CN112745548A - Low-temperature-resistant polyethylene composite material and preparation method and application thereof - Google Patents
Low-temperature-resistant polyethylene composite material and preparation method and application thereof Download PDFInfo
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- CN112745548A CN112745548A CN202011462370.9A CN202011462370A CN112745548A CN 112745548 A CN112745548 A CN 112745548A CN 202011462370 A CN202011462370 A CN 202011462370A CN 112745548 A CN112745548 A CN 112745548A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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Abstract
The invention discloses a low-temperature-resistant polyethylene composite material which comprises the following components in parts by weight: 50-70 parts of high-density polyethylene; 10-15 parts of metallocene linear low-density polyethylene; 20-35 parts of copolymerized olefin elastomer; 4-7 parts of carbon black. The low-temperature resistant polyethylene composite material not only has the notch impact strength requirement of more than or equal to 65kJ/m at the temperature of-45 DEG C2The coating has the advantages of collision resistance and scraping resistance under the low-temperature condition, and is suitable for pipeline shells or outer protective layers under the low-temperature environment.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a low-temperature-resistant polyethylene composite material and a preparation method and application thereof.
Background
The transportation of crude oil, finished oil and natural gas uses a large amount of steel pipelines which are subjected to anticorrosion treatment, and the polyethylene anticorrosion, heat preservation, anti-collision and anti-scraping layer (3 LPE) technology with a three-layer structure is the most advanced pipeline anticorrosion technology which is developed in recent years. The bottom layer of 3LPE is epoxy paint, the middle layer is adhesive, and the surface layer is polyethylene. The epoxy powder is sprayed on the surface of the steel pipe which is heated after shot blasting and rust removal to form a bottom layer of a sintered epoxy layer, and the bottom layer has excellent corrosion resistance and cathodic disbonding resistance; the middle layer adhesive is wound outside the epoxy bottom layer through lateral extrusion, and the epoxy layer and the outermost polyethylene layer are firmly bonded together; the polyethylene is extruded and wound on the steel pipe in the side direction, and finally, the polyethylene is cooled to form a complete three-layer anti-corrosion structure. The polyethylene is a non-polar polymer, has high crystallinity, excellent chemical medium corrosion resistance, aging resistance and biological corrosion resistance, extremely low permeability, can effectively prevent the corrosion of substances such as water and the like, and plays a vital role in a three-layer anticorrosive structure.
The corrosion-resistant steel pipe is inevitably collided and scraped in the use process in a low-temperature environment, and the corrosion-resistant polyethylene is required to have enough toughness so that the damage can be controlled within an acceptable range. Aiming at the problems in northeast pipe network construction in recent years, the industrial anti-corrosion polyethylene material for natural gas pipelines (Guermu-Lassa pipelines) in high and cold regions such as Qinghai-Tibet plateau has high low-temperature impact resistance requirement, and the requirement of notch impact strength at-45 ℃ is more than or equal to 65kJ/m2. At present, the notch impact strength of the common anticorrosive polyethylene meeting GB/T23257-2017 at-45 ℃ is only less than 15kJ/m2. The research and development of polyethylene special for pipelines in alpine regions with design requirements become an urgent solution in the industryTo a problem of (a).
Disclosure of Invention
The invention aims to provide a low-temperature-resistant polyethylene composite material which has the advantages of good low-temperature impact resistance, and low-temperature collision and scratch resistance.
The invention also aims to provide a preparation method and application of the low-temperature-resistant polyethylene composite material.
The invention is realized by the following technical scheme:
the low-temperature-resistant polyethylene composite material comprises the following components in parts by weight:
50-70 parts of high-density polyethylene;
10-15 parts of metallocene linear low-density polyethylene;
20-35 parts of copolymerized olefin elastomer;
4-7 parts of carbon black.
The density range of the high-density polyethylene is 0.940-0.955g/cm high-speed cultivation
The metallocene linear low density polyethylene has the density of 0.915-0.925g/cm through thin-wall cultivation. Metallocene linear low density polyethylene is polyethylene obtained by polymerizing ethylene monomer, 1-hexene monomer or 1-octene monomer by metallocene catalysis.
The copolymerized olefin elastomer is at least one of ethylene propylene rubber and ethylene propylene diene monomer rubber.
Ethylene propylene rubber EPR: melting point: the ethylene-propylene rubber is copolymerized into the ethylene-propylene rubber by monoolefine ethylene and propylene at the temperature of between 128 and 208 ℃.
Ethylene propylene diene monomer EPDM: ethylene, propylene and a small amount of non-conjugated diene are used as monomers to be copolymerized to prepare the ethylene propylene diene monomer.
Whether 0-2 parts of auxiliary agent is added or not can be determined according to actual conditions; the auxiliary agent is at least one of an antioxidant and a lubricant.
The lubricant is at least one selected from stearate lubricant, fatty acid lubricant and stearate lubricant; the stearate lubricant is at least one selected from calcium stearate, magnesium stearate and zinc stearate; the fatty acid lubricant is at least one selected from fatty acid, fatty acid derivative and fatty acid ester; the stearate lubricant is at least one selected from glyceryl monostearate and pentaerythritol stearate.
The antioxidant is at least one selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and didodecanediol thiodipropionate.
The low-temperature resistant polyethylene composite material has the notch impact strength of more than or equal to 65kJ/m at the temperature of minus 45 DEG C2And a Vicat softening point of 110 ℃ or higher.
The preparation method of the low temperature resistant polyethylene composite material is characterized by comprising the following steps: uniformly stirring high-density polyethylene resin, metallocene linear low-density polyethylene resin, a copolymerized olefin elastomer and carbon black in a high-speed mixer, and extruding and granulating through a double-screw extruder to obtain the low-temperature-resistant polyethylene composite material, wherein the temperature range of a screw is 180-220 ℃, and the rotating speed range is 380-420 RPM;
if the additive exists, stirring the mixture and the high-density polyethylene, and extruding and granulating the mixture.
The application of the low temperature resistant polyethylene composite material is characterized in that the low temperature resistant polyethylene composite material is used for preparing a pipeline shell or an outer protective layer in a low temperature environment.
The invention has the following beneficial effects:
the invention selects the compounding of the high-density polyethylene and the metallocene linear low-density polyethylene,
the compatibility of metallocene linear low density polyethylene is utilized to improve the dispersion degree of polyolefin elastomer in high density polyethylene, and the size of rubber phase is reduced to the range of 0.5-3.0 microns. The polyolefin copolymer elastomer can be tightly combined with a resin matrix in a low-temperature environment so as to be difficult to crack, and the low-temperature impact resistance effect is improved by adding a certain amount of carbon black, so that the notch impact strength of the low-temperature impact resistant polyethylene composite material is greater than or equal to 65kJ/m at the temperature of minus 45 DEG C2. Meanwhile, the polyethylene composite material has the advantages of collision resistance and scratch resistance under the low-temperature condition (the Vicat softening point is more than or equal to 110 ℃). The polyethylene composite material provided by the invention is added with a certain amount of carbon black, so that the low temperature resistance cannot be further improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the present invention are derived from commercially available products.
High density polyethylene: performing high density of 0.945 g/cm, and under the trademark of HDPE HMCRP 100N;
metallocene linear low density polyethylene: the density is 0.918 g/cm for double cropping, and the mark is as follows: LLDPE-3518 PA.
Ordinary linear low density polyethylene: performing high-density cultivation at the density of 0.920 g/cm under the brand name; LLDPE-DFDA-7042
Ultra high molecular weight polyethylene (UHMW-PE): the raw material used was of molecular weight 250 ten thousand.
Ethylene propylene rubber EPR EXXON Exxon EPR 722 ethylene propylene glycol.
Ethylene propylene diene monomer EPDM: american dow 4770R.
Carbon black: the used PLASBLAK PE2772 KF.
Antioxidant: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Lubricant: pentaerythritol stearate.
The test method comprises the following steps:
(1) low-temperature impact resistance: pressing the extruded granules into pieces with the thickness of 4mm in a mould press, washing the pieces into A-shaped notch impact strips with standard requirements by using a machine, then adjusting sample strips, placing the sample strips into a special fixture after the sample strips are adjusted, placing the special fixture into a low-temperature freezer with the temperature of-45 ℃, keeping the constant temperature for more than 4 hours, taking out the sample strips and immediately carrying out impact test, and taking the average value of the low-temperature impact strength test of at least 5 sample strips in each group
(2) Vicat softening point: the method is carried out according to the measurement standard of GB/T1633-2000 thermoplastic Vicat Softening Temperature (VST).
Examples and comparative examples preparation method of polyethylene composites: uniformly stirring high-density polyethylene resin, metallocene linear low-density polyethylene resin (or other polyethylene), a copolymerized olefin elastomer, carbon black, an antioxidant and a lubricant in a high-speed mixer, and extruding and granulating through a double-screw extruder to obtain the low-temperature-resistant polyethylene composite material, wherein the temperature range of a screw is 180-220 ℃, and the rotating speed range is 380-420 RPM;
table 1: examples polyethylene composite Material content (parts by weight) of each component and test results
From examples 1 to 4, it is understood that the technical proposal of the invention can obtain the notched impact strength of more than or equal to 69 kJ/m at the temperature of minus 45 DEG C2And a Vicat softening point of 110 ℃ or higher.
Table 2: comparative example polyethylene composite Material content of Components (parts by weight) and test results
It can be seen from comparative examples 1 to 5 that the amounts of high density polyethylene and metallocene linear low density polyethylene are also necessary technical features for achieving high-45 ℃ notched impact strength and Vicat softening point at the same time, and although the technical solutions of comparative examples 1 and 5 can also achieve Vicat softening points of more than 110 ℃, the-45 ℃ notched impact strengths of less than 60 kJ/m2And the application under extremely cold conditions cannot be met.
As can be seen from comparative example 3, the addition of carbon black not only improved the notch impact strength at-45 ℃ but also unexpectedly improved the Vicat softening point.
Continuing with Table 2: comparative example polyethylene composite Material content of Components (parts by weight) and test results
As can be seen from comparative examples 5 to 7, conventional linear low density polyethylene cannot replace metallocene linear low density polyethylene due to the difference in segment structure.
From comparative examples 8 to 9, it is clear that the ultra-high molecular weight polyethylene has a high Vicat softening point but poor low temperature impact resistance.
Claims (8)
1. The low-temperature-resistant polyethylene composite material is characterized by comprising the following components in parts by weight:
50-70 parts of high-density polyethylene;
10-15 parts of metallocene linear low-density polyethylene;
20-35 parts of copolymerized olefin elastomer;
4-7 parts of carbon black.
2. The low temperature resistant polyethylene composite of claim 1, wherein the high density polyethylene has a density in the range of from 0.940 to 0.955g/cm thin film grown under pressure.
3. The low temperature resistant polyethylene composite material of claim 1, wherein said metallocene linear low density polyethylene has a density of 0.915-0.925g/cm as obtained by thin-wall chemical vapor deposition.
4. The low temperature resistant polyethylene composite material of claim 1, wherein the copolymerized olefin elastomer is at least one selected from ethylene propylene rubber and ethylene propylene diene monomer rubber.
5. The low temperature resistant polyethylene composite material according to claim 1, further comprising 0-2 parts by weight of an auxiliary agent; the auxiliary agent is at least one of an antioxidant and a lubricant.
6. The low temperature resistant polyethylene composite material of claim 1, wherein the low temperature resistant polyethylene composite material has a notched impact strength of 65kJ/m or more at-45 ℃2And a Vicat softening point of 110 ℃ or higher.
7. The process for preparing a low temperature resistant polyethylene composite according to any one of claims 1 to 6, characterized in that it comprises the following steps: uniformly stirring high-density polyethylene resin, metallocene linear low-density polyethylene resin, a copolymerized olefin elastomer and carbon black in a high-speed mixer, and extruding and granulating through a double-screw extruder to obtain the low-temperature-resistant polyethylene composite material, wherein the temperature range of a screw is 180-220 ℃, and the rotating speed range is 380-420 RPM;
if the additive exists, stirring the mixture and the high-density polyethylene, and extruding and granulating the mixture.
8. Use of the low temperature resistant polyethylene composite material according to any one of claims 1 to 6 for the production of pipe casings, or outer protective layers, in low temperature environments.
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| CN202011462370.9A CN112745548A (en) | 2020-12-14 | 2020-12-14 | Low-temperature-resistant polyethylene composite material and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114474925A (en) * | 2021-12-29 | 2022-05-13 | 江阴申隆包装材料有限公司 | Recyclable high-barrier packaging film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747552A (en) * | 2009-12-31 | 2010-06-23 | 上海金发科技发展有限公司 | Steel-pipeline outer-layer anticorrosive polyethylene compound and preparation method thereof |
| CN103450540A (en) * | 2012-05-28 | 2013-12-18 | 中国石油天然气股份有限公司 | Special polyethylene material for 3PE corrosion prevention and preparation method thereof |
| CN106279919A (en) * | 2016-08-30 | 2017-01-04 | 中国石油天然气集团公司 | A kind of resistance to extreme low temperature ultra-toughness utilidor outer sheath material and preparation method thereof |
| CN111454505A (en) * | 2020-04-29 | 2020-07-28 | 江苏达胜热缩防护用品有限公司 | Special low-temperature high-toughness polyethylene material and preparation method thereof |
-
2020
- 2020-12-14 CN CN202011462370.9A patent/CN112745548A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747552A (en) * | 2009-12-31 | 2010-06-23 | 上海金发科技发展有限公司 | Steel-pipeline outer-layer anticorrosive polyethylene compound and preparation method thereof |
| CN103450540A (en) * | 2012-05-28 | 2013-12-18 | 中国石油天然气股份有限公司 | Special polyethylene material for 3PE corrosion prevention and preparation method thereof |
| CN106279919A (en) * | 2016-08-30 | 2017-01-04 | 中国石油天然气集团公司 | A kind of resistance to extreme low temperature ultra-toughness utilidor outer sheath material and preparation method thereof |
| CN111454505A (en) * | 2020-04-29 | 2020-07-28 | 江苏达胜热缩防护用品有限公司 | Special low-temperature high-toughness polyethylene material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114474925A (en) * | 2021-12-29 | 2022-05-13 | 江阴申隆包装材料有限公司 | Recyclable high-barrier packaging film and preparation method thereof |
| CN114474925B (en) * | 2021-12-29 | 2023-11-14 | 江阴申隆包装材料有限公司 | Recyclable high-barrier packaging film and preparation method thereof |
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