阅读说明：本技术 一种高强度耐高温氯化聚氯乙烯棒材及其制备方法 (High-strength high-temperature-resistant chlorinated polyvinyl chloride bar and preparation method thereof ) 是由 肖斌 金胜波 王曙光 孟祥昊 李胜华 董军宁 杨林 于 2021-08-27 设计创作，主要内容包括：一种高强度耐高温氯化聚氯乙烯棒材的原材料,按重量份计,包括：高聚合度CPVC树脂100份,稳定剂7.5-10份,内润滑剂1.5-3份,外润滑剂0.6-1.7份,抗冲改性剂6-7.5份,加工助剂1.2-1.7份,填料1-1.5份,颜料0.05-0.06份；所述聚氯乙烯棒材生产中使用的双螺杆挤出机采用锥形双螺杆挤出机；制备的氯化聚氯乙烯棒材的密度能达到1.51-1.52g/cm～(3),热变形温度能达到117-122℃,拉伸强度能达到60-61MPa,弯曲强度能达到72-74MPa,拉伸弹性模量能达到2780-2900MPa。(A raw material of a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar comprises the following components in parts by weight: 100 parts of high-polymerization-degree CPVC resin, 7.5-10 parts of stabilizer, 1.5-3 parts of internal lubricant, 0.6-1.7 parts of external lubricant, 6-7.5 parts of impact modifier, 1.2-1.7 parts of processing aid, 1-1.5 parts of filler and 0.05-0.06 part of pigment; the double-screw extruder used in the production of the polyvinyl chloride bar adopts a conical double-screw extruder; the density of the prepared chlorinated polyvinyl chloride bar can reach 1.51-1.52g/cm 3 The thermal deformation temperature can reach 117-122 ℃, the tensile strength can reach 60-61MPa, the bending strength can reach 72-74MPa, and the tensile elastic modulus can reach 2780-2900 MPa.)

1. The high-strength high-temperature-resistant chlorinated polyvinyl chloride bar is characterized in that the raw materials of the chlorinated polyvinyl chloride bar comprise the following components in parts by weight: 100 parts of high-polymerization-degree CPVC resin, 7.5-10 parts of stabilizer, 1.5-3 parts of internal lubricant, 0.6-1.7 parts of external lubricant, 6-7.5 parts of impact modifier, 1.2-1.7 parts of processing aid, 1-1.5 parts of filler and 0.05-0.06 part of pigment.

2. The high-strength high-temperature-resistant chlorinated polyvinyl chloride bar as claimed in claim 1, wherein the degree of polymerization of the high-degree-of-polymerization CPVC resin is 1100-1300, and the chlorine content is 68.5-70%.

3. The high-strength high-temperature-resistant chlorinated polyvinyl chloride bar material as claimed in claim 1, wherein the stabilizer is one or more of organic tin, composite calcium-zinc stabilizer, rare earth composite modified stabilizer, zeolite modified stabilizer and epoxy modified stabilizer.

4. The high-strength high-temperature-resistant chlorinated polyvinyl chloride bar as claimed in claim 1, wherein the internal lubricant is one or more of monoglyceride, monostearate, distearate, calcium stearate, glyceryl stearate, pentaerythritol ester and dodecahydroxystearic acid.

5. The high-strength high-temperature-resistant chlorinated polyvinyl chloride bar material according to claim 1, wherein the external lubricant is one or more of paraffin, chlorinated paraffin, oxidized polyethylene wax and polyethylene wax.

6. The high-strength high-temperature-resistant chlorinated polyvinyl chloride bar material according to claim 1, wherein the preparation method of the polyvinyl chloride bar material comprises the following specific steps: firstly, adding high-polymerization-degree CPVC resin into a high mixing machine, adding a stabilizer and a pigment after the material temperature in the high mixing machine reaches 40-50 ℃ after the equipment is opened, then adding all the rest auxiliaries into the high mixing machine at one time, fully mixing until the material temperature reaches 110-120 ℃, then putting the mixture into a cold mixing machine for stirring, discharging when the material temperature is cooled to 45-55 ℃, obtaining a CPVC bar material mixture, then adding the CPVC bar material mixture into a double-screw extruder for processing, and obtaining a CPVC bar material after the CPVC bar material is extruded from the double-screw extruder.

7. The high-strength high-temperature-resistant chlorinated polyvinyl chloride bar as claimed in claim 6, wherein the rotation speed of the high-speed mixer is 500-600rpm, and the stirring speed of the cold mixer is 55-65 rpm.

8. The high-strength high-temperature-resistant chlorinated polyvinyl chloride bar material as claimed in claim 6, wherein the compression ratio of the first section of the die of the twin-screw extruder is 2.6-3:1, and the compression ratio of the second section of the die is 1.1-1.2: 1;

the mould section comprises a mould 2, a mould 3 and a mould 4; the mold sections include a mold 5 and a mold 6.

9. The high-strength high-temperature-resistant chlorinated polyvinyl chloride bar as claimed in claim 6, wherein the twin-screw extruder is a conical twin-screw extruder, and the die is of a two-stage compression structure, namely, a first-stage compression and a second-stage compression.

10. The high-strength high-temperature-resistant chlorinated polyvinyl chloride bar as claimed in claim 9, wherein the melt temperature of the primary compression is 211-213 ℃, and the melt pressure is 219-221 bar; the temperature of the secondary compression melt is 207-209 ℃, and the melt pressure is 239-241 bar.

Technical Field

The invention relates to the technical field of chlorinated polyvinyl chloride, and particularly relates to a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar and a preparation method thereof.

Background

Chlorinated polyvinyl chloride (CPVC) resin is a high-performance material obtained by deeply chlorinating and modifying polyvinyl chloride (PVC) resin, the chlorine content of the modified CPVC reaches 65-72%, the heat distortion temperature of the product can reach more than 125 ℃, the tensile mechanical strength of the material can reach more than 60MPa, in addition, the corrosion resistance, the weather resistance and the flame resistance of the CPVC material are further improved, the CPVC material becomes an engineering material with excellent comprehensive performance, and the CPVC product is widely applied to a plurality of fields of chemical industry, electric power, fire fighting, building, automobiles, mining, water conveying pipelines and the like, and becomes a high-performance engineering material which is developed rapidly in recent years.

In the field of chemical industry, a plurality of chlorinated polyvinyl chloride (CPVC) parts with complex structures are needed, and the CPVC parts have comprehensive properties of high strength, high temperature resistance, corrosion resistance and the like. As is well known, the CPVC material is mainly formed by extrusion and injection molding, but many parts have complicated structures and are difficult to be processed by extrusion and injection molding techniques, so engineers process the CPVC material into a round bar and then complete the production and processing of the complex CPVC parts by turning techniques, thus solving a major problem in the industry.

From the production technology, the production and processing of the CPVC bar currently adopts the following process technologies: firstly, mixing CPVC resin and related auxiliaries according to a certain proportion to form a mixed material, then granulating by using double-screw equipment, extruding a bar by using a single-screw extruder after the granulation is finished, and finally cooling and shaping to finish the production of the CPVC bar, so that the production process is complex, the efficiency is low, and the energy consumption is improved.

From the formulation point of view, the CPVC resins used in the production of CPVC bars have a relatively low degree of polymerization, substantially below 1000; the chlorine content of the selected CPVC resin is generally below 67%, and the two factors determine that the mechanical strength and the heat distortion temperature of the current CPVC bar are relatively low, so that the application of high heat resistance and high strength is difficult to meet.

Therefore, the processing technology and difficulty of the CPVC bar are far higher than those of pipes, profiles and injection molding parts, the production and processing of the CPVC bar have higher technical requirements on raw materials, equipment and processes, at present, domestic manufacturers can only produce small-size bars with lower performance indexes, and large-diameter bars, high-strength and high-heat-resistance bars are almost imported and are expensive, so that the application and popularization of the products are limited.

Disclosure of Invention

The invention provides a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar and a preparation method thereof.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a raw material of a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar comprises the following components in parts by weight: 100 parts of high-polymerization-degree CPVC resin, 7.5-10 parts of stabilizer, 1.5-3 parts of internal lubricant, 0.6-1.7 parts of external lubricant, 6-7.5 parts of impact modifier, 1.2-1.7 parts of processing aid, 1-1.5 parts of filler and 0.05-0.06 part of pigment.

The polymerization degree of the CPVC resin with high polymerization degree is 1100-1300, and the chlorine content is 68.5-70%.

The stabilizer is one or more of organic tin, a composite calcium-zinc stabilizer, a rare earth composite modified stabilizer, a zeolite modified stabilizer and an epoxy modified stabilizer;

preferably, the stabilizer is organotin;

the internal lubricant is one or more of monoglyceride, monostearate, distearate, calcium stearate, glyceryl stearate, pentaerythritol ester and dodecahydroxystearic acid;

the external lubricant is one or more of paraffin, chlorinated paraffin, oxidized polyethylene wax and polyethylene wax;

the impact modifier is one or more of ACR, MBS, CPE, ABS and high impact HIPS;

the processing aid is one or more of acrylic processing aid, ACR201, ACR401, PA40, PA80 and ASA;

the filler is one or more of titanium dioxide, nano silicon dioxide and hydrotalcite;

the pigment is one or more of carbon black and phthalocyanine blue.

A preparation method of a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar material comprises the following steps: firstly, adding high-polymerization-degree CPVC resin into a high mixing machine, adding a stabilizer and a pigment after the material temperature in the high mixing machine reaches 40-50 ℃ after the equipment is opened, then adding all the rest auxiliaries into the high mixing machine at one time, fully mixing until the material temperature reaches 110-120 ℃, then putting the mixture into a cold mixing machine for stirring, discharging when the material temperature is cooled to 45-55 ℃, obtaining a CPVC bar material mixture, then adding the CPVC bar material mixture into a double-screw extruder for processing, and obtaining a CPVC bar material after the CPVC bar material is extruded from the double-screw extruder.

The rotating speed of the high-speed mixer is 500-600 rpm.

The stirring speed of the cold mixer is 55-65 rpm.

The processing conditions of the double-screw extruder are as follows: the temperature of the material barrel 1 is 175-182 ℃, the temperature of the material barrel 2 is 175-180 ℃, the temperature of the material barrel 3 is 170-172 ℃, the temperature of the material barrel 4 is 168-170 ℃, the temperature of the confluence core is 166-170 ℃, the temperature of the die 1 is 168-172 ℃, the temperature of the die 2 is 168-172 ℃, the temperature of the die 3 is 170-174 ℃, the temperature of the die 4 is 172-176-, the temperature of the die 5 is 178-190 ℃, the temperature of the die 6 is 190-200 ℃, the screw is 20-26 turns, the feeding is 36-65 turns, the melting temperature is 215-217 ℃, the melting pressure is 171-236bar, and the traction speed is 0.4-0.8 m/min.

The compression ratio of the first section of the die of the double-screw extruder is 2.6-3:1, and the compression ratio of the second section of the die is 1.1-1.2: 1.

The mould section comprises a mould 2, a mould 3 and a mould 4; the mold sections include a mold 5 and a mold 6.

The heat distortion temperature of the CPVC bar is 117-122 ℃, the tensile strength is 60-61MPa, the bending strength is 72-74MPa, and the elastic modulus is 2780-2900 MPa.

The double-screw extruder adopts a conical double-screw extruder, and the die adopts a two-stage compression structure, namely first-stage compression and second-stage compression.

Wherein the melt temperature of the first-stage compression is 211-213 ℃, and the melt pressure is 219-221 bar; the temperature of the secondary compression melt is 207-209 ℃, and the melt pressure is 239-241 bar.

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

(1) according to the preparation method of the high-strength high-temperature-resistant chlorinated polyvinyl chloride bar, the CPVC resin with high polymerization degree and high chlorine content is adopted for bar production, and the high-temperature-resistant high-strength CPVC bar product prepared after optimization and improvement of the formula meets higher use requirements, can be processed into special CPVC parts with complex structures, and can also be processed into high-strength corrosion-resistant plastic bolts;

(2) according to the preparation method of the high-strength high-temperature-resistant chlorinated polyvinyl chloride bar, the CPVC bar compound with good stability, good processability, high thermal deformation temperature and high tensile strength is prepared, the compound has excellent thermal stability so as to meet the requirements in the processing process, and meanwhile, the compound also has good processability, so that the processed CPVC bar has good appearance and no defects;

(3) according to the preparation method of the high-strength high-temperature-resistant chlorinated polyvinyl chloride bar material, the density of the prepared chlorinated polyvinyl chloride bar material can reach 1.51-1.52g/cm³The thermal deformation temperature can reach 117-;

(4) according to the preparation method of the high-strength high-temperature-resistant chlorinated polyvinyl chloride bar, the bar is prepared by one-step forming through improving the bar extrusion die, so that the material defects are reduced to the greatest extent, and the overall performance of the material is improved;

(5) the preparation method of the high-strength high-temperature-resistant chlorinated polyvinyl chloride bar reduces the energy consumption by 30-40%.

Drawings

FIG. 1 is a schematic diagram of portions of a twin screw apparatus;

FIG. 2 is a two-stage compression configuration of a conical twin-screw extruder.

Detailed Description

In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.

Example 1

A raw material of a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar comprises the following components in parts by weight: 100 parts of high-polymerization-degree CPVC resin, 3.5 parts of organic tin, 4 parts of calcium-zinc composite stabilizer, 1.5 parts of dodecahydroxy stearic acid, 1.5 parts of calcium stearate, 0.6 part of polyethylene wax, 4 parts of MBS, 2 parts of ABS, 4011.2 parts of ACR, 0.5 part of ASA, 1 part of titanium dioxide, 0.05 part of carbon black and 0.01 part of phthalocyanine blue.

The manufacturer of the calcium-zinc composite stabilizer is New Material science and technology Co., Ltd, Shandong Jinchang Tree, model number JCS-306.

The polymerization degree of the CPVC resin with the high polymerization degree is 1300, and the chlorine content is 68.5%.

The intrinsic viscosity of ACR401 is 2.0dL/g,25 ℃.

A preparation method of a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar comprises the following specific steps:

1. firstly, adding CPVC resin with high polymerization degree into a high mixing machine, adding organic tin and pigment after the material temperature in the high mixing machine reaches 45 ℃ after the equipment is opened, then adding all the rest auxiliaries into the high mixing machine at one time, fully mixing until the material temperature reaches 110 ℃, then putting the mixture into a cold mixing machine for stirring, and discharging the mixture when the mixture is cooled to 50 ℃ to obtain the CPVC bar material mixed material.

The pigment is carbon black and phthalocyanine blue.

The rotating speed of the high-speed mixer is 550 rpm.

The stirring speed of the cold mixer was 60 rpm.

2. And then adding the CPVC bar material mixture into a double-screw extruder for processing, wherein the processing conditions are as follows:

the twin-screw extruder is constructed as shown in FIG. 1.

Wherein, the mould section comprises a mould 2, a mould 3 and a mould 4; the mould section comprises a mould 5 and a mould 6; the compression ratio of the first section of the die is 3:1, and the compression ratio of the second section of the die is 1.2: 1.

3. And (3) extruding the CPVC bar with the phi 50 calibers from a double-screw extruder to obtain the CPVC bar with the phi 50 calibers, wherein the thermal deformation temperature of the CPVC bar is 117 ℃, the tensile strength is 60MPa, the bending strength is 72MPa, and the elastic modulus is 2800 MPa.

Example 2

A raw material of a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar comprises the following components in parts by weight: 100 parts of high-polymerization-degree CPVC resin, 4 parts of organic tin, 6 parts of calcium-zinc composite stabilizer, 0.7 part of monostearate, 0.8 part of pentaerythritol ester, 0.7 part of chlorinated paraffin, 0.4 part of paraffin, 0.6 part of oxidized polyethylene wax, 6 parts of CPE, 1.5 parts of high-impact HIPS, 2011.2 parts of ACR, 1.5 parts of nano-silica, 0.04 part of carbon black and 0.01 part of phthalocyanine blue.

The manufacturer of the calcium-zinc composite stabilizer is New Material science and technology Co., Ltd, Shandong Jinchang Tree, with the model of JCS-308.

The polymerization degree of the CPVC resin with the high polymerization degree is 1200, and the chlorine content is 69.6%.

The intrinsic viscosity of ACR401 is 2.0dL/g,25 ℃.

A preparation method of a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar comprises the following specific steps:

1. firstly, adding CPVC resin into a high mixing machine, adding organic tin and pigment after the temperature of materials in the high mixing machine reaches 45 ℃ after equipment is opened, then adding all the rest auxiliaries into the high mixing machine at one time, placing the materials in the high mixing machine into a cold mixing machine for stirring when the temperature of the materials reaches 120 ℃, and discharging when the temperature of the materials is cooled to 50 ℃ to obtain the CPVC bar material mixed material.

The pigment is carbon black and phthalocyanine blue.

The rotating speed of the high-speed mixer is 550 rpm.

The stirring speed of the cold mixer was 60 rpm.

2. Adding the CPVC bar material mixture into a double-screw extruder for processing, wherein the processing conditions are as follows:

the twin-screw extruder is constructed as shown in FIG. 1.

Wherein, the mould section comprises a mould 2, a mould 3 and a mould 4; the second mold section comprises a mold 5 and a mold 6, the compression ratio of the first mold section is 2.6:1, and the compression ratio of the second mold section is 1.1: 1.

And extruding the CPVC bar with the phi 90 calibers from a double-screw extruder to obtain the CPVC bar with the thermal deformation temperature of 119 ℃, the tensile strength of 61MPa, the bending strength of 73MPa and the elastic modulus of 2780 MPa.

Example 3

A raw material of a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar comprises the following components in parts by weight: 100 parts of CPVC resin with high polymerization degree, 3 parts of organic tin, 5 parts of calcium-zinc composite stabilizer, 1.1 parts of monoglyceride, 0.5 part of distearic acid, 0.5 part of polyethylene wax, 0.2 part of paraffin, 0.5 part of oxidized polyethylene wax, 7 parts of ACR, 2011.2 parts of ACR, 1.5 parts of nano-silica, 0.04 part of carbon black and 0.01 part of phthalocyanine blue.

The calcium-zinc composite stabilizer is a mixture of a model JCS-306 and a model JCS-308, and the mass ratio of the JCS-306 to the JCS-308 is 3: 2.

JCS-306 and JCS-308 are New materials science and technology Co., Ltd, Jinchang Tree, Shandong.

The polymerization degree of the CPVC resin with high polymerization degree is 1100, and the chlorine content is 70%.

The intrinsic viscosity of ACR401 is 2.0dL/g,25 ℃.

A preparation method of a high-strength high-temperature-resistant chlorinated polyvinyl chloride bar comprises the following specific steps:

1. firstly, adding CPVC resin into a high mixing machine, adding organic tin and pigment after the temperature of materials in the high mixing machine reaches 45 ℃ after the high mixing machine is opened, then adding all the rest auxiliaries into the high mixing machine at one time, placing the materials in the high mixing machine into cold mixing equipment for stirring when the temperature of the materials reaches 115 ℃, and discharging when the temperature of the materials is cooled to 50 ℃ to obtain the CPVC bar material mixed material.

The pigment is carbon black and phthalocyanine blue,

the rotating speed of the high-speed mixer is 550 rpm.

The stirring speed of the cold mixer was 60 rpm.

2. Adding the CPVC bar material mixture into a double-screw extruder for processing, wherein the processing conditions are as follows:

the twin-screw extruder is constructed as shown in FIG. 1.

Wherein, the mould section comprises a mould 2, a mould 3 and a mould 4; the second mold section comprises a mold 5 and a mold 6, the compression ratio of the first mold section is 3:1, and the compression ratio of the second mold section is 1.2: 1.

3. And (3) extruding the CPVC bar with the diameter of phi 32 from a double-screw extruder to obtain the CPVC bar with the heat deformation temperature of 122 ℃, the tensile strength of 60MPa, the bending strength of 74MPa and the elastic modulus of 2900 MPa.

Example 4

The twin-screw extruders of examples 1 to 3 employed tapered twin-screw extruders, and the dies employed two-stage compression structures, one-stage compression and two-stage compression, respectively, as shown in FIG. 2.

Wherein the melt temperature of the first-stage compression is 212 ℃, and the melt pressure is 220 bar; the secondary compression melt temperature was 208 ℃ and the melt pressure was 240 bar.

Example 5

The performance of the CPVC bar obtained in examples 1-3 was compared with the product of the conventional art;

the raw materials of the product in the conventional technology comprise the following components in parts by weight: 100 parts of CPVC resin, 2.7 parts of organic tin, 4.5 parts of calcium-zinc composite stabilizer, 0.7 part of dodecahydroxy stearic acid, 0.5 part of calcium stearate, 7 parts of ABS, 3 parts of MBS, 4012.5 parts of ACR, 3 parts of calcium carbonate and 0.01 part of pigment.

The CPVC resin has the polymerization degree of 950 and the chlorine content of 67.1 percent.

The pigment is carbon black and phthalocyanine blue.

The preparation method of the product by the conventional technology comprises the following specific steps:

1. firstly, adding CPVC resin into a high-speed mixer, adding organic tin after the equipment is opened, then adding a calcium-zinc composite stabilizer, ACR401, MBS and ABS when the material temperature reaches 60-70 ℃, adding dodecahydroxystearic acid, calcium stearate and calcium carbonate when the material temperature reaches 95 ℃, adding a pigment when the material temperature reaches 110 ℃, putting the material into cold mixing equipment for cooling when the material temperature reaches 120 ℃, discharging the material when the material temperature reaches 60 ℃, and obtaining a CPVC bar material mixing material;

2. and then adding the CPVC bar material mixture into a double-screw granulator for granulation, wherein the specific parameters of the double-screw granulator are as follows:

and cooling the cut particles by air cooling, and packaging the particles until the temperature of the particles reaches 60 ℃ to obtain the granules for the CPVC bar.

3. And adding the obtained granules for the CPVC bar into a hopper of a D75 single-screw extruder for CPVC bar extrusion, and cooling and shaping to obtain the CPVC bar with the diameter of 50.

The processing conditions of the D75 single-screw extruder were:

the performance comparison results are shown below:

from the data in the table above, the heat distortion temperature, tensile strength and tensile elastic modulus of the product obtained by the technology of the invention are superior to those of the product obtained by the conventional technology.

All percentages used in the present invention are mass percentages unless otherwise indicated.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.