阅读说明：本技术 一种改性聚三氟氯乙烯树脂的制造方法 (Method for preparing modified polychlorotrifluoroethylene resin ) 是由 张炉青 倪姝姝 缪璐阳 张书香 于 2021-06-25 设计创作，主要内容包括：本发明公开了一种改性聚三氟氯乙烯树脂的制造方法,包括如下步骤：称取各组分：三氟氯乙烯、高纯水、疏水性高分子系分散剂、引发剂、表面活性剂；将三氟氯乙烯、高纯水、疏水性高分子系分散剂加入反应釜中进行一次分散；在所得分散液中添加表面活性剂,进行二次分散；在所得二次分散液中添加高纯水和引发剂继续反应,所得产物经洗涤、干燥,得到聚三氟氯乙烯树脂。本发明通过制备过程中向分散液中添加表面活性剂,可以有效降低吸水时源于分散介质所散发的臭味,并且添加的油溶性氧化还原型引发剂可以保证三氟氯乙烯的链增长反应在油相中均速进行,然后析出聚三氟氯乙烯树脂,后期无需再进行造粒。(The invention discloses a method for preparing modified polychlorotrifluoroethylene resin, which comprises the following steps: weighing the following components: chlorotrifluoroethylene, high-purity water, a hydrophobic polymeric dispersant, an initiator, and a surfactant; adding chlorotrifluoroethylene, high-purity water and a hydrophobic macromolecular dispersant into a reaction kettle for primary dispersion; adding a surfactant into the obtained dispersion liquid for secondary dispersion; adding high-purity water and an initiator into the obtained secondary dispersion liquid for continuous reaction, and washing and drying the obtained product to obtain the polychlorotrifluoroethylene resin. In the invention, the surfactant is added into the dispersion liquid in the preparation process, so that the odor emitted from the dispersion medium during water absorption can be effectively reduced, the added oil-soluble redox initiator can ensure that the chain growth reaction of the chlorotrifluoroethylene can be carried out at a uniform speed in an oil phase, and then the polychlorotrifluoroethylene resin is separated out without granulation in the later period.)

1. A method for producing a modified polychlorotrifluoroethylene resin, comprising the steps of:

step 1: weighing the following components in parts by weight: 150 parts of chlorotrifluoroethylene, 1000 parts of high-purity water, 50-200 parts of hydrophobic polymer dispersant, 0.1-1 part of initiator and 1-5 parts of surfactant;

step 2: adding chlorotrifluoroethylene, high-purity water and a hydrophobic polymer dispersant into a reaction kettle for primary dispersion, wherein the stirring speed is 400-500rmp, and the dispersion lasts for 2-4 hours;

and step 3: adding a surfactant into the dispersion liquid obtained in the step 2, continuously keeping the stirring speed at 400-500rmp, and performing secondary dispersion for 1-2 hours;

and 4, step 4: adding high-purity water and an initiator into the secondary dispersion liquid obtained in the step 3, then reacting for 4-6 hours at the pressure of 0.8-2MPa and the temperature of 20-40 ℃, then adjusting the stirring speed to be 100-200rmp, heating to 50 ℃, continuing to react for 2-4 hours, washing and drying the obtained product to obtain the polychlorotrifluoroethylene resin.

2. The method of claim 1, wherein the hydrophobic polymeric dispersant is at least one of a maleic anhydride-modified ethylene-propylene copolymer, a maleic anhydride-ethylene copolymer, and a maleic anhydride-propylene copolymer.

3. The method of claim 1, wherein the initiator is an oil-soluble redox initiator.

4. The method of claim 1, wherein the half-life of the oil-soluble redox initiator is 0.1 to 8 hours at 10 to 40 ℃.

5. The method of claim 1, wherein the oil-soluble redox initiator is at least one selected from isobutyl dicarbonate, cyclohexyl dicarbonate peroxide, dibenzoyl peroxide, and disuccinic peroxide.

6. The process according to claim 1, wherein the high purity water has an electric conductivity of not more than 0.1. mu.S-cm-1 and a pH of 6.6 to 7.4.

7. The process for producing a modified polychlorotrifluoroethylene resin according to any one of claims 1 to 6 wherein the surfactant is a fluorine-containing surfactant.

Technical Field

The invention relates to the technical field of polymer production, in particular to a method for preparing modified polychlorotrifluoroethylene resin.

Background

Polychlorotrifluoroethylene, a polymer of chlorotrifluoroethylene, has excellent chemical stability, insulation and weather resistance, mechanical strength and hardness superior to those of polytetrafluoroethylene, has better transparency and lower air permeation rate when made into a film, is inert to most active chemicals at room temperature and is convenient to store, and has excellent gas barrier ability, the water vapor permeability of the film product is the lowest in all transparent plastic films, the electrical properties of the film product are similar to those of other perfluoropolymers, but the dielectric constant and the loss factor are slightly higher, and particularly at high frequency, the polychlorotrifluoroethylene can be made into thicker optically transparent products.

At present, odor is easily generated by medium dispersion of the existing polychlorotrifluoroethylene resin after water absorption, and the prepared polymers have different shapes, cannot be molded at one time, need to be re-granulated at a later stage, and have higher production cost.

Disclosure of Invention

The present invention has been made to solve the above problems occurring in the prior art, and an object of the present invention is to provide a method for producing a modified polychlorotrifluoroethylene resin.

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

a method for producing a modified polychlorotrifluoroethylene resin, comprising the steps of:

step 1: weighing the following components in parts by weight: 150 parts of chlorotrifluoroethylene, 1000 parts of high-purity water, 50-200 parts of hydrophobic polymer dispersant, 0.1-1 part of initiator and 1-5 parts of surfactant;

step 2: adding chlorotrifluoroethylene, high-purity water and a hydrophobic polymer dispersant into a reaction kettle for primary dispersion, wherein the stirring speed is 400-500rmp, and the dispersion lasts for 2-4 hours;

and step 3: adding a surfactant into the dispersion liquid obtained in the step 2, continuously keeping the stirring speed at 400-500rmp, and performing secondary dispersion for 1-2 hours;

and 4, step 4: adding high-purity water and an initiator into the secondary dispersion liquid obtained in the step 3, then reacting for 4-6 hours at the pressure of 0.8-2MPa and the temperature of 20-40 ℃, then adjusting the stirring speed to be 100-200rmp, heating to 50 ℃, continuing to react for 2-4 hours, washing and drying the obtained product to obtain the polychlorotrifluoroethylene resin.

Preferably, the hydrophobic polymeric dispersant is at least one of a maleic anhydride-modified ethylene-propylene copolymer, a maleic anhydride-ethylene copolymer, and a maleic anhydride-propylene copolymer.

Preferably, the initiator is an oil-soluble redox initiator.

Preferably, the oil-soluble redox initiator has a half-life of 0.1 to 8 hours at 10 to 40 ℃.

Preferably, the oil-soluble redox initiator is at least one of isobutyl dicarbonate, cyclohexyl dicarbonate peroxide, dibenzoyl peroxide and disuccinic peroxide.

Preferably, the high-purity water has an electric conductivity of not more than 0.1. mu.S-cm-1 and a pH value of 6.6 to 7.4.

Preferably, the surfactant is a fluorosurfactant.

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

the prepared polychlorotrifluoroethylene resin has certain water absorbability through the added hydrophobic macromolecular dispersant, the surfactant is added into the dispersion liquid in the preparation process, the odor derived from the dispersion medium and emitted in the water absorbability can be effectively reduced, the added oil-soluble redox initiator can ensure that the chain growth reaction of the chlorotrifluoroethylene is carried out at uniform speed in the oil phase, and when the chlorotrifluoroethylene monomer in the oil phase is exhausted, the separated polychlorotrifluoroethylene resin is convenient to wash and dry, and granulation is not required to be carried out in the later period.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.

Example 1

A method for producing a modified polychlorotrifluoroethylene resin, comprising the steps of:

step 1: weighing the following components in parts by weight: 100 parts of chlorotrifluoroethylene, 500 parts of high-purity water with the pH value of 7.1, 50 parts of maleic anhydride modified ethylene-propylene copolymer, 0.1 part of isobutyl dicarbonate and 1 part of fluorine-containing surfactant;

step 2: adding chlorotrifluoroethylene, high-purity water with pH of 7.1 and maleic anhydride modified ethylene-propylene copolymer into a reaction kettle for primary dispersion, wherein the stirring speed is 500rmp, and the dispersion is carried out for 3 hours;

and step 3: adding a fluorine-containing surfactant into the dispersion liquid obtained in the step 2, continuously keeping the stirring speed at 400rmp, and performing secondary dispersion for 2 hours;

and 4, step 4: adding high-purity water and isobutyl dicarbonate into the secondary dispersion liquid obtained in the step 3, reacting for 4 hours at the pressure of 2MPa and the temperature of 40 ℃, adjusting the stirring speed to 100rmp, heating to 50 ℃, continuing to react for 2 hours, washing and drying the obtained product to obtain the polychlorotrifluoroethylene resin.

Example 2

Step 1: weighing the following components in parts by weight: 100 parts of chlorotrifluoroethylene, 500 parts of high-purity water with pH of 7.1, 50 parts of maleic anhydride-ethylene copolymer, 0.1 part of isobutyl dicarbonate and 1 part of fluorine-containing surfactant;

step 2: adding chlorotrifluoroethylene, high-purity water with pH of 7.1 and maleic anhydride-ethylene copolymer into a reaction kettle for primary dispersion, wherein the stirring speed is 500rmp, and the dispersion is carried out for 3 hours;

and step 3: adding a fluorine-containing surfactant into the dispersion liquid obtained in the step 2, continuously keeping the stirring speed at 400rmp, and performing secondary dispersion for 2 hours;

and 4, step 4: adding high-purity water and isobutyl dicarbonate into the secondary dispersion liquid obtained in the step 3, reacting for 4 hours at the pressure of 2MPa and the temperature of 40 ℃, adjusting the stirring speed to 100rmp, heating to 50 ℃, continuing to react for 2 hours, washing and drying the obtained product to obtain the polychlorotrifluoroethylene resin.

Example 3

Step 1: weighing the following components in parts by weight: 100 parts of chlorotrifluoroethylene, 500 parts of high-purity water with pH of 7.1, 50 parts of maleic anhydride-propylene copolymer, 0.1 part of isobutyl dicarbonate and 1 part of fluorine-containing surfactant;

step 2: adding chlorotrifluoroethylene, high-purity water with pH of 7.1 and maleic anhydride-propylene copolymer into a reaction kettle for primary dispersion, wherein the stirring speed is 500rmp, and the dispersion is carried out for 3 hours;

and step 3: adding a fluorine-containing surfactant into the dispersion liquid obtained in the step 2, continuously keeping the stirring speed at 400rmp, and performing secondary dispersion for 2 hours;

and 4, step 4: adding high-purity water and isobutyl dicarbonate into the secondary dispersion liquid obtained in the step 3, reacting for 4 hours at the pressure of 2MPa and the temperature of 40 ℃, adjusting the stirring speed to 100rmp, heating to 50 ℃, continuing to react for 2 hours, washing and drying the obtained product to obtain the polychlorotrifluoroethylene resin.

Example 4

Step 1: weighing the following components in parts by weight: 100 parts of chlorotrifluoroethylene, 500 parts of high-purity water with the pH value of 7.1, 50 parts of maleic anhydride-propylene copolymer, 0.1 part of cyclohexyl peroxydicarbonate and 1 part of fluorine-containing surfactant;

step 2: adding chlorotrifluoroethylene, high-purity water with pH of 7.1 and maleic anhydride-propylene copolymer into a reaction kettle for primary dispersion, wherein the stirring speed is 500rmp, and the dispersion is carried out for 3 hours;

and step 3: adding a fluorine-containing surfactant into the dispersion liquid obtained in the step 2, continuously keeping the stirring speed at 400rmp, and performing secondary dispersion for 2 hours;

and 4, step 4: and (3) adding high-purity water and cyclohexyl peroxydicarbonate into the secondary dispersion liquid obtained in the step (3), then reacting for 4 hours at the pressure of 2MPa and the temperature of 40 ℃, adjusting the stirring rate to be 100rmp, heating to 50 ℃, continuing to react for 2 hours, washing and drying the obtained product, and thus obtaining the polychlorotrifluoroethylene resin.

Example 5

Step 1: weighing the following components in parts by weight: 100 parts of chlorotrifluoroethylene, 500 parts of high-purity water with the pH value of 7.1, 50 parts of maleic anhydride-propylene copolymer, 0.1 part of dibenzoyl peroxide and 1 part of fluorine-containing surfactant;

step 2: adding chlorotrifluoroethylene, high-purity water with pH of 7.1 and maleic anhydride-propylene copolymer into a reaction kettle for primary dispersion, wherein the stirring speed is 500rmp, and the dispersion is carried out for 3 hours;

and step 3: adding a fluorine-containing surfactant into the dispersion liquid obtained in the step 2, continuously keeping the stirring speed at 400rmp, and performing secondary dispersion for 2 hours;

and 4, step 4: adding high-purity water and dibenzoyl peroxide into the secondary dispersion liquid obtained in the step 3, reacting for 4 hours at the pressure of 2MPa and the temperature of 40 ℃, adjusting the stirring speed to be 100rmp, heating to 50 ℃, continuing to react for 2 hours, washing and drying the obtained product to obtain the polychlorotrifluoroethylene resin.

Example 6

Step 1: weighing the following components in parts by weight: 100 parts of chlorotrifluoroethylene, 500 parts of high-purity water with the pH value of 7.1, 50 parts of maleic anhydride-propylene copolymer, 0.1 part of disuccinic acid peroxide and 1 part of fluorine-containing surfactant;

step 2: adding chlorotrifluoroethylene, high-purity water with pH of 7.1 and maleic anhydride-propylene copolymer into a reaction kettle for primary dispersion, wherein the stirring speed is 500rmp, and the dispersion is carried out for 3 hours;

and step 3: adding a fluorine-containing surfactant into the dispersion liquid obtained in the step 2, continuously keeping the stirring speed at 400rmp, and performing secondary dispersion for 2 hours;

and 4, step 4: adding high-purity water and disuccinic acid peroxide into the secondary dispersion liquid obtained in the step 3, reacting for 4 hours at the pressure of 2MPa and the temperature of 40 ℃, adjusting the stirring rate to be 100rmp, heating to 50 ℃, continuing to react for 2 hours, washing and drying the obtained product to obtain the polychlorotrifluoroethylene resin.

Example 7

Step 1: weighing the following components in parts by weight: 100 parts of chlorotrifluoroethylene, 500 parts of high-purity water with the pH value of 7.1, 50 parts of maleic anhydride-propylene copolymer, 0.1 part of disuccinic acid peroxide and 1 part of fluorine-containing surfactant;

step 2: adding chlorotrifluoroethylene, high-purity water with pH of 7.1 and maleic anhydride-propylene copolymer into a reaction kettle for primary dispersion, wherein the stirring speed is 500rmp, and the dispersion is carried out for 3 hours;

and step 3: adding a fluorine-containing surfactant into the dispersion liquid obtained in the step 2, continuously keeping the stirring speed at 400rmp, and performing secondary dispersion for 2 hours;

and 4, step 4: adding high-purity water and disuccinic acid peroxide into the secondary dispersion liquid obtained in the step 3, reacting for 5 hours at the pressure of 2MPa and the temperature of 40 ℃, adjusting the stirring rate to be 100rmp, heating to 50 ℃, continuing to react for 2 hours, washing and drying the obtained product to obtain the polychlorotrifluoroethylene resin.

Example 8

Step 1: weighing the following components in parts by weight: 100 parts of chlorotrifluoroethylene, 500 parts of high-purity water with the pH value of 7.1, 50 parts of maleic anhydride-propylene copolymer, 0.1 part of disuccinic acid peroxide and 1 part of fluorine-containing surfactant;

step 2: adding chlorotrifluoroethylene, high-purity water with pH of 7.1 and maleic anhydride-propylene copolymer into a reaction kettle for primary dispersion, wherein the stirring speed is 500rmp, and the dispersion lasts for 2 hours;

and step 3: adding a fluorine-containing surfactant into the dispersion liquid obtained in the step 2, continuously keeping the stirring speed at 400rmp, and performing secondary dispersion for 2 hours;

and 4, step 4: adding high-purity water and disuccinic acid peroxide into the secondary dispersion liquid obtained in the step 3, reacting for 4 hours at the pressure of 1MPa and the temperature of 40 ℃, adjusting the stirring rate to be 100rmp, heating to 50 ℃, continuing to react for 2 hours, washing and drying the obtained product to obtain the polychlorotrifluoroethylene resin.

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.