阅读说明：本技术 一种高固体含量羧基丁腈胶乳的制备方法 (Preparation method of high-solid-content carboxylic butyronitrile latex ) 是由 王保祥 谭耀阳 唐开喜 于 2021-10-21 设计创作，主要内容包括：本发明公开了一种高固体含量羧基丁腈胶乳的制备方法,涉及机加工领域,其技术方案包括以下步骤：步骤一：原料准备：对丁酯、丙烯腈以及软水进称量；步骤二：物料配置：对水相进行配置,对引发剂溶液进行配置,对于乳化剂C溶液进行配置；步骤三：投料：将配方量的软水、水相、稳定剂、硫醇、和甲基丙烯酸送入聚合釜中,关闭聚合釜上其它阀门,开启丙烯腈进料阀门,通过在聚合釜内部进行聚合放热的过程中将温度控制在38-53℃,在这个温度区间内每小时固含量上涨2.5-4.5％,当反应温度50℃左右,固含量达到39.5-40.5％,从而通过对温度的控制就能够实现对丁腈胶乳高固体含量的控制,不需要额外添加其他物料,降低高固体含量羧基丁腈胶乳的制作成本。(The invention discloses a preparation method of high-solid-content carboxylic acrylonitrile butadiene latex, which relates to the field of machining and adopts the technical scheme that the preparation method comprises the following steps: the method comprises the following steps: preparing raw materials: weighing butyl ester, acrylonitrile and soft water; step two: material preparation: preparing a water phase, preparing an initiator solution, and preparing an emulsifier C solution; step three: feeding: the preparation method comprises the steps of feeding soft water, a water phase, a stabilizer, mercaptan and methacrylic acid with the formula amount into a polymerization kettle, closing other valves on the polymerization kettle, opening an acrylonitrile feeding valve, controlling the temperature to be 38-53 ℃ in the process of polymerization heat release in the polymerization kettle, increasing the solid content by 2.5-4.5% per hour in the temperature interval, and controlling the high solid content of the butyronitrile latex by controlling the temperature when the reaction temperature is about 50 ℃, wherein the solid content reaches 39.5-40.5%, so that the high solid content of the butyronitrile latex can be controlled by controlling the temperature, other materials do not need to be additionally added, and the preparation cost of the high solid content carboxylated butyronitrile latex is reduced.)

1. A preparation method of high-solid content carboxylic acrylonitrile butadiene latex is characterized by comprising the following steps:

the method comprises the following steps: preparing raw materials: weighing butyl ester, acrylonitrile and soft water;

step two: material preparation: preparing a water phase, preparing an initiator solution, and preparing an emulsifier C solution;

step three: feeding: feeding the soft water, the water phase, the stabilizer, the mercaptan and the methacrylic acid with the formula amount into a polymerization kettle, closing other valves on the polymerization kettle, opening an acrylonitrile feeding valve, and adding the acrylonitrile with the formula amount;

step four: after the addition of acrylonitrile is finished, closing an acrylonitrile feeding valve, opening a butyl ester feeding valve, adding the butyl ester with the formula amount, closing the butyl ester feeding valve after the addition of the butyl ester is finished, and confirming that all valves on the polymerization kettle are closed in place again;

step five: polymerization: starting the polymerization kettle for stirring, controlling the rotating speed at (500 plus 1000r/min), emptying water in a jacket of the polymerization kettle, introducing steam into the jacket of the polymerization kettle for heating, adding an initiator and an emulsifier solution C at 30 ℃, and stopping heating when the temperature reaches 39 ℃;

when the polymerization heat release is carried out, the reaction temperature is controlled by adopting a step temperature rise control mode from low to high, and the temperature is controlled at 38-53 ℃;

step six: after the ammonia water with the formula amount is rapidly added when the heat release of the polymerization is finished, pressing the material into a degassing kettle, flushing the polymerization kettle with soft water with the formula amount, pressing the flushing water into the degassing kettle, and closing a discharge valve of the polymerization kettle;

step seven: introducing the degassed nitrile latex into a latex storage tank.

2. The process for preparing a high solids carboxylated nitrile latex according to claim 1, wherein the soft water is pumped into the soft water metering tank.

3. The process for preparing a high-solid-content carboxylated nitrile latex according to claim 2, wherein the butyl ester raw material is fed into the butyl ester metering tank by a transfer pump.

4. The process for preparing high-solid-content carboxylated nitrile latex according to claim 3, wherein the acrylonitrile raw material is pumped into the acrylonitrile metering tank.

5. The process for preparing carboxylated nitrile latex with high solid content according to claim 4, wherein the aqueous phase is prepared by: the emulsifier E, the emulsifier B and the EDTA-2 in the formula amount are dissolved in soft water in an aqueous phase tank.

6. The method for preparing carboxylated nitrile latex with high solid content according to claim 5, wherein the initiator solution is prepared by the following steps: the formula amount of potassium persulfate was dissolved in soft water in the initiator tank.

7. The method for preparing carboxylated nitrile latex with high solid content according to claim 6, wherein the emulsifier C solution is prepared by the following steps: the emulsifier C with the formula amount is dissolved in soft water in an emulsifier C tank.

8. The method for preparing carboxylated nitrile latex with high solid content according to claim 7, wherein the vacuum treatment of the polymerization kettle is required before the polymerization kettle works, so that the internal pressure of the polymerization kettle is kept at-0.07 MPa.

9. The process for preparing carboxylated nitrile latex according to claim 8, wherein the temperature is controlled between 38 and 53 ℃ during the exothermic polymerization, the increase in solid content is controlled between 2.5 and 4.5% per hour, and the solid content is controlled between 39.5 and 40.5% at a reaction temperature of about 50 ℃.

Technical Field

The invention relates to the technical field of butyronitrile latex, in particular to a preparation method of high-solid-content carboxylic butyronitrile latex.

Background

The butyronitrile latex is a milky dispersoid of a butadiene and acrylonitrile random copolymer, comprises two types of common butyronitrile latex and carboxyl butyronitrile latex, is directly obtained by an emulsion copolymerization method, and has the solid content of 40-45 percent generally and the bound acrylonitrile content of 20-50 percent

The carboxylated nitrile latex is an anionic high-molecular polymer emulsion. The latex has uniform molecular weight and particle size distribution, oil resistance, solvent resistance, acid and alkali resistance, can be crosslinked with sulfur and metal oxide, and has better stability than natural latex. The product has no anaphylactic reaction to skin, resists sharp object puncture and scratch, and has better definite stretching and drawing force than natural latex products. The product has the characteristics of milky appearance, excellent elasticity and the like, is easy to form and release films, and is suitable for lined and unlined thin gloves, other labor protection gloves and the like.

Through retrieval, the invention patent with the Chinese patent number of CN110628104A discloses a preparation method of high-solid content carboxylic acrylonitrile butadiene latex, which is prepared from 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, wherein the preparation method of the carboxyl nitrile latex with high solid content provided by the invention adopts reasonable material proportion for production and processing, has simple and easily controlled process flow, is beneficial to high-efficiency production, improves the solid content by adding the modified starch, effectively improves the quality and performance of the latex, is beneficial to improving the alkali resistance and the oxidation resistance effect, and is beneficial to popularization and use;

however, the solid content of the above preparation method is improved by adding modified starch in actual work, but the preparation cost of the nitrile latex is increased by the investment of the modified starch, so that a preparation method of the high-solid content carboxyl nitrile latex is needed.

Disclosure of Invention

The invention aims to solve the defect that the solid content is improved by adding modified starch in the prior art, but the preparation cost of the nitrile latex is increased by adding the modified starch, and provides a preparation method of high-solid-content carboxylic nitrile latex.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of high-solid content carboxylic acrylonitrile butadiene latex comprises the following steps:

the method comprises the following steps: preparing raw materials: weighing butyl ester, acrylonitrile and soft water;

step two: material preparation: preparing a water phase, preparing an initiator solution, and preparing an emulsifier C solution;

step three: feeding: feeding the soft water, the water phase, the stabilizer, the mercaptan and the methacrylic acid with the formula amount into a polymerization kettle, closing other valves on the polymerization kettle, opening an acrylonitrile feeding valve, and adding the acrylonitrile with the formula amount;

step four: after the addition of acrylonitrile is finished, closing an acrylonitrile feeding valve, opening a butyl ester feeding valve, adding the butyl ester with the formula amount, closing the butyl ester feeding valve after the addition of the butyl ester is finished, and confirming that all valves on the polymerization kettle are closed in place again;

step five: polymerization: starting the polymerization kettle for stirring, controlling the rotating speed at (500 plus 1000r/min), emptying water in a jacket of the polymerization kettle, introducing steam into the jacket of the polymerization kettle for heating, adding an initiator and an emulsifier solution C at 30 ℃, and stopping heating when the temperature reaches 39 ℃;

when the polymerization heat release is carried out, the reaction temperature is controlled by adopting a step temperature rise control mode from low to high, and the temperature is controlled at 38-53 ℃;

step six: after the ammonia water with the formula amount is rapidly added when the heat release of the polymerization is finished, pressing the material into a degassing kettle, flushing the polymerization kettle with soft water with the formula amount, pressing the flushing water into the degassing kettle, and closing a discharge valve of the polymerization kettle;

step seven: introducing the degassed nitrile latex into a latex storage tank.

The above technical solution further comprises:

the soft water is fed into the soft water metering tank by a delivery pump.

The raw material butyl ester is sent into a butyl ester metering tank through a delivery pump.

The raw material acrylonitrile is sent into an acrylonitrile metering tank through a delivery pump.

Preparing a water phase: the emulsifier E, the emulsifier B and the EDTA-2 in the formula amount are dissolved in soft water in an aqueous phase tank.

Preparing an initiator solution: the formula amount of potassium persulfate was dissolved in soft water in the initiator tank.

Preparing an emulsifier C solution: the emulsifier C with the formula amount is dissolved in soft water in an emulsifier C tank.

The vacuum treatment is needed to be carried out on the polymerization kettle before the polymerization kettle works, so that the internal pressure of the polymerization kettle is kept at-0.07 MPa.

When the polymerization is exothermic, the temperature is controlled at 38-53 ℃, the solid content is controlled to increase by 2.5-4.5% per hour, and when the reaction temperature is about 50 ℃, the solid content is 39.5-40.5%.

Compared with the prior art, the invention has the beneficial effects that:

in the invention, in the actual preparation process, the temperature is controlled to be 38-53 ℃ in the process of carrying out polymerization heat release in a polymerization kettle, the solid content rises by 2.5-4.5% per hour in the temperature interval, and when the reaction temperature is about 50 ℃, the solid content reaches 39.5-40.5%, so that the control of the high solid content of the butyronitrile latex can be realized by controlling the temperature, other materials do not need to be additionally added, and the preparation cost of the high solid content carboxylated butyronitrile latex is reduced.

Detailed Description

Example one

The first step is as follows: soft water is sent into a soft water measuring tank through a delivery pump, raw material butyl ester is sent into a butyl ester measuring tank through the delivery pump, raw material acrylonitrile is sent into an acrylonitrile measuring tank through the delivery pump, simultaneously, the phase is configured, initiator solution is configured, and emulsifier C solution is configured;

the second step is that: firstly, carrying out vacuum treatment on a polymerization kettle to keep the internal air pressure of the polymerization kettle at-0.07 MPa, then sending the soft water, the water phase, the stabilizer, the mercaptan and the methacrylic acid in the formula amount into the polymerization kettle, closing other valves on the polymerization kettle, opening an acrylonitrile feeding valve, adding the acrylonitrile in the formula amount, closing the acrylonitrile feeding valve after the addition of the acrylonitrile is finished, opening a butyl ester feeding valve, adding the butyl ester in the formula amount, closing the butyl ester feeding valve after the addition of the butyl ester is finished, and confirming that all valves on the polymerization kettle are closed in place again;

the third step: starting the polymerization kettle for stirring, controlling the rotating speed at (500-;

when the polymerization heat release is carried out, the reaction temperature is controlled by adopting a step temperature rise control mode from low to high, and the temperature is controlled at 38-53 ℃;

after the ammonia water with the formula amount is rapidly added when the heat release of the polymerization is finished, pressing the material into a degassing kettle, washing the polymerization kettle by using soft water with the formula amount, pressing washing water into the degassing kettle, closing a discharge valve of the polymerization kettle, and introducing the degassed butyronitrile latex into a latex storage tank;

the solid content of the high-solid-content carboxylic acrylonitrile butadiene latex produced by the steps can reach 39.5-40.5%, other materials are not needed to be added only by controlling the temperature, so that the cost of the high-solid-content carboxylic acrylonitrile butadiene latex is lower, and air bubbles in the acrylonitrile butadiene latex can be discharged through the degassing kettle, so that the surface of the produced high-solid-content carboxylic acrylonitrile butadiene latex is smoother.

Example two

The first step is as follows: soft water is sent into a soft water measuring tank through a delivery pump, raw material butyl ester is sent into a butyl ester measuring tank through the delivery pump, raw material acrylonitrile is sent into an acrylonitrile measuring tank through the delivery pump, simultaneously, the phase is configured, initiator solution is configured, and emulsifier C solution is configured;

the second step is that: firstly, carrying out vacuum treatment on a polymerization kettle to keep the internal air pressure of the polymerization kettle at-0.07 MPa, then sending the soft water, the water phase, the stabilizer, the mercaptan and the methacrylic acid in the formula amount into the polymerization kettle, closing other valves on the polymerization kettle, opening an acrylonitrile feeding valve, adding the acrylonitrile in the formula amount, closing the acrylonitrile feeding valve after the addition of the acrylonitrile is finished, opening a butyl ester feeding valve, adding the butyl ester in the formula amount, closing the butyl ester feeding valve after the addition of the butyl ester is finished, and confirming that all valves on the polymerization kettle are closed in place again;

the third step: starting the polymerization kettle for stirring, controlling the rotating speed at (500 plus 1000r/min), emptying water in a jacket of the polymerization kettle, introducing steam into the jacket of the polymerization kettle for heating, adding an initiator and an emulsifier solution C at 30 ℃, and stopping heating when the temperature reaches 39 ℃;

after the ammonia water with the formula amount is rapidly added when the heat release of the polymerization is finished, pressing the material into a degassing kettle, washing the polymerization kettle by using soft water with the formula amount, pressing washing water into the degassing kettle, closing a discharge valve of the polymerization kettle, and introducing the degassed butyronitrile latex into a latex storage tank;

the solid content of the high-solid-content carboxylic acrylonitrile-butadiene latex produced by the steps can reach 28.6-30.1%, the high solid content of the acrylonitrile-butadiene latex is reduced due to lack of control on the temperature of finishing polymerization heat release, and air bubbles in the acrylonitrile-butadiene latex can be discharged through the degassing kettle, so that the surface of the produced high-solid-content carboxylic acrylonitrile-butadiene latex is smoother.

EXAMPLE III

The first step is as follows: soft water is sent into a soft water measuring tank through a delivery pump, raw material butyl ester is sent into a butyl ester measuring tank through the delivery pump, raw material acrylonitrile is sent into an acrylonitrile measuring tank through the delivery pump, simultaneously, the phase is configured, initiator solution is configured, and emulsifier C solution is configured;

the second step is that: firstly, carrying out vacuum treatment on a polymerization kettle to keep the internal air pressure of the polymerization kettle at-0.07 MPa, then sending the soft water, the water phase, the stabilizer, the mercaptan and the methacrylic acid in the formula amount into the polymerization kettle, closing other valves on the polymerization kettle, opening an acrylonitrile feeding valve, adding the acrylonitrile in the formula amount, closing the acrylonitrile feeding valve after the addition of the acrylonitrile is finished, opening a butyl ester feeding valve, adding the butyl ester in the formula amount, closing the butyl ester feeding valve after the addition of the butyl ester is finished, and confirming that all valves on the polymerization kettle are closed in place again;

the third step: starting the polymerization kettle for stirring, controlling the rotating speed at 1000-1500r/min, emptying water in a jacket of the polymerization kettle, introducing steam into the jacket of the polymerization kettle for heating, adding an initiator and an emulsifier solution C at 30 ℃, and stopping heating when the temperature reaches 39 ℃;

after the ammonia water with the formula amount is rapidly added when the heat release of the polymerization is finished, pressing the material into a degassing kettle, washing the polymerization kettle by using soft water with the formula amount, pressing washing water into the degassing kettle, closing a discharge valve of the polymerization kettle, and introducing the degassed butyronitrile latex into a latex storage tank;

the solid content of the high-solid-content carboxylic acrylonitrile-butadiene latex produced by the steps can reach 16.8-19.3%, the high solid content of the acrylonitrile-butadiene latex is reduced due to lack of control on the temperature of finishing polymerization heat release, and the rotating speed in a polymerization kettle is too high, so that the generated slurry is relatively turbid, and is incompletely condensed in a specified time, and the yield of the high-solid-content carboxylic acrylonitrile-butadiene latex generated in the subsequent steps is reduced.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.