persulfate and 40kg of water into a mixing tank with sealed stirring, and stirring and dispersing for 1.5 hours to prepare an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, the water phase, the oil phase I and the oil phase II into a reaction kettle, heating to 30 ℃, sampling and detecting, starting to dropwise add 2kg of cyclohexylamine when the conversion rate of a reaction system reaches over 90 percent, and dropwise adding for reaction for 2 hours;
a discharging step: adding 0.8kg of sodium nitrite, heating to 50 ℃, vacuumizing, degassing, cooling to 25 ℃ after degassing, discharging, filtering and packaging to obtain the finished product.
Application example 1
The understanding data measured for examples 1-3 and comparative examples 1-3 are shown in the following table:
| experimental group | D10(nm) | D50(nm) | D90(nm) |
| Example 1 | 218 | 230 | 240 |
| Example 2 | 227 | 241 | 254 |
| Example 3 | 220 | 225 | 237 |
| Comparative example 1 | 193 | 228 | 266 |
| Comparative example 2 | 200 | 233 | 272 |
| Comparative example 3 | 185 | 236 | 277 |
And (4) analyzing results: as can be seen from the above table, the particle size distribution ranges of comparative examples 1 to 3 are significantly wider, so that the present invention achieves the object of making the particle size distribution relatively within a narrow range.
Application example 2
Taking 35 parts of the finished butyronitrile latex prepared in the example 1 and the comparative examples 4-6 respectively, wherein the numbers are four groups of A, B, C and D, adding 0.01 part of liquid alkali, 0.1 part of sulfur dispersion and 0.03 part of color paste dispersion into each group, uniformly dispersing at a constant speed, mixing and dispersing for 48 hours to prepare pre-vulcanized butyronitrile latex with excellent performance, dipping the pre-vulcanized butyronitrile latex by using a proper glove mold, a coagulant and a release agent to prepare a first glove, a second glove, a third glove and a D glove which are all 0.07mm in thickness, and respectively measuring the elongation at break of the gloves, wherein the results are shown in the following table:
| measurement item | Nail gloves | Gloves for second use | Third glove | T-shaped glove |
| Elongation at break | 750％ | 460％ | 460％ | 380％ |
And (4) analyzing results: as can be seen from the above table, the elongation at break of the A glove is significantly better than that of other gloves, so the invention achieves the purpose of improving the softness and wearing comfort of the prepared nitrile latex glove.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of butyronitrile latex for soft gloves is characterized by comprising the following steps:
the preparation method of the seed emulsion comprises the following steps: adding 5-20 parts of long-chain unsaturated hydroxyl-terminated monomer and 5-20 parts of long-chain unsaturated carboxyl-terminated monomer into a reaction kettle after vacuumizing and dewatering, heating to 30-60 ℃, adding 0.05-0.1 part of catalyst, stirring at a high speed for reaction for 1-2 hours, adding 1-3 parts of anionic emulsifier, 50-70 parts of water and 0.5-0.8 part of zwitterionic emulsifier, shearing at a high speed for emulsification for 2-4 hours, cooling to 20-30 ℃, and filtering to obtain seed emulsion;
a water phase preparation step: adding 50-70 parts of water, 1-2 parts of anionic emulsifier, 0.3-1 part of zwitterionic emulsifier, 0.05-0.1 part of pH value regulator and 0.05-0.1 part of chelating agent into a mixing tank with sealed belt stirring, and stirring and dispersing for 1.5-2 hours to obtain a water phase;
preparing an oil phase I: adding 20-40 parts of acrylonitrile, 0.3-0.8 part of molecular weight regulator and 3-5 parts of unsaturated carboxylic acid monomer into a mixing tank with sealed belt stirring, stirring and mixing for 1.5-2 hours, and uniformly mixing to obtain an oil phase I;
preparing an oil phase II: adding 10-20 parts of long-chain unsaturated diolefin and 50-70 parts of butadiene into a metering tank with a sealed belt for stirring, and circularly mixing and dispersing in the tank for 1-2 hours to obtain an oil phase II;
an initiator phase preparation step: adding 0.5-1.1 parts of initiator and 20-60 parts of water into a mixing tank with sealed stirring belt, and stirring and dispersing for 1-2 hours to obtain an initiator phase;
the reaction steps are as follows: adding the prepared seed emulsion, the water phase, the oil phase I and the oil phase II into a reaction kettle, heating to 10-35 ℃, sampling and detecting, starting to dropwise add 1-3 parts of neutralizing agent when the conversion rate of a reaction system reaches more than 90%, and dropwise adding for reaction for 1-3 hours;
a discharging step: adding 0.5-1 part of terminator, heating to 30-60 ℃, vacuumizing and degassing, cooling to 20-30 ℃ after degassing, discharging, filtering and packaging to obtain a finished product;
the long-chain unsaturated hydroxyl-terminated monomer in the seed emulsion preparation step comprises hydroxyl-terminated polybutadiene, and the molecular weight of the hydroxyl-terminated polybutadiene is 3000g/mol-5000 g/mol;
the long-chain unsaturated carboxyl-terminated monomer in the seed emulsion preparation step comprises carboxyl-terminated polybutadiene, wherein the molecular weight of the carboxyl-terminated polybutadiene is 2800g/mol-4500 g/mol;
the long-chain unsaturated diene in the oil phase II preparation step comprises one or more of 2, 6-octadiene, 1, 6-heptadiene and 1, 8-nonadiene.
2. The process for preparing nitrile latex for soft gloves according to claim 1, wherein: the anionic emulsifier comprises butyl ricinoleate triethanolamine or sodium dodecyl benzene sulfonate.
3. The process for preparing nitrile latex for soft gloves according to claim 1, wherein: the zwitterionic emulsifier comprises one or more of N-dodecyl-beta-aminopropionic acid sodium, N-nonyl-beta-aminopropionic acid sodium, N-cocamidoethyl-N-hydroxyethyl glycine sodium, cocamido sulfonated betaine and N- (3-dimethylaminopropyl) -2- (1, 1, 2, 2-tetrahydroperfluorodecylthio) succinic acid.
4. The process for preparing nitrile latex for soft gloves according to claim 1, wherein: the unsaturated carboxylic acid monomer in the oil phase I preparation step comprises one or more of nonadienoic acid, 2, 4-decadienoic acid ethyl ester and butyl pentenoate.
5. The process for preparing nitrile latex for soft gloves according to claim 1, wherein: the molecular weight regulator in the oil phase I preparation step comprises one or more of ethylene glycol dimethyl ether, hydrogen, sulfur dioxide, butyl mercaptan, 1-pentanethiol, tetraethylthiuram disulfide and tetrabutylthiuram disulfide.
6. The process for preparing nitrile latex for soft gloves according to claim 1, wherein: the catalyst in the step of preparing the seed emulsion comprises tert-butyl peroxypivalate.
7. The process for preparing nitrile latex for soft gloves according to claim 1, wherein: the chelating agent in the water phase preparation step comprises ethylenediamine tetraacetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110249894.8A CN113004466B (en) | 2021-03-08 | 2021-03-08 | Preparation method of butyronitrile latex for soft gloves |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110249894.8A CN113004466B (en) | 2021-03-08 | 2021-03-08 | Preparation method of butyronitrile latex for soft gloves |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113004466A CN113004466A (en) | 2021-06-22 |
| CN113004466B true CN113004466B (en) | 2022-04-01 |
Family
ID=76408081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110249894.8A Active CN113004466B (en) | 2021-03-08 | 2021-03-08 | Preparation method of butyronitrile latex for soft gloves |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113004466B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005187544A (en) * | 2003-12-24 | 2005-07-14 | Nippon A & L Kk | Copolymer latex for use in dip molding, composition for use in dip molding, and dip-molded product |
| US20100160586A1 (en) * | 2008-12-19 | 2010-06-24 | The Sherwin-Williams Company | Low VOC Aqueous Polymer Dispersions |
| CN105778001B (en) * | 2014-12-19 | 2018-06-01 | 中国石油天然气股份有限公司 | A kind of method that emulsion polymerization prepares carboxy nitrile rubber |
| EP3353227B1 (en) * | 2015-09-22 | 2020-04-08 | Emerald Specialty Polymers, LLC | Epoxy terminated butadiene and butadiene acrylonitrile copolymers |
| CN106317336A (en) * | 2016-08-20 | 2017-01-11 | 山东成泰化工有限公司 | Carboxyl butyronitrile latex for oil resistant gloves and preparation method of carboxyl butyronitrile latex |
| KR102369383B1 (en) * | 2017-12-07 | 2022-02-28 | 주식회사 엘지화학 | Carboxylic acid modified nitrile based copolymer latex, method for preparing the copolymer latex, latex composition for dip-forming comprising the copolymer latex and article formed by the composition |
-
2021
- 2021-03-08 CN CN202110249894.8A patent/CN113004466B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113004466A (en) | 2021-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109776726B (en) | Preparation method of styrene butadiene rubber and styrene butadiene rubber | |
| CN105837752B (en) | A kind of preparation method of cold tolerant butadiene nitrile rubber | |
| CN112159497B (en) | Preparation method of fluorine-silicon modified butyronitrile latex applied to medical butyronitrile gloves | |
| CN111961157A (en) | Carboxyl butyronitrile latex for gloves and gloves produced by same | |
| CN105237682A (en) | Method for preparing high performance carboxylic acrylonitrile butadiene rubber latexes | |
| CN113004466B (en) | Preparation method of butyronitrile latex for soft gloves | |
| CN112500526B (en) | Preparation method of large-particle-size styrene-butadiene latex | |
| JPH035410B2 (en) | ||
| CN102898584A (en) | Styrene-butadiene-isoprene terpolymer integrated latex and preparation method thereof | |
| CN111961158A (en) | Production method of carboxylic acrylonitrile butadiene latex | |
| CN114395062B (en) | Preparation method of liquid polybutadiene with wide molecular weight distribution | |
| CN103626936A (en) | Water-resistant and high temperature-resistant polymer latex and preparation method thereof | |
| CN111019046A (en) | Preparation method of nitrile rubber | |
| CN113956513B (en) | Butadiene rubber and preparation method thereof | |
| CN111763285B (en) | Methyl styrene-butadiene rubber and preparation method thereof | |
| CN103951776A (en) | Catalyst charging method in neodymium polybutadiene rubber polymerization processes | |
| WO2014077236A1 (en) | Xanthogen-modified chloroprene rubber and production method therefor | |
| CN116003711B (en) | Nitrile rubber and preparation method thereof, hydrogenated nitrile rubber, nitrile rubber composition and nitrile rubber vulcanized rubber | |
| CN112940184A (en) | Preparation method of butyronitrile latex for high-strength gloves | |
| CN116217809B (en) | Preparation method of bio-based rubber and vulcanized rubber | |
| JPS6055531B2 (en) | Method for producing heat-resistant and bend-resistant rubber | |
| CN106977656B (en) | Dendritic polydiene rubber and preparation method thereof | |
| CN117487078B (en) | Halogen-free modified solution polymerized styrene-butadiene rubber and preparation method thereof | |
| CN102838705A (en) | Preparation method of acrylate type emulsion for improving monomer conversion rate | |
| CN110357988B (en) | Composition for terminating free radical polymerization reaction and preparation method of styrene butadiene rubber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |