CN108948493B - Ultralow-temperature high-density polyethylene anticorrosive material for steel pipeline and preparation method thereof - Google Patents
Ultralow-temperature high-density polyethylene anticorrosive material for steel pipeline and preparation method thereof Download PDFInfo
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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
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Abstract
The invention provides an ultralow-temperature high-density polyethylene anticorrosive material for steel pipelines, which is prepared from the following raw materials in parts by weight: 80-100 parts of high-density polyethylene, 30-50 parts of polypropylene, 7-11 parts of linear low-density polyethylene, 2-3 parts of maleic anhydride grafted polyethylene, 4-7 parts of nano calcium carbonate, 2-3 parts of titanate coupling agent, 3-4 parts of pentaerythritol stearate and 2-3 parts of antioxidant. The invention also provides a preparation method of the ultralow-temperature high-density polyethylene anticorrosive material for the steel pipeline. The invention solves the problem that the existing high-density polyethylene anticorrosive material can not meet the requirements of ultralow temperature use and construction, and the prepared product has good low-temperature anti-cracking performance.
Description
Technical Field
The invention relates to the technical field of protective materials, in particular to an ultralow-temperature high-density polyethylene anticorrosive material for a steel pipeline and a preparation method thereof.
Background
The extruded polyethylene anticorrosive layer is formed by heating and pressurizing in an extruder to ensure that polyethylene continuously passes through an extrusion die mold in a flowing state to be molded and coated on a pipeline, and the coating mode comprises longitudinal extrusion coating and lateral winding coating.
Along with the construction of oil and gas transmission pipelines in nearly two decades in China, the high-density polyethylene anticorrosive material for the steel pipelines is marked from GB23257-2009 to GB23257-2017, and the existing standard can only meet the requirements of general geographic environments, so that the high-density polyethylene anticorrosive material is not suitable for the construction of oil and gas pipelines in China in recent years. In the northern part of China, the places such as the Russian frontier, Tahe, ink river and the like are in a frozen soil alternating severe environment for a long time, the temperature is more than 20-50 ℃ below zero in 11 months, 12 months, 1 month, 2 months and 3 months every year, and the climate is extremely severe. In engineering construction, as a plurality of places are marshland, the geographical environment is complex, pipelines need to be constructed in winter. However, the low-temperature notch impact of the high-density polyethylene pipeline material at home and abroad can only meet the requirement of 20 ℃ below zero at present. The requirements of use at the temperature of below 30 ℃ below zero and construction under low temperature conditions are not met.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides an ultralow-temperature high-density polyethylene anticorrosive material for a steel pipeline and a preparation method thereof, and solves the problem that the existing high-density polyethylene anticorrosive material cannot meet the requirements of ultralow-temperature use and construction.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention firstly provides an ultralow-temperature high-density polyethylene anticorrosive material for steel pipelines, which is prepared from the following raw materials in parts by weight: 80-100 parts of high-density polyethylene, 30-50 parts of polypropylene, 7-11 parts of linear low-density polyethylene, 2-3 parts of maleic anhydride grafted polyethylene, 4-7 parts of nano calcium carbonate, 2-3 parts of titanate coupling agent, 3-4 parts of pentaerythritol stearate and 2-3 parts of antioxidant.
Preferably, the high density polyethylene is PE100 grade high density polyethylene.
Preferably, the polypropylene is one of the PPB4228, the PPB4220 or the PPB 240.
Preferably, the antioxidant is antioxidant 1010.
The invention also provides a preparation method of the ultralow-temperature high-density polyethylene anticorrosive material for the steel pipeline, which comprises the following steps of:
step [1] mixing a titanate coupling agent and ethanol to form a mixed solution A, then adding nano calcium carbonate into the ethanol to form a mixed solution B, dropwise adding the mixed solution B into the mixed solution A under a continuous stirring state, carrying out ultrasonic stirring on the mixed solution A in the dropwise adding process, continuing stirring for 30-50 minutes after the dropwise adding is finished, then putting the mixed solution A into an oven, controlling the temperature to be about 40 ℃, and keeping the temperature for 3 hours to obtain surface-modified nano calcium carbonate;
step [2] respectively thinning the high-density polyethylene, the polypropylene and the linear low-density polyethylene until the fineness reaches more than 200 meshes;
step [3] adding the refined high-density polyethylene, polypropylene, linear low-density polyethylene, surface-modified nano calcium carbonate, maleic anhydride grafted polyethylene, pentaerythritol stearate and antioxidant into a high-speed mixer, uniformly mixing, and discharging;
step [4] adding the mixture obtained in the step [3] into a double-screw extruder, and carrying out melting, mixing, extruding, cooling, granulating and packaging to obtain a finished product; wherein the temperature of each section of the extruder is as follows: the temperature of the first section is 100 ℃, the temperature of the second section is 290 ℃, the temperature of the third section is 260 ℃, the temperature of the fourth section is 290 ℃, the temperature of the fifth section is 260 ℃, the temperature of the sixth section is 230 ℃, the temperature of the VII section is 230 ℃, the temperature of the VIII section is 230 ℃, the temperature of the IX section is 235 ℃, and the temperature of the machine head is 235 ℃; the rotating speed of the screw is 300-400 rpm.
Preferably, the ethanol amount in the mixed solution A and the mixed solution B in the step [1] is half of the weight of the titanate coupling agent.
The invention has the following positive effects: the nano calcium carbonate is added into the mixture after surface modification, and plays a role of heterogeneous nucleation together with the high-density polyethylene in the blend, so that the aim of crystal refinement is achieved, meanwhile, the nano calcium carbonate has more chances of being combined with a polymer chain, and a formed combination unit can be loosened at low temperature, so that the low-temperature toughness of the product can be effectively improved; the addition of the low-density polyethylene, the maleic anhydride grafted polyethylene and the pentaerythritol stearate can reduce the melt viscosity, improve the fluidity and the compatibility of the blend, improve the processing performance, reduce the internal stress of the product, obviously improve the stress cracking resistance of the product and have excellent impact resistance at room temperature or low temperature. In addition, the nanoparticles have larger specific surface area and surface energy, stronger interface action can be generated between the nanoparticles and the polymer, and a high-low temperature circulation mode is adopted in the extruder, so that the activity of polymer chains is repeatedly enhanced and weakened, the interconnection between the polymer chains and crystal grains can be better controlled, and better low-temperature mechanical property is obtained. In a word, the product obtained by the invention has good low-temperature cracking resistance, and can meet the requirements of construction and use at extremely low temperature in winter.
Detailed Description
The following is a detailed description of preferred embodiments of the invention.
Example 1
The preferred embodiment 1 of the invention provides an ultralow-temperature high-density polyethylene anticorrosive material for steel pipelines, which is prepared from the following raw materials in parts by weight: 80 parts of high-density polyethylene, 30 parts of polypropylene, 7 parts of linear low-density polyethylene, 2 parts of maleic anhydride grafted polyethylene, 4 parts of nano calcium carbonate, 2 parts of titanate coupling agent, 3 parts of pentaerythritol stearate and 2 parts of antioxidant.
Wherein the high-density polyethylene is PE100 grade high-density polyethylene; the polypropylene is PPB 4228; the antioxidant is 1010; the titanate coupling agent is a titanate coupling agent NDZ-401, Nanjing eosin photochemical factory.
Example 2
The preferred embodiment 2 of the invention provides an ultralow-temperature high-density polyethylene anticorrosive material for steel pipelines, which is prepared from the following raw materials in parts by weight: 85 parts of high-density polyethylene, 35 parts of polypropylene, 7.5 parts of linear low-density polyethylene, 2.2 parts of maleic anhydride grafted polyethylene, 4.6 parts of nano calcium carbonate, 2.1 parts of titanate coupling agent, 3.3 parts of pentaerythritol stearate and 2.1 parts of antioxidant.
Wherein the high-density polyethylene is PE100 grade high-density polyethylene; the polypropylene is PPB 4220; the antioxidant is 1010; the titanate coupling agent is a titanate coupling agent NDZ-401, Nanjing eosin photochemical factory.
Example 3
The preferred embodiment 3 of the invention provides an ultralow-temperature high-density polyethylene anticorrosive material for steel pipelines, which is prepared from the following raw materials in parts by weight: 91 parts of high-density polyethylene, 33 parts of polypropylene, 9 parts of linear low-density polyethylene, 2.3 parts of maleic anhydride grafted polyethylene, 5.4 parts of nano calcium carbonate, 2.4 parts of titanate coupling agent, 3.5 parts of pentaerythritol stearate and 2.2 parts of antioxidant.
Wherein the high-density polyethylene is PE100 grade high-density polyethylene; the polypropylene is PPB 240; the antioxidant is 1010; the titanate coupling agent is a titanate coupling agent NDZ-401, Nanjing eosin photochemical factory.
Example 4
The preferred embodiment 4 of the invention provides an ultralow-temperature high-density polyethylene anticorrosive material for steel pipelines, which is prepared from the following raw materials in parts by weight: 95 parts of high-density polyethylene, 45 parts of polypropylene, 10 parts of linear low-density polyethylene, 2.6 parts of maleic anhydride grafted polyethylene, 6.2 parts of nano calcium carbonate, 2.7 parts of titanate coupling agent, 3.1 parts of pentaerythritol stearate and 2.5 parts of antioxidant.
Wherein the high-density polyethylene is PE100 grade high-density polyethylene; the polypropylene is PPB 4220; the antioxidant is 1010; the titanate coupling agent is a titanate coupling agent NDZ-401, Nanjing eosin photochemical factory.
Example 5
The preferred embodiment 5 of the invention provides an ultralow-temperature high-density polyethylene anticorrosive material for steel pipelines, which is prepared from the following raw materials in parts by weight: 100 parts of high-density polyethylene, 50 parts of polypropylene, 11 parts of linear low-density polyethylene, 3 parts of maleic anhydride grafted polyethylene, 7 parts of nano calcium carbonate, 3 parts of titanate coupling agent, 4 parts of pentaerythritol stearate and 3 parts of antioxidant.
Wherein the high-density polyethylene is PE100 grade high-density polyethylene; the polypropylene is PPB 4228; the antioxidant is 1010; the titanate coupling agent is a titanate coupling agent NDZ-401, Nanjing eosin photochemical factory.
Example 6
A preferred embodiment 6 of the present invention provides a method for preparing the ultra-low temperature high density polyethylene anticorrosive material for the steel pipes described in the above embodiments 1 to 5, which comprises the following steps:
step [1] mixing a titanate coupling agent and ethanol to form a mixed solution A, then adding nano calcium carbonate into the ethanol to form a mixed solution B, dropwise adding the mixed solution B into the mixed solution A under a continuous stirring state, carrying out ultrasonic stirring on the mixed solution A in the dropwise adding process, continuing stirring for 30-50 minutes after the dropwise adding is finished, then putting the mixed solution A into an oven, controlling the temperature to be about 40 ℃, and keeping the temperature for 3 hours to obtain surface-modified nano calcium carbonate;
step [2] respectively thinning the high-density polyethylene, the polypropylene and the linear low-density polyethylene until the fineness reaches more than 200 meshes;
step [3] adding the refined high-density polyethylene, polypropylene, linear low-density polyethylene, surface-modified nano calcium carbonate, maleic anhydride grafted polyethylene, pentaerythritol stearate and antioxidant into a high-speed mixer, uniformly mixing, and discharging;
step [4] adding the mixture obtained in the step [3] into a double-screw extruder, and carrying out melting, mixing, extruding, cooling, granulating and packaging to obtain a finished product; wherein the temperature of each section of the extruder is as follows: the temperature of the first section is 100 ℃, the temperature of the second section is 290 ℃, the temperature of the third section is 260 ℃, the temperature of the fourth section is 290 ℃, the temperature of the fifth section is 260 ℃, the temperature of the sixth section is 230 ℃, the temperature of the VII section is 230 ℃, the temperature of the VIII section is 230 ℃, the temperature of the IX section is 235 ℃, and the temperature of the machine head is 235 ℃; the rotating speed of the screw is 300-400 rpm.
In the step (1), the ethanol amount in the mixed solution A and the mixed solution B is half of the weight of the titanate coupling agent.
The products of examples 1 to 5 prepared by the above method were applied to the outer anticorrosive layer of a freshly made pipe by a high temperature melt extrusion coating method, and were free-dropped from a height of 3m by a 5kg weight impact bar for 2 times at-50 ℃ without cracking.
Comparative example
The comparative example provides a high-density polyethylene anticorrosive material, which comprises 210 parts of PE 100-grade high-density polyethylene resin, 120 parts of ethylene-vinyl acetate copolymer, 50 parts of dynamically vulcanized ethylene propylene diene monomer, 50 parts of polypropylene and 40 parts of mica; wherein the mass percentage content of the vinyl acetate in the ethylene-vinyl acetate copolymer is 20%, and the mass flow rate of the ethylene-vinyl acetate copolymer melt is 2-3 g/10 min.
The preparation method comprises the following steps: adding polypropylene, high-density polyethylene and ethylene propylene diene monomer rubber in sequence on an open mill, uniformly mixing, adding mica powder treated by titanate coupling agent NDZ-401, continuously mixing uniformly, and granulating.
The product prepared by the comparative example is coated on the outer anticorrosive layer of a steel pipe by a high-temperature melting extrusion coating method, and is subjected to free drop hammer for 2 times from a height of 3m by a 5kg impact bar under the environment of-50 ℃, so that the product is cracked.
The above embodiments are only preferred embodiments of the present invention, and it should be understood that the above embodiments are only for assisting understanding of the method and the core idea of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalents and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. The ultra-low temperature high density polyethylene anticorrosive material for the steel pipeline is characterized by being prepared from the following raw materials in parts by weight: 80-100 parts of high-density polyethylene, 30-50 parts of polypropylene, 7-11 parts of linear low-density polyethylene, 2-3 parts of maleic anhydride grafted polyethylene, 4-7 parts of nano calcium carbonate, 2-3 parts of titanate coupling agent, 3-4 parts of pentaerythritol stearate and 2-3 parts of antioxidant; the polypropylene is one of PPB4228, PPB4220 or PPB 240.
2. The ultra-low temperature high density polyethylene anticorrosive material for the steel pipeline as claimed in claim 1, wherein: the high-density polyethylene is PE100 grade high-density polyethylene.
3. The ultra-low temperature high density polyethylene anticorrosive material for the steel pipeline as claimed in claim 1, wherein: the antioxidant is antioxidant 1010.
4. A preparation method of the ultralow-temperature high-density polyethylene anticorrosive material for the steel pipeline, which is characterized by comprising the following steps of:
step [1] mixing a titanate coupling agent and ethanol to form a mixed solution A, then adding nano calcium carbonate into the ethanol to form a mixed solution B, dropwise adding the mixed solution B into the mixed solution A under a continuous stirring state, carrying out ultrasonic stirring on the mixed solution A in the dropwise adding process, continuing stirring for 30-50 minutes after the dropwise adding is finished, then putting the mixed solution A into an oven, controlling the temperature to be about 40 ℃, and keeping the temperature for 3 hours to obtain surface-modified nano calcium carbonate; wherein, the ethanol amount in the mixed solution A and the mixed solution B is half of the weight of the titanate coupling agent;
step [2] respectively thinning the high-density polyethylene, the polypropylene and the linear low-density polyethylene until the fineness reaches more than 200 meshes;
step [3] adding the refined high-density polyethylene, polypropylene, linear low-density polyethylene, surface-modified nano calcium carbonate, maleic anhydride grafted polyethylene, pentaerythritol stearate and antioxidant into a high-speed mixer, uniformly mixing, and discharging;
step [4] adding the mixture obtained in the step [3] into a double-screw extruder, and carrying out melting, mixing, extruding, cooling, granulating and packaging to obtain a finished product; wherein the temperature of each section of the extruder is as follows: the temperature of the first section is 100 ℃, the temperature of the second section is 290 ℃, the temperature of the third section is 260 ℃, the temperature of the fourth section is 290 ℃, the temperature of the fifth section is 260 ℃, the temperature of the sixth section is 230 ℃, the temperature of the VII section is 230 ℃, the temperature of the VIII section is 230 ℃, the temperature of the IX section is 235 ℃, and the temperature of the machine head is 235 ℃; the rotating speed of the screw is 300-400 rpm.
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| CN110305392A (en) * | 2019-07-23 | 2019-10-08 | 武汉唯康管业有限公司 | A kind of high-density polytene pipeline and its preparation process |
| CN116285115A (en) * | 2022-09-08 | 2023-06-23 | 福建俊榕能源有限公司 | Multilayer composite modified polypropylene power tube and preparation method thereof |
| CN115368782A (en) * | 2022-09-27 | 2022-11-22 | 肖建江 | Preparation method of corrosion-resistant hydrophobic anticorrosive material |
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Effective date of registration: 20200115 Address after: 266000 east side of Yanqing Road, Jiangshan Town, Laixi City, Qingdao, Shandong Applicant after: Qingdao Wedonk Polymer Material Co.,Ltd. Applicant after: Qingdao weidongke New Material Technology Co., Ltd Address before: 266000 east side of Yanqing Road, Jiangshan Town, Laixi City, Qingdao, Shandong Applicant before: Qingdao Wedonk Polymer Material Co.,Ltd. |
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