Composite heat stabilizer, chlorinated polyvinyl chloride pipe and preparation method thereof

文档序号：562153 发布日期：2021-05-18 浏览：15次中文

阅读说明：本技术 一种复合热稳定剂、氯化聚氯乙烯管材及其制备方法 (Composite heat stabilizer, chlorinated polyvinyl chloride pipe and preparation method thereof ) 是由董智贤张新国方景辉何安华于 2021-02-25 设计创作，主要内容包括：本发明适用于管材制备技术领域,提供了一种复合热稳定剂、氯化聚氯乙烯管材及其制备方法,该复合热稳定剂包括以下组分：有机锡类热稳定剂、硬脂酸锌、硬脂酸钙和镁铝水滑石。另外,该氯化聚氯乙烯管材包括以下组分：氯化聚氯乙烯树脂、复合热稳定剂、润滑剂、抗冲击改性剂、无机填料、偶联剂、颜料。本发明提供的氯化聚氯乙烯管材的维卡软化温度不低于110℃,具有耐高温、耐腐蚀、高强度、无污染、不易老化等优点,加工性能良好,可作为工业用管,以用于石油、化工、污水处理与水处理、电力电子、冶金、采矿、造纸等工业管道领域。(The invention is applicable to the technical field of pipe preparation, and provides a composite heat stabilizer, a chlorinated polyvinyl chloride pipe and a preparation method thereof, wherein the composite heat stabilizer comprises the following components: organotin heat stabilizer, zinc stearate, calcium stearate and magnesium aluminum hydrotalcite. In addition, the chlorinated polyvinyl chloride pipe comprises the following components: chlorinated polyvinyl chloride resin, a composite heat stabilizer, a lubricant, an impact resistance modifier, an inorganic filler, a coupling agent and a pigment. The chlorinated polyvinyl chloride pipe provided by the invention has the Vicat softening temperature of not less than 110 ℃, has the advantages of high temperature resistance, corrosion resistance, high strength, no pollution, difficult aging and the like, has good processing performance, and can be used as an industrial pipe for the industrial pipeline fields of petroleum, chemical industry, sewage treatment and water treatment, power electronics, metallurgy, mining, paper making and the like.)

1. The composite heat stabilizer is characterized by comprising an organic tin heat stabilizer, zinc stearate, calcium stearate and magnesium aluminum hydrotalcite; the mass ratio of the organic tin heat stabilizer to the zinc stearate to the calcium stearate to the magnesium aluminum hydrotalcite is 1 (0.5-2.5) to 1-6 (0.5-2.0).

2. The composite heat stabilizer according to claim 1, wherein the organotin-based heat stabilizer is one or more selected from the group consisting of methyltin mercaptide, dimethyltin chloride, butyltin mercaptide, dibutyltin dichloride, dibutyltin oxide, dibutyltin dilaurate, dibutyltin laurate maleate, dibutyltin maleate, octyltin mercaptide, octyltin oxide, dioctyltin dilaurate and dioctyltin maleate.

3. The composite heat stabilizer according to claim 1 or 2, wherein the organotin-based heat stabilizer is tin methyl mercaptide.

4. A chlorinated polyvinyl chloride pipe material, which comprises a chlorinated polyvinyl chloride resin and is characterized by further comprising the composite heat stabilizer as claimed in any one of claims 1 to 3.

5. The chlorinated polyvinyl chloride pipe material according to claim 4, comprising the following raw materials in parts by weight: 100 parts of chlorinated polyvinyl chloride resin, 4-10 parts of composite heat stabilizer, 3-4 parts of lubricant, 8-20 parts of impact modifier, 1-10 parts of inorganic filler, 0.05-0.1 part of coupling agent and 0.5-5 parts of pigment.

6. The chlorinated polyvinyl chloride pipe material according to claim 5, wherein the lubricant is one or more of stearic acid, stearic acid monoglyceride, paraffin wax, polyethylene wax, oxidized polyethylene wax, chlorinated paraffin wax, stearic acid amide, methylene bis stearamide, ethylene bis stearamide, hydroxyethyl ethylene bis stearamide;

the impact modifier is one or more of chlorinated polyethylene, ethylene-vinyl acetate copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer and acrylate copolymer;

the inorganic filler is one or more of calcium carbonate, talcum powder, mica powder, white carbon black, wollastonite, barium sulfate powder, kaolin, bentonite, zirconium phosphate, montmorillonite, glass beads, white mud, magnesium hydroxide and aluminum hydroxide;

the coupling agent is one or more of aluminate coupling agent and titanate coupling agent;

the pigment is one or more of titanium dioxide, lithopone, zinc oxide and lithopone.

7. The chlorinated polyvinyl chloride pipe material of claim 6, wherein the lubricant comprises stearic acid, ethylene bis stearamide and oxidized polyethylene wax, and the mass part ratio of the stearic acid, the ethylene bis stearamide and the oxidized polyethylene wax is 1 (1-5) to (1-5);

the impact modifier comprises chlorinated polyethylene and a methyl methacrylate-butadiene-styrene copolymer, and the mass ratio of the chlorinated polyethylene to the methyl methacrylate-butadiene-styrene copolymer is (1-3) to 1;

the inorganic filler is calcium carbonate and/or barium sulfate powder;

the aluminate coupling agent is isopropoxy distearoyl acyloxy aluminate; the titanate coupling agent is one or more of isopropyl tri (dioctyl acyloxy phosphate) titanate, isopropyl tri (dioctyl acyloxy pyrophosphate) titanate and tetraisopropyl di (dioctyl acyloxy phosphite) titanate;

the pigment is rutile titanium dioxide.

8. A method for preparing a chlorinated polyvinyl chloride pipe material according to any one of claims 5 to 7, comprising the following steps:

weighing chlorinated polyvinyl chloride resin, a composite heat stabilizer, a lubricant, an impact modifier, an inorganic filler, a coupling agent and a pigment according to the mass parts of the components;

drying the inorganic filler, mixing the inorganic filler with a coupling agent, and then thermally mixing the inorganic filler, the chlorinated polyvinyl chloride resin, the composite heat stabilizer, the lubricant, the impact modifier and the pigment at a temperature of 90-110 ℃ to obtain a mixture;

and (3) placing the mixture at the temperature of 40-55 ℃ for cold mixing, and then carrying out extrusion plasticizing and cooling shaping treatment to obtain the chlorinated polyvinyl chloride pipe.

9. The method for preparing a composite heat stabilizer according to claim 8, wherein in the step of extruding and plasticizing, the temperature of the extruder barrel in the first zone is as follows: 190-200 ℃, and the second zone is as follows: 180-190 ℃; the third area is: 175-185 ℃, and the four zones are: 170-180 ℃, and the five zones are as follows: 165-175 ℃; the transition section temperature is: 160-170 ℃; the first mold temperature zone is: 170-185 ℃, and the second zone is: 170-180 ℃, and three zones are as follows: 175-185 ℃; the temperature of the neck ring mold is as follows: 160-210 ℃; the rotating speed of the main machine is as follows: 10-30 r/min; the rotating speed of the feeder is as follows: 10-30 r/min; the melt pressure was: 15 to 25 MPa.

10. The chlorinated polyvinyl chloride pipe prepared by the preparation method according to any one of claims 8 to 9, wherein the Vicat softening temperature of the chlorinated polyvinyl chloride pipe is not lower than 110 ℃.

Technical Field

The invention belongs to the technical field of pipe preparation, and particularly relates to a composite heat stabilizer, a chlorinated polyvinyl chloride pipe and a preparation method thereof.

Background

The chlorinated polyvinyl chloride resin is a high polymer material formed by chlorination modification of polyvinyl chloride, and the chlorine content is increased from 56-59% (mass percent) to 63-75% (mass percent). As the chlorine content increases, the density of the chlorinated polyvinyl chloride resin increases, the softening point increases, the heat resistance increases, the corrosivity against acids, alkalis, salts, oxidizing agents, and the like increases, and the rigidity and tensile strength increase. The good comprehensive performance makes the chlorinated polyvinyl chloride resin become one of the best engineering materials of industrial pipelines, cold and hot water pipelines and fireproof pipelines, and can be used for manufacturing various matching systems such as valves, pipe fittings and the like.

However, the chlorinated polyvinyl chloride resin has high melt viscosity, high plasticizing temperature, large friction among molten resin particles and low thermal stability, and brings great difficulty to extrusion molding processing; meanwhile, the problems of increased brittleness and low impact strength exist in the aspect of mechanical property.

Disclosure of Invention

The embodiment of the invention aims to provide a composite heat stabilizer, and aims to solve the problems in the background art.

The embodiment of the invention is realized in such a way that the composite heat stabilizer comprises an organic tin heat stabilizer, zinc stearate, calcium stearate and magnesium aluminum hydrotalcite; the mass ratio of the organic tin heat stabilizer to the zinc stearate to the calcium stearate to the magnesium aluminum hydrotalcite is 1 (0.5-2.5) to 1-6 (0.5-2.0).

As a preferable mode of the embodiment of the present invention, the organotin-based heat stabilizer is one or more of methyltin mercaptide, dimethyltin chloride, butyltin mercaptide, dibutyltin dichloride, dibutyltin oxide, dibutyltin dilaurate, dibutyltin laurate maleate, dibutyltin maleate, octyltin mercaptide, octyltin oxide, dioctyltin dilaurate, and dioctyltin maleate.

In another preferred embodiment of the present invention, the organotin-based heat stabilizer is tin methyl mercaptide.

Another objective of the embodiments of the present invention is to provide a chlorinated polyvinyl chloride pipe, which includes a chlorinated polyvinyl chloride resin, and further includes the composite heat stabilizer.

As another preferred scheme of the embodiment of the invention, the chlorinated polyvinyl chloride pipe comprises the following raw materials in parts by weight: 100 parts of chlorinated polyvinyl chloride resin, 4-10 parts of composite heat stabilizer, 3-4 parts of lubricant, 8-20 parts of impact modifier, 1-10 parts of inorganic filler, 0.05-0.1 part of coupling agent and 0.5-5 parts of pigment.

As another preferable scheme of the embodiment of the present invention, the lubricant is one or more of stearic acid, stearic acid monoglyceride, paraffin, polyethylene wax, oxidized polyethylene wax, chlorinated paraffin, stearic acid amide, methylene bis stearamide, ethylene bis stearamide, and hydroxyethyl ethylene bis stearamide;

the impact modifier is one or more of Chlorinated Polyethylene (CPE), ethylene-vinyl acetate copolymer (EVA), methyl methacrylate-butadiene-styrene copolymer (MBS), acrylonitrile-butadiene-styrene copolymer (ABS) and Acrylate Copolymer (ACR);

the coupling agent is one or more of aluminate coupling agent and titanate coupling agent;

the pigment is one or more of titanium dioxide, lithopone, zinc oxide and lithopone.

As another preferable scheme of the embodiment of the invention, the lubricant comprises stearic acid, ethylene bis stearamide and oxidized polyethylene wax, and the mass part ratio of the stearic acid, the ethylene bis stearamide and the oxidized polyethylene wax is 1 (1-5) to (1-5);

the inorganic filler is calcium carbonate and/or barium sulfate powder;

the pigment is rutile titanium dioxide.

Another objective of the embodiments of the present invention is to provide a method for preparing the chlorinated polyvinyl chloride pipe, which includes the following steps:

As another preferable scheme of the embodiment of the present invention, in the step, during the extrusion plasticizing, the first zone of the temperature of the extruder barrel is: 190-200 ℃, and the second zone is as follows: 180-190 ℃; the third area is: 175-185 ℃, and the four zones are: 170-180 ℃, and the five zones are as follows: 165-175 ℃; the transition section temperature is: 160-170 ℃; the first mold temperature zone is: 170-185 ℃, and the second zone is: 170-180 ℃, and three zones are as follows: 175-185 ℃; the temperature of the neck ring mold is as follows: 160-210 ℃; the rotating speed of the main machine is as follows: 10-30 r/min; the rotating speed of the feeder is as follows: 10-30 r/min; the melt pressure was: 15-25M Pa.

Another object of the embodiments of the present invention is to provide a chlorinated polyvinyl chloride pipe prepared by the above preparation method. Wherein the Vicat softening temperature of the chlorinated polyvinyl chloride pipe is not lower than 110 ℃.

The composite heat stabilizer provided by the embodiment of the invention can be used for preparing chlorinated polyvinyl chloride pipes, the prepared chlorinated polyvinyl chloride pipes have the Vicat softening temperature of not less than 110 ℃, have the advantages of high temperature resistance, corrosion resistance, high strength, no pollution, difficult aging and the like, have good processing performance, and can be used as industrial pipes for the industrial pipe fields of petroleum, chemical industry, sewage treatment and water treatment, power electronics, metallurgy, mining, papermaking and the like.

The raw materials used in the technical scheme of the invention are all nontoxic and harmless substances, are environment-friendly, do not produce pollution and secondary pollution, and can be directly used. The four environment-friendly heat stabilizers of organotin heat stabilizers, zinc stearate, calcium stearate and magnesium aluminum hydrotalcite are reasonably combined to achieve synergistic effect, so that the use amounts of tin methyl mercaptide, zinc stearate and calcium stearate are reduced. The advantage of good thermal stability of the expensive organic tin is fully exerted, and the problems of cost and poor lubricity caused by large-scale use are avoided; meanwhile, the problem of zinc burning of zinc stearate and the problem of brittleness of products caused by calcium stearate are reduced.

In addition, the preparation method provided by the embodiment of the invention has the advantages of clear and simple process flow, excellent quality of the produced pipe, low cost and safe production through optimization of the formula and the production process.

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

The embodiment provides a preparation method of a chlorinated polyvinyl chloride pipe, which comprises the following steps:

s1, weighing 1000g of chlorinated polyvinyl chloride resin, 90g of composite heat stabilizer, 30g of lubricant, 100g of impact modifier, 50g of inorganic filler, 0.5g of coupling agent and 50g of pigment according to the mass parts of the components for later use;

the lubricant is a mixture of stearic acid, oxidized polyethylene wax and ethylene bis stearamide; the mass part ratio of the stearic acid, the ethylene bis stearamide and the oxidized polyethylene wax is 1:5: 4;

the impact modifier is a mixture of Chlorinated Polyethylene (CPE) and methyl methacrylate-butadiene-styrene copolymer (MBS), and the mass ratio of the chlorinated polyethylene to the methyl methacrylate-butadiene-styrene copolymer is 1.5: 1; the inorganic filler is calcium carbonate; the coupling agent is isopropoxy distearoyl acyloxy aluminate H Y-988; the pigment is rutile type titanium dioxide.

S2, placing the weighed inorganic filler into a blast drying oven, drying at 105 ℃ until the water content is lower than 0.3%, then placing into a high-speed mixer (preheating to the material temperature of 100 ℃), slowly adding the weighed coupling agent while stirring at the rotating speed of 800 revolutions per minute, then quickly stirring and modifying at the speed of 800 revolutions per minute for 15 minutes, then sequentially adding the weighed chlorinated polyvinyl chloride resin, the composite heat stabilizer, the lubricant, the impact modifier and the pigment, stirring uniformly, introducing into a hot mixer, and hot mixing at the temperature of 100 ℃ to obtain a mixture.

And S3, discharging the obtained mixture into a cold mixer at 50 ℃, carrying out low-speed cold mixing at the speed of 200 r/min, then sending the mixture into a parallel double-screw extruder with an oil cooling device to extrude the mixture into a die, and then carrying out cooling shaping, traction cutting and inspection to obtain the finished chlorinated polyvinyl chloride pipe. Wherein, during extrusion plasticization, the first zone of the temperature of the extruder cylinder is as follows: 195 ℃, zone two: 185 ℃ of temperature; the third area is: 180 ℃, and the four zones are: 175 ℃ and five zones: 170 ℃; the transition section temperature is: 165 ℃; the first mold temperature zone is: 180 ℃, and the second zone is: 175 ℃, three zones are: 180 ℃; the temperature of the neck ring mold is as follows: 185 ℃ of temperature; the rotating speed of the main machine is as follows: 20 r/min; the rotating speed of the feeder is as follows: 20 r/min; the melt pressure was: 20 MPa.

Examples 2 to 8

The preparation methods and process parameters of examples 2 to 8 are the same as those of example 1, except that the amounts of the components are different, and specifically, the amounts of the components and the amounts thereof used in examples 1 to 8 are shown in table 1.

TABLE 1

Example 9

The embodiment provides a preparation method of a chlorinated polyvinyl chloride pipe, which comprises the following steps:

s1, weighing 1000g of chlorinated polyvinyl chloride resin, 40g of composite heat stabilizer, 30g of lubricant, 80g of impact modifier, 10g of inorganic filler, 0.5g of coupling agent and 5g of pigment according to the mass parts of the components for later use;

wherein the composite heat stabilizer comprises an organic tin heat stabilizer, zinc stearate, calcium stearate and magnesium aluminum hydrotalcite; the mass ratio of the organotin heat stabilizer to the zinc stearate to the calcium stearate to the magnesium aluminum hydrotalcite is 1:0.5:1: 0.5; the organotin heat stabilizer is a mixture of dimethyltin chloride, butyltin mercaptide and dibutyltin dichloride in equal mass ratio; the lubricant is stearic acid monoglyceride; the impact modifier is acrylate copolymer; the inorganic filler is a mixture of calcium carbonate and barium sulfate powder in equal mass ratio; the coupling agent is a mixture of aluminate coupling agent and titanate coupling agent in equal mass ratio; the aluminate coupling agent is isopropoxy distearoyl acyloxy aluminate; the titanate coupling agent is isopropyl tri (dioctyl phosphate acyloxy) titanate; the pigment is a mixture of lithopone, zinc oxide and lithopone in equal mass ratio.

S2, placing the weighed inorganic filler into a forced air drying oven, drying at 100 ℃ until the water content is lower than 0.3%, then placing into a high-speed mixer (preheating to the material temperature of 90 ℃), slowly adding the weighed coupling agent while stirring at the rotating speed of 500 revolutions per minute, then quickly stirring and modifying at the speed of 500 revolutions per minute for 5 minutes, then sequentially adding the weighed chlorinated polyvinyl chloride resin, the composite heat stabilizer, the lubricant, the impact modifier and the pigment, stirring uniformly, introducing into a hot mixer, and hot mixing at the temperature of 90 ℃ to obtain a mixture.

S3, discharging the obtained mixture into a cold mixer at 40 ℃, carrying out low-speed cold mixing at the speed of 100 r/min, then sending the mixture into a parallel double-screw extruder with an oil cooling device to extrude into a die, and then carrying out cooling shaping, traction cutting and inspection to obtain the finished chlorinated polyvinyl chloride pipe. Wherein, during extrusion plasticization, the first zone of the temperature of the extruder cylinder is as follows: 190 ℃ and the second zone is: 180 ℃; the third area is: 175 ℃, four zones are: 170 ℃ and five zones: 165 ℃; the transition section temperature is: 160 ℃; the first mold temperature zone is: 170 ℃ and the second zone is: 170 ℃ and three zones: 175 ℃; the temperature of the neck ring mold is as follows: 160 ℃; the rotating speed of the main machine is as follows: 10 r/min; the rotating speed of the feeder is as follows: 10 r/min; the melt pressure was: 15 MPa.

Example 10

The embodiment provides a preparation method of a chlorinated polyvinyl chloride pipe, which comprises the following steps:

s1, weighing 1000g of chlorinated polyvinyl chloride resin, 100g of composite heat stabilizer, 40g of lubricant, 200g of impact modifier, 100g of inorganic filler, 1g of coupling agent and 50g of pigment according to the mass parts of the components for later use;

wherein the composite heat stabilizer comprises an organic tin heat stabilizer, zinc stearate, calcium stearate and magnesium aluminum hydrotalcite; the mass ratio of the organotin heat stabilizer to the zinc stearate to the calcium stearate to the magnesium aluminum hydrotalcite is 1:2.5:6: 2; the organic tin heat stabilizer is a mixture of dibutyltin oxide and dibutyltin dilaurate in equal mass ratio; the lubricant is a mixture of stearic acid, oxidized polyethylene wax and ethylene bis stearamide; the mass part ratio of the stearic acid, the ethylene bis stearamide and the oxidized polyethylene wax is 1:1: 1; the impact modifier is a mixture of ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer and acrylate copolymer in equal mass ratio; the inorganic filler is a mixture of talcum powder, mica powder and white carbon black in equal mass ratio; the coupling agent is titanate coupling agent; the titanate coupling agent is a mixture of isopropyl tri (dioctyl acyloxy phosphate) titanate, isopropyl tri (dioctyl acyloxy pyrophosphate) titanate and tetraisopropyl di (dioctyl acyloxy phosphite) titanate in equal mass ratio; the pigment is a mixture of rutile titanium dioxide and lithopone in equal mass ratio.

S2, placing the weighed inorganic filler into a forced air drying oven, drying at 110 ℃ until the water content is lower than 0.3%, then placing into a high-speed mixer (preheating to the material temperature of 110 ℃), slowly adding the weighed coupling agent while stirring at the rotating speed of 1000 r/min, then quickly stirring and modifying at the speed of 1000 r/min for 30 minutes, then sequentially adding the weighed chlorinated polyvinyl chloride resin, the composite heat stabilizer, the lubricant, the impact modifier and the pigment, stirring uniformly, introducing into a hot mixer, and hot mixing at the temperature of 110 ℃ to obtain a mixture.

S3, discharging the obtained mixture into a cold mixer at 55 ℃, carrying out low-speed cold mixing at the speed of 300 r/min, then sending the mixture into a parallel double-screw extruder with an oil cooling device to extrude the mixture into a die, and then carrying out cooling shaping, traction cutting and inspection to obtain the finished chlorinated polyvinyl chloride pipe. Wherein, during extrusion plasticization, the first zone of the temperature of the extruder cylinder is as follows: 200 ℃, and the second zone is: 190 ℃; the third area is: 185 ℃ and four zones: 180 ℃, and the five zones are: 175 ℃; the transition section temperature is: 170 ℃; the first mold temperature zone is: 185 ℃ and the second zone is: the three zones at 180 ℃ are: 185 ℃ of temperature; the temperature of the neck ring mold is as follows: at 210 ℃; the rotating speed of the main machine is as follows: 30 r/min; the rotating speed of the feeder is as follows: 30 r/min; the melt pressure was: 25 MPa.

Example 11