CN106009157B - A kind of high-performance polyethylene based composites and its preparation method and application - Google Patents

Abstract

The invention relates to a polyethylene-based composite material, in particular to a high-performance polyethylene-based composite material. The invention uses high-density polyethylene (HDPE) as the basic material, and adds high polymers such as chlorinated polyethylene (CPE) to its Perform blending modification, and then add active ceramic whiskers, ceramic microspheres and other materials in a multi-phase blending method to prepare high-corrosion petrochemical pipelines with high strength, high wear resistance, heat insulation and other functions. The material, the preparation method mainly includes the steps of preparing active ceramic whisker/ceramic microsphere composite material-A material, preparing HDPE/PP/CPE high-filling masterbatch-B material and preparing high-performance polyethylene-based composite material. The high-performance polyethylene-based composite material has high strength, high wear resistance and heat insulation functions, and can be used for petrochemical pipeline anticorrosion, and its performance is better than that of pure HDPE anticorrosion materials.

Description

A kind of high-performance polyethylene-based composite material and its preparation method and application

technical field

The invention relates to a polyethylene-based composite material and its preparation method and application, in particular to a high-performance polyethylene-based composite material and its preparation method and application.

Background technique

At present, metal steel pipes are mainly used in the process of onshore and offshore oil and gas exploration and transportation in my country. The anti-corrosion measures for metal steel pipes, especially the inner and outer walls of steel pipes, are mainly sprayed with epoxy resin, phenolic resin, etc., or alloy steel pipes or nitriding steel pipes. The main disadvantages of epoxy resin materials are poor high temperature resistance, poor wear resistance, puncture and collision damage performance; phenolic resin has relatively improved temperature resistance, but poor wear resistance, and relatively low heat insulation function, which makes oil wells The heat loss rate of injected high-pressure water vapor is almost equivalent to that of pure steel pipe. If alloy steel pipe or nitriding steel pipe is used for mining, although the corrosion problem is solved, the price is expensive, and the problems of eccentric wear and heat insulation cannot be solved.

The present invention aims to solve the above defects of commonly used anti-corrosion materials, and develops micron-scale active ceramic whiskers and ceramics with high strength, high temperature resistance, high wear resistance and thermal insulation properties based on polyethylene-based resin alloys. Microspheres, to prepare new functional anti-corrosion materials. The main technical feature of this new material is that it inherits the high anti-corrosion performance of the traditional high polymer resin, and at the same time greatly improves its high temperature resistance, wear resistance and thermal insulation performance. The material can be widely used in anti-corrosion, anti-wear and thermal insulation of the inner and outer walls of metal pipelines such as oil and gas exploration pipelines and transmission pipelines.

Contents of the invention

The present invention aims to solve the above problems, and provides a polyethylene-based composite material and its preparation method and application. The prepared polyethylene-based composite material has certain improvements in tensile strength, elongation at break, and microcard softening point. At the same time, the thermal conductivity is low, and the wear quality is reduced by about 50%. The technical scheme adopted is as follows:

A high-performance polyethylene-based composite material, comprising the following components in parts by weight:

HDPE 90~110 parts

Material B 30~40 parts

The B material is HDPE/PP/CPE high-filling masterbatch, and the B material contains the following components in parts by weight:

The A material is a ceramic whisker/ceramic microsphere composite material, and the A material comprises the following components in parts by weight:

The silane coupling agent solution is a solution formed by diluting the silane coupling agent with absolute ethanol, and the volume fraction ratio of the absolute ethanol to the silane coupling agent is 8:1˜10:1.

Preferably, the ceramic whiskers are magnesium salt whiskers, the diameter of the single crystal fiber is ≤1 μm, and the length is 10 μm to 80 μm; the ceramic microspheres are hollow and sealed microspheres, and the particle size of the ceramic microspheres is 1000 mesh ~2500 mesh.

Preferably, the amount of ceramic whiskers in the material A is 100 parts, and that of ceramic microspheres is 80 parts.

The ceramic whiskers and ceramic microsphere components in high-performance polyethylene-based composite materials can greatly improve the heat resistance, wear resistance and mechanical properties of the material, making it more suitable for anti-corrosion of oil exploration pipelines, while reducing The melt fluidity and melt index of the system. Because ceramic whiskers and ceramic microspheres have better affinity after activation treatment, their spherical particle size, size distribution and "ball effect" all contribute to the fluidity of the melt; ceramic whiskers and ceramic microspheres also endow The outstanding thermal insulation and flame retardant performance of high-performance polyethylene-based composite materials, because the thermal conductivity of the ceramic whiskers and ceramic microspheres added to the system is very low, and the infrared transmittance is very small, which is very good. Insulation material; in addition, the ceramic microspheres specially added to achieve the thermal insulation performance of the composite material system are hollow and closed microspheres, and the inside of the microspheres is a thin gas. The density and thermal conductivity of the two different materials are different, so they have a unique thermal insulation properties.

Preferably, 50 parts of HDPE and 100 parts of PP in the material B are used to ensure the high anti-corrosion performance of the high-performance polyethylene-based composite material.

A preparation method of the above-mentioned high-performance polyethylene-based composite material, comprising the following steps:

(1) To prepare material A, carry out high-speed shear kneading of ceramic whiskers, ceramic microspheres and silane coupling agent solution, the kneading temperature is ≤50°C, the kneading time is 10min-12min, and then add dispersant or lubricant to continue high-speed Knead for 3 minutes to 5 minutes to make material A;

(2) Prepare material B, put HDPE, PP, CPE and material A into a plastic mill for mixing, the temperature of the front roller of the mill is 160°C-170°C, and the temperature of the rear roller is 150°C-160°C , the mixing time is 10min ~ 12min, after mixing, the slices are unloaded and parked for 12h ~ 24h, and then broken into small pieces to make B material;

(3) To prepare a high-performance polyethylene-based composite material, put HDPE and material B into a twin-screw extruder for blending and granulation, and the temperature of each section of the twin-screw extruder is set to 130°C, 150°C, 170°C, 180°C, 190°C and 180°C, the screw speed is 60r/min~100r/min, the strand pelletizing is carried out by water-cooling pelletizing, the cooling water temperature is 20°C~40°C, and the high performance polymer is obtained after pelletizing. Vinyl composite.

Through the high-speed shear kneading of ceramic whiskers, ceramic microspheres and silane coupling agent solution, and the mixing when preparing material B, the ceramic whiskers and ceramic microspheres are fully dispersed in the high-performance polyethylene-based composite material, The "agglomeration" particles are greatly reduced, which greatly improves the comprehensive performance of the composite material.

A high-performance polyethylene-based composite material prepared by the above-mentioned preparation method of a high-performance polyethylene-based composite material.

The above-mentioned high-performance polyethylene-based composite materials are used for pipeline anticorrosion, such as laying high-performance polyethylene-based composite materials on the inner and outer walls of pipelines, or preparing high-performance polyethylene-based composite materials into inner and outer high-corrosion composite liners .

Detailed ways

Below in conjunction with example the present invention will be further described:

The following detailed descriptions of the embodiments of the present invention are only for explaining the present invention, but should not be construed as limiting the present invention.

In describing the present invention, it is to be understood that the term "HDPE" means high density polyethylene, the term "PP" means polypropylene, and the term "CPE" means chlorinated polyethylene.

A high-performance polyethylene-based composite material, comprising the following components in parts by weight:

HDPE 90~110 parts

Material B 30~40 parts

Material B is HDPE/PP/CPE high-filling masterbatch, and material B contains the following components by weight:

Material A is a ceramic whisker/ceramic microsphere composite material, and material A contains the following components in parts by weight:

The silane coupling agent solution is a solution formed by diluting the silane coupling agent with absolute ethanol, and the volume fraction ratio of the absolute alcohol and the silane coupling agent is 8:1 to 10:1;

The lubricant is preferably polyethylene wax;

Sources of the above components:

HDPE (high density polyethylene), grade DGDB2480OH, Qilu Petrochemical Company;

PP (polypropylene powder), grade PPR4220, Yanshan Petrochemical Company;

CPE (chlorinated polyethylene), chlorine content 35%, grade is H135, Shandong Linzi Yixiang Chemical Co., Ltd.;

Ceramic whiskers, magnesium salt whiskers, chemical formula MgSO ₄ 5MgO 8H ₂ O, produced by Shanghai Gerunya Nano Materials Co., Ltd.;

Ceramic microspheres, the main components are SiO ₂ and Al ₂ O ₃ , the real density is 2.3g/cm ³ , Shanghai Gerunya Nano Materials Co., Ltd.;

Silane coupling agent, brand: KH550, Nanjing Xuanhao New Material Technology Co., Ltd.;

Lubricant, brand: polyethylene wax A-C6A, Shanghai Kaiyin Chemical Co., Ltd.;

Dispersant, brand: LUBDE360B, Shanghai Kaiyin Chemical Co., Ltd.

In the test, it was found that when the amount of ceramic whiskers in the material A was 100 parts, and that of ceramic microspheres was 80 parts, the high-performance polyethylene-based composite material had the best strength, wear resistance and thermal insulation.

In order to further improve the strength, wear resistance and thermal insulation properties of high-performance polyethylene-based composite materials, the ceramic whiskers are magnesium salt whiskers, the diameter of single crystal fibers is ≤1 μm, and the length is 10 μm to 80 μm; the ceramic whiskers The microspheres are hollow and sealed microspheres, and the particle diameter of the ceramic microspheres is 1000 mesh to 2500 mesh.

In order to ensure the high anti-corrosion performance of the high-performance polyethylene-based composite material, HDPE is 50 parts and PP is 100 parts in the B material.

The preparation method of the above-mentioned high-performance polyethylene-based composite material comprises the following steps:

(1) Prepare material A, put ceramic whiskers and ceramic microspheres into an electric oven, and dry at a temperature of about 100°C for 3 to 5 hours to make the moisture content ≤ 1%. After drying, ceramic whiskers and ceramic microspheres And silane coupling agent solution is put into CNF-A1 type 50 liters of supersonic high-speed shear kneaders (Qingdao University of Science and Technology Polymer Engineering Material Research Institute develops), simultaneously adds silane coupling agent solution, carries out high-speed shear kneading, for example The rotating speed of the stirring blade of the kneader is 800-1200 rpm, the kneading temperature is ≤50°C, the kneading time is 10min-12min, then add a dispersant or lubricant and continue kneading at a high speed for 3min-5min to make material A;

(2) To prepare material B, put HDPE, PP, CPE and material A into XK-300 open plastic open mill for mixing, the temperature of the front roll of the XK-300 open plastic open mill is 160 ℃ ~ 170 ℃ , the temperature of the rear stick is 150 ℃ ~ 160 ℃, the mixing time is 10min ~ 12min, the mixing process is fully kneaded, so that the components are evenly dispersed, after mixing, the slices are unloaded and parked for 12h ~ 24h, and then the sliced materials Put it into a SPW700HB plastic grinder (produced by Taizhou Panshi Machinery Co., Ltd.) and crush it into small pieces to make B material;

(3) To prepare a high-performance polyethylene-based composite material, put HDPE and B material into a TSE-65D twin-screw extrusion granulator for blending and granulation, and the temperature of each section of the TSE-65D twin-screw extrusion granulator Set to 130°C, 150°C, 170°C, 180°C, 190°C and 180°C respectively, the screw speed is 60r/min~100r/min, adopt the water-cooled pelletizing method for strand cutting, the cooling water temperature is 20°C~40 ℃, high-performance polyethylene-based composite materials were obtained after pelletizing.

The application of the above-mentioned high-performance polyethylene-based composite material, using the high-performance polyethylene-based composite material for pipeline anticorrosion, for example, laying high-performance polyethylene-based composite material on the inner and outer walls of the pipeline, or applying high-performance polyethylene-based composite material The composite material is prepared into inner and outer high anti-corrosion composite liners, and can be widely used in other anti-corrosion engineering fields.

Example 1:

Prepare material A, weigh ceramic whiskers (single crystal fiber diameter ≤ 1 μm, length 10 μm ~ 80 μm) 10kg, ceramic microspheres (1250 mesh) 8kg, silane coupling agent solution 300g, polyethylene wax 200g, put into CNF-A1 Type 50 liter ultrasonic high-speed shear kneader, kneading for 11 minutes under the conditions of kneader stirring blade rotation speed 1000 rpm, kneading temperature ≤ 50 ℃, then add dispersant and continue high-speed kneading for 4 minutes, then discharge and cool to room temperature. into material A;

To prepare material B, weigh 5kg of HDPE, 10kg of PP, 1.5kg of CPE, and 12kg of material A, and put them into an XK-300 open plastic open mill for mixing. 150°C～160°C, full kneading during the mixing process, the mixing time is 11min, and then the slices are unloaded and parked for 12h, and the blended slices that have been parked to eliminate internal stress are put into a plastic SWP700HB plastic crusher for crushing into small pieces. into material B.

To prepare high-performance polyethylene-based composite materials, weigh 20kg of HDPE and 2kg of material B, and put them into a CNF-A1 50-liter ultrasonic high-speed shear kneader. The stirring blade speed of the kneader is 1000 rpm. After blending and kneading for 3 minutes at 80°C, unload the material, and then put the blended material into the TSE-65D twin-screw extrusion granulator through the automatic feeding auxiliary machine for blending and granulation. The temperature of each section of the twin-screw extruder Set at 130°C, 150°C, 170°C, 180°C, 190°C and 180°C respectively, use water-cooled pelletizing method to carry out strand pelletizing, cooling water temperature is 20°C-40°C, and produce high-performance polyethylene after pelletizing base composite material.

Example 2

The preparation method of A material and B material is the same as above-mentioned embodiment 1.

Prepare high-performance polyethylene-based composite materials, take HDPE 20kg, B material 4kg, put into CNF-A1 type 50 liter ultrasonic high-speed shearing kneader, stir the blade speed in the kneader at 1000 rev/min, kneading temperature ≥ After blending and kneading for 3 minutes at 80°C, unload the material, and then put the blended material into the TSE-65D twin-screw extrusion granulator through the automatic feeding auxiliary machine for blending and granulation. The temperature of each section of the twin-screw extruder The subsections are set as: 130°C, 150°C, 170°C, 180°C, 190°C, 180°C, the water-cooled pelletizing method is used for strand pelletizing, the cooling water temperature is 20°C-40°C, and high-performance pellets are obtained after pelletizing. Polyethylene based composite.

Example 3

The preparation method of A material and B material is the same as above-mentioned embodiment 1.

Prepare high-performance polyethylene-based composite materials, take HDPE 20kg, B material 6kg, put into CNF-A1 type 50 liters of ultrasonic high-speed shear kneader, in the kneader, the stirring blade speed is 1000 rpm, at the kneading temperature ≥ After blending and kneading for 3 minutes at 80°C, unload the material, and then put the blended material into the TSE-65D twin-screw extrusion granulator through an automatic feeding auxiliary machine for blending and granulation. The temperature of each section of the extruder is divided into The setting is: 130°C, 150°C, 170°C, 180°C, 190°C, 180°C, the water-cooled pelletizing method is used for strand pelletizing, the cooling water temperature is 20°C-40°C, and high-performance polyethylene is obtained after pelletizing base composite material.

Example 4

Performance tests were performed on the high-performance polyethylene-based composite materials prepared in Examples 1-3.

Abrasion resistance is characterized by volume wear, tested according to GB/T 3960-1983 plastic sliding friction and wear test method; low temperature impact strength is tested according to GB/T17748-2008 standard; heat resistance is characterized by Vicat softening point, according to GB /T 8802-2001 Determination of Vicat softening temperature of thermoplastic pipes and pipe fittings; tensile strength is tested according to GB/T 1040-1992 plastic tensile properties test method; tensile elongation at break is tested according to GB/T 1040.1-2006 standard Test; adhesion test, measured according to GB/T 11211-2009; heat resistance test, measured according to CNS 10757 (1995) standard; acid immersion test, measured according to CNS 10757 (1995) standard; oil resistance test, measured according to CNS 10757 (1995) standard determination.

The thermal insulation performance is characterized by infrared transmittance, tested according to the standard GB10294-1988, using LS102/LS103A optical transmittance measuring instrument, the test principle is to use ultraviolet light source, infrared light source and visible light source to irradiate the transparent material to be tested, and the sensors detect respectively The incident light intensity of the three light sources and the light intensity after passing through the transparent material to be measured, the ratio of the transmitted light intensity to the incident light intensity is the transmittance, expressed as a percentage.

The above test methods were used to perform performance tests on pure HDPE and the high-performance polyethylene-based composite materials prepared in Examples 1 to 3, and the results were as follows:

Performance test results of high-performance polyethylene-based composite materials

It can be seen from the test data that the tensile strength of the high-performance polyethylene-based composite material is 10% to 28% higher than that of pure HDPE, the elongation at break is 13% to 15%, and the microcard softening point is 11% to 14%. Wear mass is reduced by 56%.

The present invention has been described above by way of examples, but the present invention is not limited to the above specific embodiments, and any changes or modifications made based on the present invention fall within the scope of protection of the present invention.

Claims (7)

1. A high-performance polyethylene-based composite material, characterized in that it comprises the following components in parts by weight: HDPE 90~110 parts Material B 30~40 parts The B material is HDPE/PP/CPE high-filling masterbatch, and the B material contains the following components in parts by weight: The A material is a ceramic whisker/ceramic microsphere composite material, and the A material comprises the following components in parts by weight: The silane coupling agent solution is a solution formed by diluting the silane coupling agent with absolute ethanol, and the volume fraction ratio of the absolute ethanol to the silane coupling agent is 8:1˜10:1. 2. The high-performance polyethylene-based composite material according to claim 1, characterized in that 100 parts of ceramic whiskers and 80 parts of ceramic microspheres in the A material. 3. The high-performance polyethylene-based composite material according to claim 1, wherein the ceramic whiskers are magnesium salt whiskers, the diameter of the single crystal fiber is ≤1 μm, and the length is 10 μm to 80 μm; the ceramic microspheres are hollow and airtight Type microspheres, the particle size of the ceramic microspheres is 1000 mesh to 2500 mesh. 4. The high-performance polyethylene-based composite material according to claim 3, characterized in that, in the B material, HDPE is 50 parts, and PP is 100 parts. 5. A method for preparing the high-performance polyethylene-based composite material according to any one of claims 1 to 4, characterized in that it comprises the following steps: (1) To prepare material A, carry out high-speed shear kneading of ceramic whiskers, ceramic microspheres and silane coupling agent solution, the kneading temperature is ≤50°C, the kneading time is 10min-12min, and then add dispersant or lubricant to continue high-speed Knead for 3 minutes to 5 minutes to make material A; (2) Prepare material B, put HDPE, PP, CPE and material A into a plastic mill for mixing, the temperature of the front roll of the mill is 160°C-170°C, and the temperature of the rear roll is 150°C-160°C , the mixing time is 10min ~ 12min, after mixing, the slices are unloaded and parked for 12h ~ 24h, and then broken into small pieces to make B material; (3) To prepare a high-performance polyethylene-based composite material, put HDPE and material B into a twin-screw extruder for blending and granulation, and the temperature of each section of the twin-screw extruder is set to 130°C, 150°C, 170°C, 180°C, 190°C and 180°C, the screw speed is 60r/min～100r/min, the water-cooled pelletizing method is used for strand pelletizing, and high-performance polyethylene-based composite materials are obtained after pelletizing. 6. A high-performance polyethylene-based composite material prepared by the preparation method of the high-performance polyethylene-based composite material according to claim 5. 7. The application of the high-performance polyethylene-based composite material according to claim 6, characterized in that, the high-performance polyethylene-based composite material is used for pipeline anticorrosion.