CN115895347B - Weld cracking-resistant low-temperature leveling polyethylene powder and preparation method and application thereof - Google Patents
Weld cracking-resistant low-temperature leveling polyethylene powder and preparation method and application thereof Download PDFInfo
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- CN115895347B CN115895347B CN202211126782.4A CN202211126782A CN115895347B CN 115895347 B CN115895347 B CN 115895347B CN 202211126782 A CN202211126782 A CN 202211126782A CN 115895347 B CN115895347 B CN 115895347B
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
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- 238000012360 testing method Methods 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
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- FAIIFDPAEUKBEP-UHFFFAOYSA-N Nilvadipine Chemical compound COC(=O)C1=C(C#N)NC(C)=C(C(=O)OC(C)C)C1C1=CC=CC([N+]([O-])=O)=C1 FAIIFDPAEUKBEP-UHFFFAOYSA-N 0.000 description 2
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to polyethylene powder for external corrosion prevention of a steel pipeline and a preparation method thereof. The polyethylene powder consists of the following raw materials in parts by weight: 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 auxiliary agent, and obtaining the polyethylene powder with weld cracking resistance and low temperature leveling through blending, double screw melting granulation and mechanical grinding. The polyethylene powder disclosed by the invention can be used for preserving and leveling steel pipes at low temperature, has excellent cracking resistance, and can be suitable for preserving steel pipes with large surface weld heights and poor regularity. The polyethylene powder steel pipeline outer wall corrosion prevention or repair method is suitable for coating at the temperature of 190-210 ℃ on the outer wall of the steel pipe, and is particularly suitable for low-temperature corrosion prevention of outer PE and inner epoxy corrosion prevention steel pipes.
Description
Technical Field
The invention relates to the field of steel pipe corrosion prevention, in particular to a polyethylene powder coating for steel pipe external corrosion prevention, and a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the 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 already known to those of ordinary skill in the art.
The plastic-coated steel pipe has the characteristics of corrosion resistance and long service life, and is widely applied to water administration and water conservancy construction. The plastic coated steel tube with the anticorrosion of the outer polyethylene powder and the inner epoxy powder is the most commonly used anticorrosion mode at present. The polyethylene powder is used for corrosion prevention of the outer wall of the steel pipe, so that the steel pipe can be effectively protected from being corroded by the soil and other external environments; the inner wall of the steel pipe is preserved by the inner epoxy powder, and the thermosetting epoxy coating can effectively protect the steel pipe from being corroded by a conveying medium. The most commonly used anticorrosion flow of the external polyethylene powder and internal epoxy powder anticorrosion steel pipe at present is as follows: heating the steel pipe in a heating furnace at 260-300 ℃ after sand blasting and rust removal, controlling the surface temperature of the steel pipe to 220-240 ℃, performing polyethylene corrosion prevention on the outer wall of the steel pipe by means of spray coating, fluidized tank roll coating and the like, and then realizing leveling of a polyethylene corrosion prevention layer by means of waste heat of the steel pipe; and (3) when the temperature of the inner wall of the steel pipe is 170-200 ℃, performing anticorrosion of inner epoxy powder by roll coating or spray coating, and realizing leveling and solidification of epoxy by means of waste heat of the steel pipe to obtain the anticorrosion steel pipe with the inner epoxy and the outer polyethylene. The polyethylene powder used in the existing corrosion prevention process has the following problems: (1) In order to ensure the leveling of the outer polyethylene powder, the waste heat temperature of the steel pipe is required to be increased to more than 250 ℃, the excessive temperature easily causes thermal aging degradation of the polyethylene powder in the leveling process, and when the welding seam of the steel pipe is particularly large in height or irregular in shape, the polyethylene coating formed by the polyethylene powder at the welding seam is easy to crack due to the existence of stress or the aging of the polyethylene caused by high Wen Liuping; (2) After the outer polyethylene is preserved, a waiting process is needed, the temperature of the steel pipe is reduced to 170-200 ℃, and the preservation of the inner epoxy powder can be performed, otherwise, the epoxy powder can be cured too quickly due to the high temperature of the steel pipe, the leveling effect is poor, and the like.
Disclosure of Invention
In order to solve the problems of low corrosion prevention efficiency and the like caused by long waiting process time of polyethylene powder for corrosion prevention of the outer wall epoxy of a steel pipe, which is easy to heat aging and degrade due to the fact that the polyethylene powder is used for corrosion prevention of the outer wall of the steel pipe and needs to be subjected to corrosion prevention at 220-240 ℃ or even higher, the invention provides cracking-resistant low-temperature leveling polyethylene powder, and a preparation method and application thereof.
The invention is realized by the following technical scheme:
In a first aspect of the invention, there is provided a crack resistant, low temperature leveling 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 auxiliary agent;
The maleic anhydride grafted and modified polyolefin elastomer copolymer is prepared by mixing a matrix, an organic peroxide initiator and maleic anhydride, and then extruding the mixture through a double screw reaction at 160-220 ℃;
the grafting rate of the maleic anhydride grafted and modified polyolefin elastomer copolymer is 0.5-1.5%.
Preferably, the maleic anhydride grafted and modified polyolefin elastomer copolymer takes at least two of polyethylene butene copolymer, polyethylene octene copolymer, ethylene-vinyl acetate copolymer and propenyl elastomer as a matrix, wherein one of the two is propenyl elastomer; the ratio of the propenyl elastomer is 20-50 parts, and the rest matrix is 50-80 parts.
Preferably, the melt mass flow rate of the maleic anhydride graft modified polyolefin elastomer copolymer is 3-12g/10min (190 ℃,2.16kg weight).
Preferably, the ethylene acrylic acid copolymer has an acrylic acid content of 5% to 30%; the melt mass flow rate is 5-300g/10min (190 ℃,2.16kg weight).
Preferably, the rotomoulding grade linear low density polyethylene has a density of 0.93 to 0.94g/cm 3 and a melt mass flow rate of 4 to 10g/10min (190 ℃ C., 2.16kg weight).
Preferably, the high-flow polyethylene is at least one of low-density polyethylene and linear low-density polyethylene with a melt mass flow rate of 40-70g/min (190 ℃ C., 2.16kg weight).
Preferably, the functional auxiliary agent is at least one of an antioxidant, an ultraviolet light stabilizer, a color master, a leveling agent, an anti-caking agent and a filler for powder.
In a second aspect, the invention provides a method for preparing cracking-resistant low-temperature leveling polyethylene powder, which is characterized by comprising the following steps: the maleic anhydride grafted modified polyolefin elastomer copolymer, ethylene acrylic acid copolymer, rotational molding grade linear low density polyethylene, high fluidity polyethylene and functional auxiliary agent are mixed according to a certain proportion, the temperature is 130-160 ℃ when the mixture is extruded by a screw extruder, the screw rotating speed is 350-600rpm, the mixture is melted, blended and granulated, and then the mixture is milled by a mechanical mill, and a 40-80-mesh screen is selected according to the requirement, so that polyethylene powder with the required fineness is obtained.
In a third aspect of the invention, the invention provides a cracking-resistant low-temperature leveling polyethylene powder and/or an application of a preparation method of the cracking-resistant low-temperature leveling polyethylene powder in corrosion prevention or repair of an outer wall of a steel pipeline, which is suitable for coating at the temperature of 190-210 ℃ of the outer wall of a steel pipe, and is preferably suitable for low-temperature corrosion prevention of an outer PE (polyethylene) and an inner epoxy anti-corrosion steel pipe.
The technical scheme has the following beneficial effects:
1) The polyethylene butene copolymer, the polyethylene octene copolymer, the ethylene-vinyl acetate copolymer and the propenyl elastomer are used as a matrix, and the maleic anhydride graft modified copolymer prepared at 160-220 ℃ is extruded through twin-screw reaction, so that the adhesion force of polyethylene powder to a steel pipe is improved. 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 disclosed by the invention is not more than 100 ℃, so that the adhesion and leveling at low temperature are more facilitated.
2) The maleic anhydride grafting modification is carried out by taking polyethylene butene copolymer, polyethylene octene copolymer, ethylene-vinyl acetate copolymer and propenyl elastomer as matrix reaction extrusion, and propenyl elastomer is degraded by propenyl unit under the action of organic peroxide initiator, so that the cross-linking 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 relieved to a certain extent, the grafting rate of the maleic anhydride grafting modified polyolefin elastomer copolymer is controlled to be 0.5% -1.5%, the melt mass flow rate of the maleic anhydride grafting modified polyolefin elastomer copolymer is 3-12g/10min (190 ℃ and 2.16kg weight) and the influence of excessive cross-linking of the maleic anhydride grafting copolymer elastomer after grafting modification on the leveling of polyethylene powder is avoided.
3) The ethylene propylene copolymer and the maleic anhydride graft copolymer elastomer cooperate to provide excellent bonding effect for the polyethylene powder. The melting point of the ethylene propylene copolymer is 70-100 ℃, which is favorable for leveling polyethylene powder at a lower temperature; the ethylene acrylic acid copolymer is a polar polymer formed by copolymerization, the content of the polar monomer acrylic acid is adjustable between 5% and 30%, and the adhesive force to metal is good.
4) The linear low density polyethylene of rotational molding grade is selected to replace metallocene polyethylene widely used in the prior art, and provides good environmental stress cracking resistance for polyethylene powder. The rotational molding grade linear polyethylene has good leveling property and excellent environmental stress cracking resistance. Compared with the metallocene polyethylene in the prior art, the defects of narrow molecular weight distribution and high leveling temperature of the metallocene polyethylene are avoided. Meanwhile, the maleic anhydride grafted copolymer elastomer increases the toughness of polyethylene powder, so that the powder has excellent toughness, can adapt to steel pipes with different calibers and high weld heights, and avoids the problem that a coating formed at a weld 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 modified polyolefin elastomer copolymer, ethylene acrylic acid copolymer, rotational molding grade linear low-density polyethylene, high-fluidity polyethylene and functional auxiliary agent used in the invention are all components with low melting point and good fluidity, and the components are matched, so that low-temperature bonding and leveling are realized.
6) The polyethylene powder has the comprehensive properties of excellent adhesive force, good toughness, excellent low-temperature leveling property and the like, and the steel pipeline outer wall preserved by using the polyethylene powder can be applied to preservation or repair at the temperature of more than 190 ℃, and the ageing and degradation of a polyethylene preservative layer are effectively avoided through low-temperature preservation, so that the service life of the preservative layer is longer.
Detailed Description
The invention will be further illustrated with reference to 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, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
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 the exemplary embodiments according to the present disclosure. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
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 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 auxiliary agent;
The maleic anhydride grafted and modified polyolefin elastomer copolymer is prepared by mixing a matrix, an organic peroxide initiator and maleic anhydride, and then extruding the mixture through a double screw reaction at 160-220 ℃;
the grafting rate of the maleic anhydride grafted and modified polyolefin elastomer copolymer is 0.5-1.5%.
In yet another embodiment of the present invention, the maleic anhydride grafted elastomeric copolymer has a composition of ethylene octene copolymer ENGAGE 8137 (dow chemical) 60%, propylene based elastomer Vistamaxx 3000 (exkesen mobil) 40%; or, ethylene-vinyl acetate copolymer UE633 (taiwan polymerization chemicals limited) 80%, propylene-based elastomer Vistamaxx 3980 (exkesen mobil) 20%; or, polyethylene octene copolymer SolumerTM 8730 (LG chemistry) 20%, ethylene-vinyl acetate copolymer 14J6 (yankee petrochemical) 50%, propylene-based elastomer VERSIFY TM 3000 (dow chemistry) 30%; or, in yet another embodiment of the present invention, the polyethylene octene copolymer SolumerTM 8730 (LG chemistry) 50% and the ethylene-vinyl acetate copolymer 14J6 (crape chemical) 50%.
The invention researches find that the polyethylene powder in the prior art is mainly formed by blending maleic anhydride grafted polyethylene, high-density polyethylene, metallocene polyethylene, linear low-density polyethylene, low-density polyethylene and an antioxidant.
For example, patent CN 113278329A discloses a modified polyethylene powder comprising the following components: 10-30 parts of maleic anhydride grafted high-density polyethylene, 40-70 parts of linear low-density polyethylene, 5-30 parts of metallocene linear polyethylene, 3-15 parts of thermoplastic elastomer, 1-3 parts of color masterbatch and 0.3-1 part of additive.
For another example, patent CN 110256909A discloses a thermoplastic electrostatically-sprayed polyethylene powder comprising the composition: 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 brightening agent and 2-4.8% of degasifying agent, wherein polyethylene powder is sprayed on a substrate through an electrostatic spray gun, and is plasticized and leveled after being baked for 10-15min at 195-210 ℃.
The maleic anhydride grafted polyethylene is easy to excessively crosslink and crosslink by-products under the action of an organic peroxide initiator, so that the leveling of polyethylene powder is affected;
The melting point of the high-density polyethylene is 131 ℃, the melting point is high, and the high-density polyethylene can be leveled at high temperature;
Metallocene polyethylenes have poor flowability and also require higher temperatures to ensure leveling of the polyethylene powder of the coating.
The invention uses the low-melting point copolymer elastomer and the propenyl elastomer as the matrix to carry out maleic anhydride grafting modification, and the prepared low-melting point maleic anhydride grafting modifier provides the powder with good low-temperature bonding performance to the steel pipe. The combined action of the rotational molding grade linear low density polyethylene and the elastomer graft modified copolymer provides the cracking resistance of the polyethylene powder when the steel pipe forms a coating. The polyethylene powder is particularly suitable for the application of the steel pipeline outer wall in corrosion prevention or repair at the temperature of more than 190 ℃.
The invention uses polyethylene butene copolymer, polyethylene octene copolymer, ethylene-vinyl acetate copolymer and propenyl elastomer as matrix, and the maleic anhydride graft modified copolymer prepared at 160-220 ℃ is extruded by twin-screw reaction, so as to improve the adhesive force of polyethylene powder to steel pipes. 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 disclosed by the invention is not more than 100 ℃, so that the adhesion and leveling at low temperature are more facilitated.
The maleic anhydride grafted copolymer elastomer increases the toughness of polyethylene powder, so that the powder has excellent toughness, can adapt to steel pipes with different calibers and high weld heights, and avoids the problem that a coating formed by a polyethylene coating at a weld joint cracks due to stress.
The maleic anhydride is extruded by taking polyethylene butene copolymer, polyethylene octene copolymer, ethylene-vinyl acetate copolymer and propenyl elastomer as matrix reaction, and the propenyl elastomer is degraded by the propenyl unit under the action of an organic peroxide initiator, so that the cross-linking 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 relieved to a certain extent, the grafting rate of the maleic anhydride grafting modified polyolefin elastomer copolymer is controlled to be 0.5-1.5%, the melt mass flow rate of the maleic anhydride grafting modified polyolefin elastomer copolymer is 3-12g/10min (190 ℃ and 2.16kg weight) and the excessive cross-linking of the maleic anhydride grafting copolymer elastomer after grafting modification is avoided to influence the leveling of polyethylene powder.
In yet another embodiment of the 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 yet another embodiment of the present invention, the ethylene acrylic acid copolymer has an acrylic acid content of 5% to 30%; further, the melt mass flow rate was 5-300g/10min (190 ℃,2.16kg weight).
The ethylene acrylic acid copolymer is a polar polymer formed by copolymerization, the content of the polar monomer acrylic acid is adjustable between 5% and 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 groups have good bonding effect on metals, and the ethylene-propylene copolymer and the maleic anhydride graft copolymer elastomer are cooperated to provide excellent bonding effect for polyethylene powder. The melting point of the ethylene propylene copolymer is 70-100 ℃, which is favorable for leveling polyethylene powder at a lower temperature; the ethylene acrylic acid copolymer is a polar polymer formed by copolymerization, the content of the polar monomer acrylic acid is adjustable between 5% and 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 and a melt mass flow rate of 4 to 10g/10min (190 ℃ C., 2.16kg weight).
The linear low density polyethylene of rotational molding grade is selected to replace metallocene polyethylene widely used in the prior art, and provides good environmental stress cracking resistance for polyethylene powder. The rotational molding grade linear polyethylene has good leveling property and excellent environmental stress cracking resistance. The existing metallocene polyethylene has poor fluidity, the leveling of polyethylene powder of the coating can be ensured at a higher temperature, and compared with the metallocene polyethylene in the prior art, the rotational molding-grade linear polyethylene avoids the defects of narrow molecular weight distribution and high leveling temperature of the metallocene polyethylene. Meanwhile, the maleic anhydride grafted copolymer elastomer increases the toughness of polyethylene powder, so that the powder has excellent toughness, can adapt to steel pipes with different calibers and high weld heights, and avoids the problem that a coating formed at a weld of a polyethylene coating cracks due to stress.
In yet 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 40-70g/min (190 ℃ C., 2.16kg weight).
In another specific embodiment of the invention, the functional auxiliary agent is at least one of an antioxidant, an ultraviolet light stabilizer, a color master, a leveling agent, an anti-caking agent and a filler for powder.
In still another embodiment of the present invention, a method for preparing the above crack-resistant, low temperature leveling polyethylene powder is provided, comprising: the maleic anhydride grafted modified polyolefin elastomer copolymer, ethylene acrylic acid copolymer, rotational molding grade linear low density polyethylene, high fluidity polyethylene and functional auxiliary agent are mixed according to a certain proportion, the temperature is 130-160 ℃ when the mixture is extruded by a screw extruder, the screw rotating speed is 350-600rpm, the mixture is melted, blended and granulated, and then the mixture is milled by a mechanical mill, and a 40-80-mesh screen is selected according to the requirement, so that polyethylene powder with the required fineness is obtained.
In a further specific embodiment of the invention, the application of the polyethylene powder and/or the preparation method of the polyethylene powder in corrosion prevention or repair of the outer wall of a steel pipeline is provided, and the polyethylene powder is suitable for coating at the temperature of 190-210 ℃ of the outer wall of a steel pipe, and is particularly suitable for low-temperature corrosion prevention of an outer PE (polyethylene) and inner epoxy anti-corrosion steel pipe.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting. The parts are mass parts.
Example 1
The polyethylene powder was composed according to table 1:
Table 1 polyethylene powder formulation in example 1
The information on the raw materials used in example 1 is as follows:
The maleic anhydride grafted elastomer copolymer (E-g-MAH) is prepared by mixing ethylene octene copolymer ENGAGE TM 8137 (Dow chemical) 60%, propylene elastomer Vistamaxx 3000 (Exxon Mobil) 40%, dicumyl peroxide initiator 0.08% and maleic anhydride 1.5%, and extruding at 180deg.C to obtain maleic anhydride grafted elastomer copolymer with melt mass flow rate of 6.2g/10min and 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 synthetic chemistry;
Rotational molding grade PE:7151U, density 0.935g/cm 3, melt mass flow rate 5g/10min, qilu petrochemical company, china;
high flow PE: LD450, melt mass flow rate 40g/10min, yanshan petrochemical;
carbon black masterbatch: EM105G, carbon black content 42%, shandong macropipe company limited;
Silicon micropowder: GSF-2, anhui Gray New Material technologies Co., ltd;
An antioxidant: 215, beijing polar chemical industry Co., ltd.
The preparation method of the polyethylene powder comprises the following specific steps:
The components are uniformly mixed by a mixer according to the proportion, are added into a double-screw extruder, are subjected to melt blending at 150 ℃, and are granulated to obtain modified polyethylene particles, and then are subjected to grinding by a mechanical grinding machine and pass through a 50-mesh screen to obtain polyethylene powder.
Testing and application of polyethylene powder:
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.
And (3) selecting a DN1820 steel pipe, performing shot blasting on the steel pipe, and coating the outer wall of the steel pipe through a curtain coating process, wherein the rolling coating is performed when the temperature of the surface of the steel pipe is 200 ℃, the thickness of the coating is controlled to be 1.8-2.2cm, and the peeling strength and the appearance of the coating after coating are shown in Table 4.
Example 2
The raw materials used in example 2 are as follows, the polyethylene powder composition according to Table 2:
table 2 polyethylene powder formulation in example 2
Maleic anhydride graft copolymer elastomer (E-g-MAH-1): mixing ethylene-vinyl acetate copolymer UE633 (Taiwan polymerization chemical Co., ltd.) 80%, propylene-based elastomer Vistamaxx 3980 (Exxon Mobil) 20%, tert-butyl cumyl peroxide initiator 0.05% and maleic anhydride 2.0%, and performing reaction extrusion at 160deg.C by using an extruder to obtain maleic anhydride grafted elastomer copolymer with melt mass flow rate of 12.0g/10min and maleic anhydride grafting rate of 1.5%;
Maleic anhydride grafted copolymer elastomer (E-g-MAH-2) is prepared by mixing polyethylene butene copolymer LC565 (LG chemical) 50%, propylene-based elastomer VERSIFY 2300 (Dow chemical) 50%, di-t-butyl peroxide initiator 0.1% and maleic anhydride 1.0%, and extruding at 200deg.C to obtain maleic anhydride grafted elastomer copolymer with melt mass flow rate of 4.5g/10min and maleic anhydride grafting rate of 0.8%;
Maleic anhydride graft copolymer elastomer (E-g-MAH-3) comprising mixing polyethylene octene copolymer Solumer TM 8730 (LG chemical) 20%, ethylene-vinyl acetate copolymer 14J6 (Yangshan petrochemical) 50%, propylene-based elastomer VERSIFY TM 3000 (Dow chemical) 30%,2, 5-di-tert-butyl peroxy-2, 5-dimethylhexane initiator 0.06% and maleic anhydride 1.2%, and then extruding by an extruder at 190℃to obtain maleic anhydride graft elastomer copolymer having a melt mass flow rate of 3.8g/10min and a maleic anhydride graft ratio of 1.0%;
ethylene acrylic acid copolymer (EAA): escor TM 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, qilu petrochemical company, china;
High flow PE: LLDPE2650 with melt mass flow rate of 50g/10min, and the China petrochemical Tianjin division;
carbon black masterbatch: EM105G, carbon black content 42%, shandong macropipe company limited;
calcium carbonate: heavy calcium carbonate, 1250 mesh, langfang city, bimatose chemical company, inc;
an antioxidant: 1010, beijing polar chemical industry Co., ltd.
The preparation method of the polyethylene powder comprises the following specific steps:
The components are uniformly mixed by a mixer according to the proportion, are added into a double-screw extruder, are subjected to melt blending at 130 ℃, and are granulated to obtain modified polyethylene particles, and then are subjected to grinding by a mechanical grinding machine and pass through a 60-mesh screen to obtain polyethylene powder.
Testing and application of polyethylene powder:
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.
And (3) selecting a DN1820 steel pipe, performing shot blasting on the steel pipe, and coating the outer wall of the steel pipe through a fluidized bed roll coating process, wherein the roll coating is performed when the surface temperature 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 coating after coating are shown in Table 4.
Comparative example 1
The polyethylene powder was composed according to table 3:
table 3 polyethylene powder formulation in comparative example 1
Maleic anhydride graft copolymer elastomer (E-g-MAH-3) comprising mixing polyethylene octene copolymer SolumerTM 8730 (LG chemical) 20%, ethylene-vinyl acetate copolymer 14J6 (Yangshan petrochemical) 50%, propylene-based elastomer VERSIFY TM 3000 (Dow chemical) 30%,2, 5-di-tert-butyl peroxy-2, 5-dimethylhexane initiator 0.06% and maleic anhydride 1.2%, and then extruding by an extruder at 190℃to obtain maleic anhydride graft elastomer copolymer having a melt mass flow rate of 3.8g/10min and a maleic anhydride graft ratio of 1.0%;
maleic anhydride graft copolymer elastomer (E-g-MAH-4) comprising mixing polyethylene octene copolymer SolumerTM 8730 (LG chem.) 50%, ethylene-vinyl acetate copolymer 14J6 (Yanshan petrochemical) 50%, 2, 5-di-tert-butyl peroxy-2, 5-dimethylhexane initiator 0.06% and maleic anhydride 1.2%, and extruding at 190℃by an extruder to obtain maleic anhydride graft elastomer copolymer having a melt mass flow rate of 1.8g/10min and a maleic anhydride grafting rate 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, qilu petrochemical company, china;
High flow PE: LLDPE2650 with melt mass flow rate of 50g/10min, and the China petrochemical Tianjin division;
carbon black masterbatch: EM105G, carbon black content 42%, shandong macropipe company limited;
calcium carbonate: heavy calcium carbonate, 1250 mesh, langfang city, bimatose chemical company, inc;
an antioxidant: 1010, beijing polar chemical industry Co., ltd.
The preparation method of the polyethylene powder comprises the following specific steps:
The components are uniformly mixed by a mixer according to the proportion, are added into a double-screw extruder, are subjected to melt blending at 130 ℃, and are granulated to obtain modified polyethylene particles, and then are subjected to grinding by a mechanical grinding machine and pass through a 60-mesh screen to obtain polyethylene powder.
Testing and application of polyethylene powder:
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.
And (3) selecting a DN1820 steel pipe, performing shot blasting on the steel pipe, and coating the outer wall of the steel pipe through a fluidized bed roll coating process, wherein the roll coating is performed when the surface temperature 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 coating after coating are shown in Table 4.
Table 4 test and application effect data for examples and comparative examples
According to the embodiment 1-embodiment 2, all indexes of the prepared polyethylene powder meet the requirements of GB/T28897-2021, particularly the peeling strength of a coating, and the adhesive force of the coating to a steel pipe can be greatly improved by adding the maleic anhydride graft copolymer elastomer and the ethylene acrylic acid copolymer, and meanwhile, the coating can be bright. From examples 1A-1F, it is clear that even at 190℃coating temperature, the polyethylene powder still forms a clear polyethylene coating on the outer wall of DN1820 steel pipe.
As is clear from 2C and 3A, 3A without ethylene acrylic acid copolymer added, the gloss of the coating after leveling is deteriorated; as can be seen from 2C and 3B, the coating layer has a crack at the weld joint although the peel strength of the coating layer meets the standard requirement without adding a maleic anhydride graft copolymer elastomer and with an ethylene acrylic acid copolymer as an adhesive component; 2C and 3C show that the maleic anhydride grafted copolymer elastomer is not added with a propylene-based 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 serious orange peel, and the leveling of polyethylene powder is affected; it is known from 2C and 3D that substitution of DuPont maleic anhydride grafted polyethylene for the maleic anhydride grafted copolymer elastomer of the present invention results in severe orange peel appearance of the coating formed by the plastic coating at 210℃and cracking of the coating at the weld; it is known from a comparison of 2C and 3E that the substitution of metallocene polyethylene for the rotomoulding grade linear low density polyethylene of the present invention resulted in severe orange peel of the coating formed by the plastics coating at 210 ℃. As is clear from comparative examples 1,2 and 1, the low-melting point maleic anhydride graft modification prepared by graft modification of maleic anhydride with the low-melting point copolymer elastomer and the acryl-based elastomer as a matrix provides the powder with good low-temperature adhesion property to steel pipes. The combined action of the rotational molding grade linear low density polyethylene and the elastomer graft modified copolymer provides the cracking resistance of the polyethylene powder when the steel pipe forms a coating. The polyethylene powder is particularly suitable for the application of the steel pipeline outer wall in corrosion prevention or repair at the temperature of more than 190 ℃.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. 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 cracking-resistant low-temperature leveling polyethylene powder is characterized by comprising the following raw materials in parts by mass:
5-15 parts of maleic anhydride grafted and 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 functional auxiliary agent;
The maleic anhydride grafted and modified polyolefin elastomer copolymer is prepared by mixing a matrix, an organic peroxide initiator and maleic anhydride, and then extruding the mixture through a twin-screw reaction at 160-220 ℃;
the grafting rate of the maleic anhydride grafting modified polyolefin elastomer copolymer is 0.5% -1.5%;
the maleic anhydride grafted modified polyolefin elastomer copolymer takes at least two of polyethylene butene copolymer, polyethylene octene copolymer, ethylene-vinyl acetate copolymer and propenyl elastomer as a matrix, and one of the two is propenyl elastomer.
2. A crack resistant, low temperature leveling polyethylene powder according to claim 1 wherein said propylene based elastomer comprises 20 to 50 parts of said matrix and 50 to 80 parts of the remaining matrix.
3. A crack resistant, low temperature leveling polyethylene powder according to claim 1, wherein said maleic anhydride graft modified polyolefin elastomer copolymer has a melt mass flow rate of 3 to 12g/10min, said melt mass flow rate being tested at 190 ℃ and said melt mass flow rate being tested under a load of 2.16kg weight.
4. The cracking resistant, low temperature leveling polyethylene powder of claim 1, wherein said ethylene acrylic acid copolymer comprises from 5% to 30% acrylic acid;
The melt mass flow rate is 5-300g/10min, the test temperature of the melt mass flow rate is 190 ℃, and the test load of the melt mass flow rate is 2.16kg weight.
5. The crack resistant, low temperature leveling polyethylene powder of claim 1, wherein said rotomolding grade linear low density polyethylene has a density of 0.93-0.94g/cm3, a melt mass flow rate of 4-10g/10min, a test temperature of 190 ℃, and a test load of 2.16kg weight.
6. The cracking resistant, low temperature leveling polyethylene powder of claim 1, wherein said high flow polyethylene is at least one of a low density polyethylene having a melt mass flow rate of 40-70g/min, a linear low density polyethylene, a test temperature of 190 ℃, and a test load of 2.16kg weight.
7. The cracking-resistant low-temperature leveling polyethylene powder according to claim 1, wherein the functional auxiliary agent is at least one of an antioxidant, an ultraviolet stabilizer, a color master, a leveling agent, an anti-caking agent and a filler for the powder.
8. A process for the preparation of a crack resistant, low temperature leveling polyethylene powder according to any one of claims 1 to 7, comprising: the maleic anhydride grafted modified polyolefin elastomer copolymer, ethylene acrylic acid copolymer, rotational molding grade linear low density polyethylene, high fluidity polyethylene and functional auxiliary agent are mixed according to a certain proportion, the temperature is 130-160 ℃ when the mixture is extruded by a screw extruder, the screw rotating speed is 350-600rpm, the mixture is melted, blended and granulated, and then the mixture is milled by a mechanical mill, and a 40-80-mesh screen is selected according to the requirement, so that polyethylene powder with the required fineness is obtained.
9. Use of a crack-resistant, low temperature levelling polyethylene powder according to any of claims 1 to 7 for the corrosion protection or repair of steel pipe outer walls, characterized in that the coating is carried out at a steel pipe outer wall temperature of 190-210 ℃.
10. Use according to claim 9 for low temperature corrosion protection of outer PE, inner epoxy corrosion protection 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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