CN115895347A - Welding seam cracking resistant and low-temperature leveling polyethylene powder and preparation method and application thereof - Google Patents
Welding seam cracking resistant and low-temperature leveling polyethylene powder and preparation method and application thereof Download PDFInfo
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- CN115895347A CN115895347A CN202211126782.4A CN202211126782A CN115895347A CN 115895347 A CN115895347 A CN 115895347A CN 202211126782 A CN202211126782 A CN 202211126782A CN 115895347 A CN115895347 A CN 115895347A
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 20
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- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
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Abstract
The invention relates to polyethylene powder for external corrosion prevention of steel pipelines and a preparation method thereof. The polyethylene powder comprises the following raw materials in parts by weight: 5-15 parts of maleic anhydride graft modified polyolefin elastomer copolymer, 2-5 parts of ethylene acrylic acid copolymer, 10-20 parts of rotational molding grade linear low density polyethylene, 52-80 parts of high-fluidity polyethylene and 3-8 parts of functional auxiliary agent, and the polyethylene powder with the characteristics of weld crack resistance and low-temperature leveling is obtained by blending, twin-screw melting granulation and mechanical grinding. The polyethylene powder disclosed by the invention can be used for corrosion prevention of a steel pipe, can be leveled at a low temperature, has excellent cracking resistance, and can be suitable for corrosion prevention of the steel pipe with large height of a welding seam on the surface of the steel pipe and poor regularity. The application of the polyethylene powder steel pipeline outer wall in corrosion prevention or damage repair is suitable for coating the outer wall of a steel pipe at the temperature of 190-210 ℃, and is particularly suitable for low-temperature corrosion prevention of outer PE and inner epoxy anticorrosive steel pipes.
Description
Technical Field
The invention relates to the field of corrosion prevention of steel pipes, in particular to a polyethylene powder coating for external corrosion prevention of a steel pipeline, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The plastic-coated steel pipe has the characteristics of corrosion resistance and long service life, so that the plastic-coated steel pipe is widely applied to water administration and water conservancy construction. The plastic-coated steel pipe with the outer polyethylene powder and the inner epoxy powder for corrosion prevention is the most common corrosion prevention mode at present. The polyethylene powder is used for preventing corrosion on the outer wall of the steel pipe, so that the steel pipe can be effectively protected from corrosion of soil and the like; the inner epoxy powder can effectively protect the steel pipe from being corroded by the conveying medium. The most common anticorrosion process of the prior outer polyethylene powder and inner epoxy powder anticorrosion steel pipe is as follows: after the steel pipe is subjected to sand blasting and rust removal, the steel pipe is heated in a heating furnace at 260-300 ℃, the surface temperature of the steel pipe is controlled to be 220-240 ℃, polyethylene corrosion prevention is carried out on the outer wall of the steel pipe by using modes of spray coating, fluidized tank roll coating and the like, and then the leveling of a polyethylene corrosion prevention layer is realized by means of the waste heat of the steel pipe; and when the temperature of the inner wall of the steel pipe reaches 170-200 ℃, performing corrosion prevention on the inner epoxy powder through roller coating or spraying, and realizing leveling and curing of epoxy by means of the waste heat of the steel pipe to obtain the corrosion-resistant steel pipe with the inner epoxy powder and the outer polyethylene powder. The polyethylene powder used in the existing anticorrosion process has the following problems: (1) In order to ensure the leveling of the outer polyethylene powder, the residual heat temperature of the steel pipe needs to be raised to more than 250 ℃, the excessive temperature easily causes the polyethylene powder to be subjected to thermal aging degradation in the leveling process, and when the height of a welding seam of the steel pipe is large or the shape of the welding seam is irregular, a polyethylene coating formed by the polyethylene powder at the welding seam is easy to crack due to the existence of stress or the polyethylene aging caused by high-temperature leveling; (2) After the outer polyethylene is used for corrosion prevention, a waiting process is needed, the corrosion prevention of the inner epoxy powder can be carried out when the temperature of the steel pipe is reduced to 170-200 ℃, otherwise, the problems of too fast curing, poor leveling effect and the like can occur due to the high temperature of the steel pipe in the epoxy powder corrosion prevention.
Disclosure of Invention
The invention provides a cracking-resistant low-temperature leveling polyethylene powder and a preparation method and application thereof, aiming at solving the problems that in the prior art, when the polyethylene powder is used for the external corrosion prevention of a steel pipe, the polyethylene is easy to be subjected to thermal aging and degradation due to the fact that the polyethylene is subjected to corrosion prevention at 220-240 ℃ or even higher, and the corrosion prevention efficiency is low due to the fact that the waiting process time for epoxy corrosion prevention of an inner wall is long when the polyethylene is cooled to 170-200 ℃.
The invention is realized by the following technical scheme:
in a first aspect of the invention, there is provided a crack resistant, low temperature levelling polyethylene powder comprising: 5-15 parts of maleic anhydride grafted modified polyolefin elastomer copolymer, 2-5 parts of ethylene acrylic acid copolymer, 10-20 parts of rotational molding grade linear low density polyethylene, 52-80 parts of high-fluidity polyethylene and 3-8 parts of functional additive;
the maleic anhydride graft modified polyolefin elastomer copolymer is prepared by blending a matrix, an organic peroxide initiator and maleic anhydride and then extruding the mixture at 160-220 ℃ through double-screw reaction;
the grafting rate of the maleic anhydride graft modified polyolefin elastomer copolymer is 0.5-1.5%.
Preferably, the maleic anhydride graft modified polyolefin elastomer copolymer takes at least two of polyethylene butene copolymer, polyethylene octene copolymer, ethylene-vinyl acetate copolymer and propylene-based elastomer as matrixes, wherein one of the polyethylene butene copolymer, the polyethylene octene copolymer, the ethylene-vinyl acetate copolymer and the propylene-based elastomer is propylene-based elastomer; the proportion of the propenyl elastomer is 20-50 parts, and the rest of the matrix is 50-80 parts.
Preferably, the melt mass flow rate of the maleic anhydride graft-modified polyolefin elastomer copolymer is 3 to 12g/10min (190 ℃,2.16kg weight).
Preferably, the content of acrylic acid in the ethylene acrylic acid copolymer is 5-30%; the melt mass flow rate was 5-300g/10min (190 ℃,2.16kg weight).
Preferably, the rotomolding grade linear low density polyethylene has a density of from 0.93 to 0.94g/cm 3 The melt mass flow rate was 4-10g/10min (190 ℃,2.16kg weight).
Preferably, the high flow polyethylene is at least one of low density polyethylene and linear low density polyethylene with melt mass flow rate of 40-70g/min (190 ℃,2.16kg weight).
Preferably, the functional auxiliary agent is at least one of an antioxidant, an ultraviolet light stabilizer, a color master batch, a leveling agent, an anti-blocking agent and a filler for powder.
In a second aspect of the present invention, there is provided a method for preparing a crack-resistant, low-temperature leveling polyethylene powder, comprising: mixing the maleic anhydride grafted and modified polyolefin elastomer copolymer, the ethylene acrylic acid copolymer, the rotational molding level linear low density polyethylene, the high-fluidity polyethylene and the functional auxiliary agent in proportion, extruding by using a screw extruder at the temperature of 130-160 ℃ and the rotating speed of 350-600rpm, carrying out melt blending granulation, grinding by using a mechanical grinding mill, and selecting a 40-80 mesh screen according to requirements to obtain polyethylene powder with required fineness.
The third aspect of the invention provides application of the cracking-resistant and low-temperature leveling polyethylene powder and/or the preparation method of the cracking-resistant and low-temperature leveling polyethylene powder in corrosion prevention or damage repair of the outer wall of a steel pipeline, which is suitable for coating the outer wall of a steel pipe at the temperature of 190-210 ℃, and is preferably suitable for low-temperature corrosion prevention of outer PE and inner epoxy anticorrosive steel pipes.
One or more of the technical schemes have the following beneficial effects:
1) The maleic anhydride graft modified copolymer prepared at 160-220 ℃ is extruded by double-screw reaction by using a polyethylene butene copolymer, a polyethylene octene copolymer, an ethylene-vinyl acetate copolymer and a propenyl elastomer as matrixes, so that the adhesion force of polyethylene powder to a steel pipe is improved. Compared with the polyethylene (the melting point is generally 120-131 ℃) grafted and modified by maleic anhydride in the prior art, the melting point of the maleic anhydride grafted copolymer elastomer is not more than 100 ℃, so that the maleic anhydride grafted copolymer elastomer is more beneficial to realizing bonding and leveling at low temperature.
2) The maleic anhydride graft modification method comprises the steps of performing reaction extrusion by using a polyethylene butene copolymer, a polyethylene octene copolymer, an ethylene-vinyl acetate copolymer and a propylene-based elastomer as matrixes to perform maleic anhydride graft modification, wherein the propylene-based elastomer is subjected to degradation reaction of a propylene unit under the action of an organic peroxide initiator, so that the crosslinking side reaction of the polyethylene butene copolymer, the polyethylene octene copolymer and the ethylene-vinyl acetate copolymer under the action of the organic peroxide initiator can be slowed down to a certain extent, the grafting rate of the maleic anhydride graft modified polyolefin elastomer copolymer is controlled to be 0.5-1.5%, the melt mass flow rate of the maleic anhydride graft modified polyolefin elastomer copolymer is 3-12g/10min (190 ℃,2.16kg weight), and the phenomenon that the leveling of polyethylene powder is influenced by excessive crosslinking of the grafted maleic anhydride graft copolymer elastomer after graft modification is avoided.
3) The ethylene propylene copolymer and the maleic anhydride graft copolymer elastomer act synergistically to provide excellent adhesion to polyethylene powder. The melting point of the ethylene-propylene copolymer is 70-100 ℃, which is beneficial to leveling the polyethylene powder at a lower temperature; the ethylene acrylic acid copolymer is a polar polymer formed by copolymerization, the content of polar monomer acrylic acid is adjustable within 5-30%, and the adhesive force to metal is good.
4) The rotational molding linear low-density polyethylene is selected to replace widely used metallocene polyethylene in the prior art, and good environmental stress cracking resistance is provided for polyethylene powder. The rotational molding linear polyethylene has good leveling property and excellent environmental stress cracking resistance. Compared with metallocene polyethylene in the prior art, the defects of narrow molecular weight distribution and high leveling temperature of the metallocene polyethylene are overcome. Meanwhile, the maleic anhydride graft copolymer elastomer increases the toughness of the polyethylene powder, so that the powder has excellent toughness, can adapt to steel pipes with different calibers and high weld joint heights, and avoids the problem that a coating formed at a weld joint of a polyethylene coating cracks due to stress.
5) Compared with the defects of high leveling temperature and poor leveling caused by high-density polyethylene and metallocene polyethylene used in the prior art, the maleic anhydride grafted and modified polyolefin elastomer copolymer, the ethylene acrylic acid copolymer, the rotational molding grade linear low-density polyethylene, the high-fluidity polyethylene and the functional additive used in the invention are all components with low melting point and good fluidity, and the components are matched to facilitate low-temperature bonding and leveling.
6) The polyethylene powder has excellent adhesive force, good toughness, excellent low-temperature leveling property and other comprehensive properties, the outer wall of the steel pipeline using the polyethylene powder for corrosion prevention can be applied to corrosion prevention or damage repair at the temperature of more than 190 ℃, and the aging and degradation of a polyethylene anticorrosive coating are effectively avoided through low-temperature corrosion prevention, so that the service life of the anticorrosive coating is longer.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be noted that the examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In one embodiment of the present invention, there is provided a crack resistant, low temperature leveling polyethylene powder comprising: 5-15 parts of maleic anhydride graft modified polyolefin elastomer copolymer, 2-5 parts of ethylene acrylic acid copolymer, 10-20 parts of rotational molding grade linear low density polyethylene, 52-80 parts of high-fluidity polyethylene and 3-8 parts of functional auxiliary agent;
the polyolefin elastomer copolymer grafted and modified by maleic anhydride is prepared by blending a matrix, an organic peroxide initiator and maleic anhydride and then extruding the mixture at 160-220 ℃ through double-screw reaction;
the grafting rate of the maleic anhydride graft modified polyolefin elastomer copolymer is 0.5-1.5%.
In yet another embodiment of the present invention, the composition of the maleic anhydride grafted elastomeric copolymer is 60% of ethylene octene copolymer ENGAGE 8137 (Dow chemical), 40% of propylene based elastomer Vistamaxx 3000 (Exxon Mobil); or, ethylene-vinyl acetate copolymer UE633 (taiwan polymeric chemicals, ltd.) 80%, propylene-based elastomer Vistamaxx 3980 (exxonmobil) 20%; or polyethylene octene copolymer Solumer 8730 (LG chemical) 20%, ethylene-vinyl acetate copolymer 14J6 (Yanshan petrochemical) 50%, propylene-based elastomer VERSIFY TM 3000 (Dow chemical) 30%; alternatively, in yet another embodiment of the present invention, the polyethylene octene copolymer solumer (tm) 8730 (LG chemical) 50% and ethylene vinyl acetate 14J6 (yanshan petrochemical) 50%.
The research of the invention discovers that the polyethylene powder in the prior art is mainly prepared by blending maleic anhydride grafted polyethylene, high-density polyethylene, metallocene polyethylene, linear low-density polyethylene, low-density polyethylene and antioxidant.
For example, patent No. CN 113278329A discloses a modified polyethylene powder, which comprises the following components: 10 to 30 parts of maleic anhydride grafted high-density polyethylene, 40 to 70 parts of linear low-density polyethylene, 5 to 30 parts of metallocene linear polyethylene, 3 to 15 parts of thermoplastic elastomer, 1 to 3 parts of color master and 0.3 to 1 part of additive.
For another example, patent No. CN 110256909A discloses a thermoplastic electrostatic sprayed polyethylene powder, which comprises: 40-50% of low-density polyethylene, 20-30% of metallocene polyethylene, 10-15% of maleic anhydride grafted polyethylene, 04-0.8% of antioxidant, 1-4% of conductive agent, 2-5% of wetting agent, 0.2-0.4% of brightener and 2-4.8% of degassing agent, wherein polyethylene powder is sprayed on a substrate through an electrostatic spray gun and baked at 195-210 ℃ for 10-15 min for plasticizing and leveling.
The maleic anhydride grafted polyethylene is easy to excessively crosslink and has a crosslinking side reaction under the action of an organic peroxide initiator, so that the leveling of polyethylene powder is influenced;
the melting point of the high-density polyethylene is 131 ℃, the melting point is high, and the high-density polyethylene can be leveled only by high temperature;
metallocene polyethylene has poor flowability and also requires higher temperatures to ensure leveling of the coated polyethylene powder.
The low-melting-point maleic anhydride grafted modifier is prepared by taking the low-melting-point copolymer elastomer and the propenyl elastomer as matrixes to perform maleic anhydride grafted modification, and provides good low-temperature bonding performance for the powder to the steel pipe. The co-action of the rotational molding grade linear low density polyethylene and the elastomer graft modified copolymer provides the anti-cracking capability of the polyethylene powder when the steel pipe is coated. The polyethylene powder is particularly suitable for being applied to the outer wall of a steel pipeline and can be used for corrosion prevention or damage repair at the temperature of more than 190 ℃.
The invention utilizes the polyethylene butene copolymer, the polyethylene octene copolymer, the ethylene-vinyl acetate copolymer and the propenyl elastomer as the matrix, and extrudes the maleic anhydride graft modified copolymer prepared at 160-220 ℃ through the double-screw reaction, thereby improving the adhesive force of the polyethylene powder to the steel pipe. Compared with the polyethylene grafted and modified by maleic anhydride (the melting point is generally 120-131 ℃), the melting point of the maleic anhydride grafted copolymer elastomer of the invention is not more than 100 ℃, thus being more beneficial to realizing bonding and leveling at low temperature.
The maleic anhydride graft copolymer elastomer increases the toughness of the polyethylene powder, so that the powder has excellent toughness, can adapt to steel pipes with different calibers and high weld joint heights, and avoids the problem that a coating formed on a weld joint of a polyethylene coating cracks due to stress.
The preparation method comprises the steps of taking a polyethylene butene copolymer, a polyethylene octene copolymer, an ethylene-vinyl acetate copolymer and a propylene-based elastomer as matrixes, reacting and extruding to obtain maleic anhydride, wherein the propylene-based elastomer is subjected to degradation reaction of a propylene-based unit under the action of an organic peroxide initiator, so that the crosslinking side reaction of the polyethylene butene copolymer, the polyethylene octene copolymer and the ethylene-vinyl acetate copolymer under the action of the organic peroxide initiator can be slowed down to a certain extent, the grafting rate of the maleic anhydride graft modified polyolefin elastomer copolymer is controlled to be 0.5-1.5%, the melt mass flow rate of the maleic anhydride graft modified polyolefin elastomer copolymer is 3-12g/10min (190 ℃,2.16kg weight), and the maleic anhydride graft copolymer elastomer after graft modification is prevented from being excessively crosslinked to influence the leveling of the polyethylene powder.
In still another embodiment of the present invention, the melt mass flow rate of the maleic anhydride graft-modified polyolefin elastomer copolymer is 3 to 12g/10min (190 ℃,2.16kg weight).
In another embodiment of the present invention, the content of acrylic acid in the ethylene acrylic acid copolymer is 5% to 30%; further, the melt mass flow rate was 5 to 300g/10min (190 ℃,2.16kg weight).
The ethylene acrylic acid copolymer is a polar polymer formed by copolymerization, the content of polar monomer acrylic acid is adjustable within 5-30%, and the adhesive force to metal is good.
The ethylene-propylene copolymer contains acrylic acid groups, the maleic anhydride graft contains maleic anhydride groups, both the two groups have good bonding effect on metal, and the ethylene-propylene copolymer and the maleic anhydride graft copolymer elastomer have synergistic effect to provide excellent bonding effect for polyethylene powder. The melting point of the ethylene-propylene copolymer is 70-100 ℃, which is beneficial to leveling the polyethylene powder at a lower temperature; the ethylene acrylic acid copolymer is a polar polymer formed by copolymerization, the content of polar monomer acrylic acid is adjustable within 5-30%, and the adhesive force to metal is good.
In yet another embodiment of the present invention, the rotomolding grade linear low density polyethylene has a density of 0.93 to 0.94g/cm 3 The melt mass flow rate was 4-10g/10min (190 ℃,2.16kg weight).
The rotational molding linear low-density polyethylene is selected to replace widely used metallocene polyethylene in the prior art, and good environmental stress cracking resistance is provided for polyethylene powder. The rotational molding linear polyethylene has good leveling property and excellent environmental stress cracking resistance. Compared with the metallocene polyethylene in the prior art, the rotational molding linear polyethylene avoids the defects of narrow molecular weight distribution and high leveling temperature of the metallocene polyethylene. Meanwhile, the maleic anhydride graft copolymer elastomer increases the toughness of the polyethylene powder, so that the powder has excellent toughness, can adapt to steel pipes with different calibers and high weld joint heights, and avoids the problem that a coating formed at a weld joint of a polyethylene coating cracks due to stress.
In still another embodiment of the present invention, the high flow polyethylene is at least one of a low density polyethylene and a linear low density polyethylene having a melt mass flow rate of 40 to 70g/min (190 ℃,2.16kg weight).
In another embodiment of the present invention, the functional additive is at least one of an antioxidant, an ultraviolet light stabilizer, a color masterbatch, a leveling agent, an anti-blocking agent, and a filler for powder.
In another embodiment of the present invention, there is provided a method for preparing the above-mentioned crack-resistant, low-temperature leveling polyethylene powder, comprising: mixing a maleic anhydride grafted modified polyolefin elastomer copolymer, an ethylene acrylic acid copolymer, rotational molding grade linear low-density polyethylene, high-fluidity polyethylene and a functional auxiliary agent in proportion, extruding by using a screw extruder at the temperature of 130-160 ℃ and the rotating speed of 350-600rpm, carrying out melt blending granulation, grinding by using a mechanical grinding mill, and selecting a 40-80-mesh screen according to needs to obtain polyethylene powder with the required fineness.
In another embodiment of the present invention, the application of the polyethylene powder and/or the preparation method of the polyethylene powder in corrosion prevention or repair of outer walls of steel pipelines is provided, which is suitable for coating outer walls of steel pipes at 190-210 ℃, and is especially suitable for low temperature corrosion prevention of outer PE and inner epoxy corrosion-resistant steel pipes.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting. The parts are parts by mass.
Example 1
The polyethylene powder consisted of the following components in table 1:
table 1 polyethylene powder preparation of example 1
The information on the raw materials used in example 1 is as follows:
maleic anhydride grafted elastomeric copolymer (E-g-MAH) ethylene octene copolymer ENGAGE TM 8137 (Dow chemical) 60%, propylene-based elastomer Vistamaxx 3000 (Exxon Mobil) 40%, dicumyl peroxide initiator 0.08% and maleic anhydride 1.5%, mixing, and performing reactive extrusion at 180 ℃ by using an extruder to obtain a maleic anhydride grafted elastomer copolymer with a melt mass flow rate of 6.2g/10min and a maleic anhydride grafting rate of 1.2%;
ethylene acrylic acid copolymer (EAA): PRIMACOR 1430, melt mass flow rate of 5.0g/10min, acrylic acid content of 9.7%, SK integrated chemistry;
rotational molding grade PE:7151U, density 0.935g/cm 3 Melt mass flow rate 5g/10min, china petrochemical company;
high flow PE: LD450, melt mass flow rate 40g/10min, yanshan petrochemical;
carbon black masterbatch: EM105G, carbon black content 42%, shandong Macro tubes, inc.;
silicon micropowder: GSF-2, new materials science and technology Limited, anhui Gerui;
antioxidant: 215, beijing very advanced chemical Co.
The preparation method of the polyethylene powder comprises the following specific steps:
uniformly mixing the components according to the proportion by using a mixer, adding the mixture into a double-screw extruder, carrying out melt blending at 150 ℃, granulating to obtain modified polyethylene particles, grinding the modified polyethylene particles by using a mechanical grinder, and sieving the ground polyethylene particles by using a 50-mesh screen to obtain polyethylene powder.
Testing and application of polyethylene powder:
the melt flow rate, tensile strength, elongation at break, vicat softening point were measured according to GB/T28897-2021 and the relevant data are shown in Table 4.
Selecting a DN1820 steel pipe, performing shot blasting and rust removal on the steel pipe, coating the outer wall of the steel pipe by a curtain coating process, performing roll coating when the temperature of the surface of the steel pipe is 200 ℃, controlling the thickness of the coating to be 1.8-2.2cm, and showing the peel strength and the appearance of the coated coating in Table 4.
Example 2
The information on the raw materials used in example 2 is as follows, the polyethylene powder having the composition according to table 2:
table 2 polyethylene powder preparation in example 2
Maleic anhydride graft copolymer elastomer (E-g-MAH-1): mixing 80% of an ethylene-vinyl acetate copolymer UE633 (Taiwan Polymer chemical Co., ltd., china), 20% of a propylene-based elastomer Vistamaxx 3980 (Exxon Mobil), 0.05% of a tert-butyl cumyl peroxide initiator and 2.0% of maleic anhydride, and then carrying out reaction extrusion at 160 ℃ by using an extruder to obtain a maleic anhydride grafted elastomer copolymer with a melt mass flow rate of 12.0g/10min and a maleic anhydride grafting rate of 1.5%;
maleic anhydride graft copolymer elastomer (E-g-MAH-2) prepared by mixing 50% of polyethylene-butene copolymer LC565 (LG chemical), 50% of propylene-based elastomer VERSIFY 2300 (Dow chemical), 0.1% of di-tert-butyl peroxide initiator and 1.0% of maleic anhydride, and subjecting the mixture to reactive extrusion at 200 ℃ by using an extruder to obtain a maleic anhydride graft elastomer copolymer with a melt mass flow rate of 4.5g/10min and a maleic anhydride grafting rate of 0.8%;
maleic anhydride graft copolymer elastomer (E-g-MAH-3) prepared by mixing polyethylene octene copolymer Solumer TM 8730 (LG CHEMICAL) 20%, ethylene-vinyl acetate copolymer 14J6 (Yanshan petrochemical) 50%, propylene-based elastomer VERSIFY TM 3000 (Dow chemical) 30%, 0.06% of 2, 5-di-tert-butylperoxy-2, 5-dimethylhexane initiator and 1.2% of maleic anhydride are mixed and then are subjected to reactive extrusion at 190 ℃ by using an extruder to obtain a maleic anhydride grafted elastomer copolymer with the melt mass flow rate of 3.8g/10min and the maleic anhydride grafting rate of 1.0%;
ethylene acrylic acid copolymer (EAA): escor TM 5110, melt mass flow rate of 14g/10min, acrylic acid content of 11%, exxonmobil;
rotational molding grade PE: DNDB7149, density 0.934g/cm3, melt mass flow rate 4g/10min, china petro-chemical Qilu petrochemical company;
high flow PE: LLDPE2650 with a melt mass flow rate of 50g/10min, tianjin division of petrochemical industry in China;
carbon black masterbatch: EM105G, carbon black content 42%, shandong Macro tubes, inc.;
calcium carbonate: ground calcium carbonate, 1250 mesh, double horse chemical limited in corridor city;
antioxidant: 1010, beijing very easily chemical Co., ltd.
The preparation method of the polyethylene powder comprises the following specific steps:
uniformly mixing the components according to the proportion by using a mixer, adding the mixture into a double-screw extruder, carrying out melt blending at 130 ℃, granulating to obtain modified polyethylene particles, grinding the modified polyethylene particles by using a mechanical grinder, and sieving the ground polyethylene particles by using a 60-mesh screen to obtain polyethylene powder.
Testing and application of polyethylene powder:
the melt flow rate, tensile strength, elongation at break, vicat softening point were measured according to GB/T28897-2021 and the data are shown in Table 4.
Selecting a DN1820 steel pipe, performing shot blasting and rust removal on the steel pipe, coating the outer wall of the steel pipe by a fluidized tank roll coating process, wherein the roll coating is performed when the temperature of the surface of the steel pipe is 210 ℃, the thickness of the coating is controlled to be 1.8-2.2cm, and the peel strength and the appearance of the coated coating are shown in Table 4.
Comparative example 1
The polyethylene powder consisted of the following components in table 3:
table 3 polyethylene powder preparation of comparative example 1
Maleic anhydride graft copolymer elastomer (E-g-MAH-3) is prepared from polyethylene octene copolymer Solumer 8730 (LG chemical) 20%, ethylene-vinyl acetate copolymer 14J6 (Yanshan petrochemical) 50%, and propylene-based elastomer VERSIFY TM 3000 (Dow chemical) 30%, 0.06% of 2, 5-di-tert-butylperoxy-2, 5-dimethylhexane initiator and 1.2% of maleic anhydride are mixed and then are subjected to reactive extrusion at 190 ℃ by using an extruder to obtain a maleic anhydride grafted elastomer copolymer with the melt mass flow rate of 3.8g/10min and the maleic anhydride grafting rate of 1.0%;
maleic anhydride graft copolymer elastomer (E-g-MAH-4) prepared by mixing 50% of polyethylene octene copolymer (Solumer TM 8730 (LG chemical), 50% of ethylene-vinyl acetate copolymer (14J 6 (Yanshan petrochemical)), 0.06% of 2, 5-di-tert-butylperoxy-2, 5-dimethylhexane initiator and 1.2% of maleic anhydride, and performing reaction extrusion at 190 deg.C by using an extruder to obtain maleic anhydride graft elastomer copolymer with melt mass flow rate of 1.8g/10min and maleic anhydride graft ratio of 1.0%;
maleic anhydride grafted polyethylene:
e589, dupont;
ethylene acrylic acid copolymer (EAA): escor 5110, melt mass flow rate of 14g/10min, acrylic acid content of 11%, exxon Mobil;
rotational molding grade PE: DNDB7149, density 0.934g/cm3, melt mass flow rate 4g/10min, china petro-chemical Qilu petrochemical company;
high flow PE: 2650 of LLDPE, with a melt mass flow rate of 50g/10min, china petrochemical Tianjin division;
carbon black masterbatch: EM105G, carbon black content 42%, shandong Macro tubes, inc.;
calcium carbonate: heavy calcium carbonate, 1250 mesh, double-horse chemical limited in corridor city;
antioxidant: 1010, beijing very easily chemical Co., ltd.
The preparation method of the polyethylene powder comprises the following specific steps:
uniformly mixing the components according to the proportion by using a mixer, adding the mixture into a double-screw extruder, carrying out melt blending at 130 ℃, granulating to obtain modified polyethylene particles, grinding the modified polyethylene particles by using a mechanical grinder, and sieving the ground polyethylene particles by using a 60-mesh screen to obtain polyethylene powder.
Testing and application of polyethylene powder:
the melt flow rate, tensile strength, elongation at break, vicat softening point were measured according to GB/T28897-2021 and the data are shown in Table 4.
Selecting a DN1820 steel pipe, performing shot blasting and rust removal on the steel pipe, coating the outer wall of the steel pipe by a fluidized tank roll coating process, wherein the roll coating is performed when the temperature of the surface of the steel pipe is 210 ℃, the thickness of the coating is controlled to be 1.8-2.2cm, and the peel strength and the appearance of the coated coating are shown in Table 4.
TABLE 4 test and application Effect data of examples and comparative examples
The embodiment 1-embodiment 2 show that all indexes of the prepared polyethylene powder meet the requirements of GB/T28897-2021, particularly the peeling strength of the coating, and the addition of the maleic anhydride graft copolymer elastomer and the ethylene acrylic acid copolymer can greatly improve the adhesion of the coating to the steel pipe and can ensure that the coating is bright. As can be seen from examples 1A to 1F, the polyethylene powder can form a bright polyethylene coating on the outer wall of DN1820 steel pipe even at a plastic coating temperature of 190 ℃.
From 2C and 3A, it is clear that the gloss of the coating after leveling becomes poor without adding 3A of the ethylene acrylic acid copolymer; 2C and 3B show that although the peel strength of the coating reaches the standard requirement, the coating at the welding seam has the cracking problem by taking the ethylene acrylic acid copolymer as the bonding component without adding the maleic anhydride graft copolymer elastomer; according to the results of 2C and 3C, no propenyl elastomer is added into the maleic anhydride grafted copolymer elastomer, so that the melt mass flow rate of the maleic anhydride grafted copolymer elastomer is reduced, a coating formed by plastic coating at 210 ℃ has severe orange peel wrinkles, and the leveling of polyethylene powder is influenced; from 2C and 3D, the maleic anhydride grafted polyethylene of DuPont is used for replacing the maleic anhydride grafted copolymer elastomer, so that the coating formed by plastic coating at 210 ℃ has serious orange peel, and the coating cracks at a welding seam; it is clear from the comparison of 2C with 3E that the replacement of the rotomolding grade of linear low density polyethylene of the present invention with metallocene polyethylene results in severe orange peel appearance of the coating formed by coating at 210 ℃. It is understood from comparative examples 1 and 2 and comparative column 1 that the low melting point maleic anhydride graft modified product obtained by maleic anhydride graft modification using the low melting point copolymer elastomer and the acryl-based elastomer as the matrix provides the powder with good low temperature adhesion to the steel pipe. The co-action of the rotational molding grade linear low density polyethylene and the elastomer graft modified copolymer provides the anti-cracking capability of the polyethylene powder when the steel pipe is coated. The polyethylene powder is particularly suitable for the application of the outer wall of the steel pipeline in corrosion prevention or damage repair at the temperature of more than 190 ℃.
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 modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. 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.
Claims (10)
1. The polyethylene powder with crack resistance and low-temperature leveling property is characterized by comprising the following raw materials in parts by mass:
5-15 parts of maleic anhydride graft modified polyolefin elastomer copolymer;
2-5 parts of ethylene acrylic acid copolymer;
10-20 parts of rotational molding grade linear low-density polyethylene;
52-80 parts of high-fluidity polyethylene;
3-8 parts of a functional auxiliary agent;
the maleic anhydride graft modified polyolefin elastomer copolymer is prepared by blending a matrix, an organic peroxide initiator and maleic anhydride and then extruding the mixture at 160-220 ℃ through double-screw reaction;
the grafting rate of the maleic anhydride graft modified polyolefin elastomer copolymer is 0.5-1.5%.
2. The crack-resistant, low temperature leveling polyethylene powder of claim 1 wherein the maleic anhydride graft modified polyolefin elastomer copolymer is based on at least two of polyethylene butene copolymer, polyethylene octene copolymer, ethylene-vinyl acetate copolymer, propylene based elastomer, and one of them is propylene based elastomer.
3. The crack resistant, low temperature leveling polyethylene powder of claim 2 wherein the propylene based elastomer is present in the matrix in a ratio of 20 to 50 parts, the remainder of the matrix being 50 to 80 parts.
4. The crack resistant, low temperature leveling polyethylene powder of claim 1 wherein the maleic anhydride graft modified polyolefin elastomer copolymer melt mass flow rate is 3 to 12g/10min.
5. The crack-resistant low-temperature leveling polyethylene powder according to claim 1, wherein the content of acrylic acid in the ethylene acrylic acid copolymer is 5% -30%;
further, the melt mass flow rate is 5 to 300g/10min.
6. The crack resistant, low temperature leveling polyethylene powder of claim 1 wherein the rotomolding grade linear low density polyethylene has a density of 0.93 to 0.94g/cm 3 The melt mass flow rate is 4-10g/10min.
7. The crack-resistant, low temperature leveling polyethylene powder of claim 1 wherein the high flow polyethylene is at least one of a low density polyethylene, linear low density polyethylene having a melt mass flow rate of 40-70 g/min.
8. The crack-resistant, low temperature leveling polyethylene powder of claim 1 wherein the functional additive is at least one of an antioxidant, an ultraviolet light stabilizer, a color concentrate, a leveling agent, an antiblocking agent, and a filler for the powder.
9. A process for the preparation of a crack resistant, low temperature levelling polyethylene powder according to any one of claims 1 to 8 comprising: mixing the maleic anhydride grafted and modified polyolefin elastomer copolymer, the ethylene acrylic acid copolymer, the rotational molding level linear low density polyethylene, the high-fluidity polyethylene and the functional auxiliary agent in proportion, extruding by using a screw extruder at the temperature of 130-160 ℃ and the rotating speed of 350-600rpm, carrying out melt blending granulation, grinding by using a mechanical grinding mill, and selecting a 40-80 mesh screen according to requirements to obtain polyethylene powder with required fineness.
10. Use of the crack resistant, low temperature leveling polyethylene powder of any one of claims 1 to 8 and/or the method of preparation of the crack resistant, low temperature leveling polyethylene powder of claim 9 for corrosion protection or repair of steel pipe outer walls, suitable for coating at a steel pipe outer wall temperature of 190-210 ℃, preferably for low temperature corrosion protection of outer PE, inner epoxy corrosion resistant steel pipes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002138240A (en) * | 2000-11-01 | 2002-05-14 | Sumitomo Seika Chem Co Ltd | Polyethylene resin powder coating material |
| CN109880445A (en) * | 2019-03-25 | 2019-06-14 | 金旸（厦门）新材料科技有限公司 | A kind of high bonding force polyethylene powder coating and its preparation method and application |
| CN111019444A (en) * | 2019-12-27 | 2020-04-17 | 上海邦中新材料有限公司 | Pressure-resistant tank polyethylene powder coating for pipeline and preparation method thereof |
| CN115011022A (en) * | 2022-07-04 | 2022-09-06 | 山东东宏管业股份有限公司 | Special anti-aging 3PE anti-corrosion material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138240A (en) * | 2000-11-01 | 2002-05-14 | Sumitomo Seika Chem Co Ltd | Polyethylene resin powder coating material |
| CN109880445A (en) * | 2019-03-25 | 2019-06-14 | 金旸（厦门）新材料科技有限公司 | A kind of high bonding force polyethylene powder coating and its preparation method and application |
| CN111019444A (en) * | 2019-12-27 | 2020-04-17 | 上海邦中新材料有限公司 | Pressure-resistant tank polyethylene powder coating for pipeline and preparation method thereof |
| CN115011022A (en) * | 2022-07-04 | 2022-09-06 | 山东东宏管业股份有限公司 | Special anti-aging 3PE anti-corrosion material and preparation method and application thereof |
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