CN113278329A - Modified polyethylene and preparation method and application thereof - Google Patents
Modified polyethylene and preparation method and application thereof Download PDFInfo
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- CN113278329A CN113278329A CN202110565355.5A CN202110565355A CN113278329A CN 113278329 A CN113278329 A CN 113278329A CN 202110565355 A CN202110565355 A CN 202110565355A CN 113278329 A CN113278329 A CN 113278329A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09D123/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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- 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
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention belongs to the technical field of powder coatings, and particularly relates to modified polyethylene and a preparation method and application thereof. The modified polyethylene provided by the invention comprises the following components in parts by mass: 40-70 parts of linear low-density polyethylene; 5-30 parts of metallocene linear polyethylene; 10-30 parts of maleic anhydride grafted high-density polyethylene; 3-15 parts of a thermoplastic elastomer; 1-3 parts of color master batch; 0.3-1 part of additive. The coating obtained from the modified polyethylene provided by the invention has excellent tensile strength and adhesion. The results of the examples show that the tensile strength of the coating formed by the modified polyethylene serving as the powder coating on the surface of the hot-dip galvanized metal substrate part is 13.3-13.8 MPa, and the adhesive force is 0 grade or 1 grade.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to modified polyethylene and a preparation method and application thereof.
Background
The polyethylene powder coating is widely applied due to cheap raw materials, excellent chemical resistance, electric insulation and low temperature resistance, and is mainly used for the anticorrosive coating of refrigerator baskets such as the shells of the refrigerators, the guardrails of the highways, the separation fences of the highways, iron wires, steel-plastic composite electric power threading pipes, large steel containers and the like. Different fields have different requirements on the polyethylene powder coating, wherein when the polyethylene powder coating is applied to hot galvanized workpieces such as highway guardrails, separation fences and the like, the application is limited due to the problems of poor mechanical strength and poor adhesive force of the formed coating.
Chinese patent CN107793848A discloses a super-weather-resistant polyethylene powder coating, but the main research on how to improve the weather resistance of the polyethylene coating is to improve the mechanical strength and the adhesion of the coating is not reported.
Disclosure of Invention
In view of the above, the invention provides modified polyethylene, and a preparation method and an application thereof.
The invention provides modified polyethylene which comprises the following components in parts by mass:
preferably, the linear low density polyethylene has a trade mark of one or more of DFDA7042, TJZS-2650, LLDPE3224, DNDA8320, M1840, M2320, YLF-1802 and LLO220 KJ.
Preferably, the metallocene linear polyethylene has one or more of the designations QX5983, Sp1071C, 5815, BPD3801, Sp2040 and M3581 UV.
Preferably, the thermoplastic elastomer is one or more of polyester elastomer, polyolefin elastomer, acrylate elastomer and ethylene-vinyl acetate copolymer elastomer.
Preferably, the additives include antioxidants, light stabilizers and lubricants.
Preferably, the mass ratio of the antioxidant to the light stabilizer to the lubricant is 1 (1-2) to 1-2.
The invention provides a preparation method of modified polyethylene in the technical scheme, which comprises the following steps:
mixing, melt extruding and granulating linear low-density polyethylene, metallocene linear polyethylene, maleic anhydride grafted high-density polyethylene, thermoplastic elastomer, color master batch and additive to obtain the modified polyethylene.
Preferably, the extrusion is carried out in a single screw extruder, the body of which is divided into eight sections;
the temperature of the first section is 110-140 ℃, the temperature of the second section is 120-150 ℃, the temperature of the third section is 130-160 ℃, the temperature of the fourth-seventh sections is 120-160 ℃ independently, and the temperature of the eighth section is 120-150 ℃.
Preferably, the mixing time is 10-15 min, the mixing is carried out under the stirring condition, and the rotating speed of the stirring machine is 40-60 r/min.
The invention provides application of the modified polyethylene in the technical scheme or the modified polyethylene prepared by the preparation method in the technical scheme as a powder coating.
The invention provides modified polyethylene which comprises the following components in parts by mass: 40-70 parts of linear low-density polyethylene, 5-30 parts of metallocene linear polyethylene, 10-30 parts of maleic anhydride grafted high-density polyethylene, 3-15 parts of thermoplastic elastomer, 1-3 parts of color master batch and 0.3-1 part of additive. The modified polyethylene provided by the invention takes linear low-density polyethylene as a base material, and the addition amount of the metallocene linear polyethylene improves the tensile strength and toughness of the modified polyethylene when used as a powder coating; the maleic anhydride grafted high-density polyethylene introduces strong polar side group maleic anhydride on a nonpolar polyethylene molecular chain, so that the maleic anhydride grafted high-density polyethylene effectively improves the cohesiveness and compatibility of the coating and a substrate material, thereby greatly improving the adhesive force of the modified polyethylene to the substrate when the modified polyethylene is used as a powder coating; the thermoplastic elastomer further improves the strength and adhesion of a coating formed when the modified polyethylene is used as a powder coating. Therefore, the modified polyethylene provided by the application has excellent tensile strength and adhesion, and has high mechanical strength and strong adhesion with a matrix when used as a powder coating. The results of the examples show that the tensile strength of the coating formed by the modified polyethylene serving as the powder coating on the surface of the hot-dip galvanized metal substrate part is 13.3-13.8 MPa, and the adhesive force is 0 grade or 1 grade.
Detailed Description
The invention provides modified polyethylene which comprises the following components in parts by mass:
the modified polyethylene provided by the invention comprises 40-70 parts by mass of linear low-density polyethylene, preferably 45-65 parts by mass, and more preferably 50-60 parts by mass; in the present invention, the linear low density polyethylene is preferably one or more of DFDA7042, TJZS-2650, LLDPE3224, DNDA8320, M1840, M2320, YLF-1802, and LLO220KJ, more preferably any two of DFDA7042 or TJZS-2650, LLDPE3224, DNDA8320, M1840, M2320, YLF-1802, and LLO220KJ, and in the present invention, when the linear low density polyethylene is preferably any two of TJZS-2650, LLDPE3224, DNDA8320, M1840, M2320, YLF-1802, and LLO220KJ, particularly TJZS-2650 and LLDPE3224, the mass ratio is preferably 1: 1, or specifically M1840 and YLF-1802, preferably in a mass ratio of 1: 1. the source of the linear low density polyethylene is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used.
The modified polyethylene provided by the invention takes linear low-density polyethylene as a main base material.
Based on linear low-density polyethylene, the modified polyethylene provided by the invention comprises 5-30 parts of metallocene linear polyethylene, preferably 10-25 parts, and more preferably 15-20 parts; in the present invention, the metallocene linear polyethylene is preferably one or more of QX5983, Sp1071C, 5815, BPD3801, Sp2040, and M3581UV, and more preferably one or more of 5815, BPD3801, and M3581UV, and when the metallocene linear polyethylene preferably includes two or more of the above specific substances, the present invention does not particularly require the mass ratio of the above substances. The source of the metallocene linear polyethylene is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used.
According to the invention, the metallocene linear polyethylene is added and the addition amount of the metallocene linear polyethylene is controlled, so that the tensile strength and toughness of the modified polyethylene as a powder coating are improved.
Based on linear low-density polyethylene, the modified polyethylene provided by the invention comprises 10-30 parts of maleic anhydride grafted high-density polyethylene, preferably 15-25 parts, and more preferably 17.5-21.5 parts; the source of the maleic anhydride grafted high density polyethylene is not particularly required in the present invention, and commercially available products well known to those skilled in the art can be used.
According to the invention, the maleic anhydride grafted high-density polyethylene component is added, and the addition amount of the maleic anhydride grafted high-density polyethylene component is controlled, and the maleic anhydride grafted high-density polyethylene component is a bridge for improving the cohesiveness and compatibility of the coating and the substrate material because the maleic anhydride grafted high-density polyethylene introduces strong polar side-group maleic anhydride into a nonpolar polyethylene molecular chain, so that the adhesion force of the modified polyethylene to the substrate when the modified polyethylene is used as a powder coating is greatly improved.
Based on linear low-density polyethylene, the modified polyethylene provided by the invention comprises 3-15 parts of thermoplastic elastomer, more preferably 4.5-10 parts, and most preferably 5-8.5 parts; in the present invention, the thermoplastic elastomer is preferably one or more of a polyester-based elastomer, a polyolefin-based elastomer, an acrylate-based elastomer, and an ethylene-vinyl acetate copolymer elastomer, and more preferably a polyolefin-based elastomer and/or an ethylene-vinyl acetate copolymer; in the present invention, but when the thermoplastic elastomer includes a polyolefin-based elastomer and an ethylene-vinyl acetate copolymer, the mass ratio of the polyolefin-based elastomer and the ethylene-vinyl acetate copolymer is preferably 1: (1-2); in the present invention, the polyolefin-based elastomer is preferably an ethylene-octene copolymer. The source of the thermoplastic elastomer is not particularly critical to the present invention and commercially available products well known to those skilled in the art may be used.
According to the invention, the strength and the adhesive force of a coating formed by using the modified polyethylene as the powder coating are further improved by adding the thermoplastic elastomer and controlling the addition amount of the thermoplastic elastomer.
Based on linear low-density polyethylene, the modified polyethylene provided by the invention comprises 1-3 parts of color master, preferably 1.5-2.5 parts; in the invention, the color master batch is used for color development, and is preferably purchased from Dinghai plastic chemical industry Co., Ltd, Dongguan city, and the product model is Dinghai 81030.
Based on linear low-density polyethylene, the modified polyethylene provided by the invention comprises 0.3-1 part of additive, and more preferably 0.5-0.8 part; in the present invention, the additives preferably include an antioxidant, a light stabilizer and a lubricant, and the antioxidant is preferably a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphite-based antioxidant and a thioester/ether-based antioxidant, and more preferably a hindered amine-based antioxidant and a thioester/ether-based antioxidant, and in the present invention, when the antioxidant is preferably a hindered amine-based antioxidant and a thioester/ether-based antioxidant, the mass ratio of the hindered amine-based antioxidant and the thioester/ether-based antioxidant is preferably 1: (0.1-0.2), in the specific embodiment of the invention, the antioxidant is purchased from Beijing addition auxiliary research institute, and the product model is antioxidant PKB-225.
In the present invention, the light stabilizer is preferably a polymeric hindered amine light stabilizer, and in a specific embodiment of the present invention, the light stabilizer is purchased from Beijing addition Assistant research institute and has a product model number of GW-944.
In the present invention, the lubricant is preferably one or more of a fatty acid amide, a fatty acid ester and an aliphatic hydrocarbon, more preferably a fatty acid amide, and most preferably an oleamide. The source of the lubricant is not particularly critical to the present invention and commercially available products well known to those skilled in the art may be used.
In the invention, the mass ratio of the antioxidant to the light stabilizer to the lubricant is preferably 1 (1-2) to 1-2, more preferably 1: (1.35-1.6): (1.35-1.6).
In the invention, the antioxidant and the light stabilizer improve the weather resistance of the modified polyethylene, and the lubricant improves the service performance of the modified polyethylene.
The invention provides a preparation method of modified polyethylene in the technical scheme, which comprises the following steps:
mixing, melt extruding and granulating linear low-density polyethylene, metallocene linear polyethylene, maleic anhydride grafted high-density polyethylene, thermoplastic elastomer, color master batch and additive.
Mixing the raw materials to obtain a mixed material; in the invention, the mixing time is preferably 10-15 min, the mixing is preferably carried out under stirring conditions, the stirring speed is preferably 40-60 r/min, and in the specific embodiment of the invention, the mixing is preferably carried out in a stirrer. The invention mixes the raw materials evenly by mixing.
After the mixed material is obtained, the mixed material is subjected to melt extrusion and granulation to obtain modified polyethylene; in the invention, the melt extrusion is preferably carried out in a single screw extruder, and the machine body of the single screw extruder is preferably divided into eight sections, wherein the first section is a feeding zone, the second section and the third section are heating zones, the fourth section to the seventh section are mixing zones, and the eighth section is a machine head zone; in the invention, the temperature of the first section is preferably 110-140 ℃, more preferably 120-130 ℃, the temperature of the second section is preferably 120-150 ℃, more preferably 130-140 ℃, the temperature of the third section is preferably 130-160 ℃, more preferably 140-150 ℃, the temperature of the fourth section is preferably 120-160 ℃, more preferably 130-140 ℃, the temperature of the fifth section, the temperature of the sixth section and the temperature of the seventh section are preferably the same as the temperature of the fourth section, and the temperature of the eighth section is preferably 120-150 ℃, more preferably 130-140 ℃.
The present invention does not require any particular implementation of the granulation process, and can be carried out by procedures known to those skilled in the art.
The invention provides application of the modified polyethylene in the technical scheme or the modified polyethylene prepared by the preparation method in the technical scheme as a powder coating.
According to the invention, the modified polyethylene powder prepared by the technical scheme is preferably ground to obtain the modified polyethylene powder, and the modified polyethylene powder is used as a powder coating.
In the present invention, the particle size of the modified polyethylene powder is preferably 0.212 to 0.3 mm.
In the present invention, the milling is preferably carried out in a mill, and the present invention has no particular requirement on the specific implementation of the milling.
In the invention, the application is preferably to use the modified polyethylene powder coating for preparing a substrate surface coating.
In the present invention, the substrate is preferably a hot galvanized metal substrate.
In the present invention, the preparation method is preferably hot dip molding.
In the present invention, the preparation method preferably includes the steps of:
preheating the substrate to obtain a preheated part;
dipping the preheated part in the modified polyethylene powder to obtain a plastic dipped part;
and curing the plastic impregnated part to form a coating on the surface of the substrate.
The substrate is preferably subjected to a pretreatment, the pretreatment preferably comprises washing and drying, the invention has no special requirements on the specific implementation of the washing, the invention removes oil stains and impurities on the surface of the substrate by washing, and the invention has no special requirements on the specific implementation process of the drying.
Preheating the substrate to obtain a preheated part; in the invention, the preheating temperature is preferably 150-250 ℃, and the preheating time is preferably 10-30 min.
After a preheating piece is obtained, the preheating piece is soaked in the modified polyethylene powder to obtain a plastic-impregnated piece; the invention has no special requirements on the specific implementation process of the impregnation, and the impregnated substrate is vibrated after the impregnation so as to remove the residual powder.
After a plastic dipping part is obtained, the plastic dipping part is solidified to form a modified polyethylene coating on the surface of a substrate; in the invention, the curing is preferably carried out in a curing chamber, the curing temperature is preferably 130-200 ℃, and the curing time is preferably 10-15 min.
In the invention, the thickness of the modified polyethylene coating is preferably less than or equal to 1.5mm, and more preferably 400-600 μm.
When the modified polyethylene powder coating is used for preparing a coating on the surface of a substrate, the traditional phosphating procedure can be omitted, the process flow is shortened, and the process flow is simplified.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 70kg of linear low density polyethylene (with the brand number of DFDA7042), 10kg of metallocene linear polyethylene (with the brand number of QX5983), 13kg of maleic anhydride grafted high density polyethylene, 7kg of ethylene-octene copolymer, 2.5kg of color masterbatch (Dinghai plastic chemical Co., Ltd., Toguan city, the product model of Dinghai 81030), 0.16kg of antioxidant (Beijing addition agent institute, the product model of antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition agent institute, the product model of GW-944), 0.2kg of oleamide, pouring into a stirrer, stirring for 15min, and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Example 2
Weighing 70kg of linear low density polyethylene (with the brand number of DFDA7042), 10kg of metallocene linear polyethylene (with the brand number of QX5983), 13kg of maleic anhydride grafted high density polyethylene, 3.5kg of ethylene-octene copolymer, 3.5g of ethylene-vinyl acetate copolymer, 2.5kg of color masterbatch (Dinghai plastic chemical Co., Ltd., Toguan city, product model number of Dinghai 81030), 0.16kg of antioxidant (Beijing addition agent institute, product model number of antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition agent institute, product model number of GW-944), 0.2kg of oleamide and pouring into a stirrer, stirring for 15min and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Example 3
Weighing 65kg of linear low-density polyethylene (with the brand number of DFDA7042), 8kg of metallocene linear polyethylene (with the brand number of QX5983), 15kg of maleic anhydride grafted high-density polyethylene, 5kg of polyester elastomer, 2.5kg of color master (Dinghai plastic chemical Co., Ltd., Toguan City, the product model of Dinghai 81030), 0.16kg of antioxidant (Peking addition auxiliary research institute, the product model of antioxidant PKB-225), 0.2kg of light stabilizer (Peking addition auxiliary research institute, the product model of GW-944), and 0.2kg of oleamide, pouring into a stirrer, stirring for 15min, and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Example 4
Weighing 65kg of linear low density polyethylene (with the brand numbers of TJZS-2650 and LLDPE3224, the mass ratio of the two is 1: 1), 10kg of metallocene linear polyethylene (with the brand number of BPD3801), 15kg of maleic anhydride grafted high density polyethylene, 10kg of acrylate elastomer, 2.5kg of color masterbatch (Dinghai plastic chemical Co., Ltd., product model number of Dinghai 81030), 0.16kg of antioxidant (Beijing addition agent institute, product model number of antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition agent institute, product model number of GW-944), 0.2kg of oleamide and pouring into a stirrer, stirring for 15min and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Example 5
Weighing 65kg of linear low density polyethylene (with the brands of M1840 and YLF-1802, the mass ratio of the two is 1: 1), 10kg of metallocene linear polyethylene (with the brands of BPD3801), 15kg of maleic anhydride grafted high density polyethylene, 10kg of ethylene-vinyl acetate copolymer, 2.5kg of color master batch (Dinghai plastic chemical Co., Ltd., Toguan city, product model of Dinghai 81030), 0.16kg of antioxidant (Beijing addition agent institute, product model of antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition agent institute, product model of GW-944), 0.2kg of oleamide and pouring into a stirrer, stirring for 15min and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Comparative example 1
Weighing 85kg of linear low-density polyethylene (with the brand number of DFDA7042), 8kg of metallocene linear polyethylene (with the brand number of QX5983), 15kg of maleic anhydride grafted high-density polyethylene, 2.5kg of color master (Dinghai plastic chemical Co., Ltd., Toguan City, the product model of Dinghai 81030), 0.16kg of antioxidant (Peking addition agent institute, the product model of antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition agent institute, the product model of GW-944), 0.2kg of oleamide and pouring into a stirrer, stirring for 15min and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Comparative example 2
Weighing 70kg of linear low density polyethylene (with the brand number of DFDA7042), 23kg of metallocene linear polyethylene (with the brand number of QX5983), 7kg of ethylene-octene copolymer, 2.5kg of color masterbatch (Dinghai plastic chemical Co., Ltd., Dongguan city, the product model of Dinghai 81030), 0.16kg of antioxidant (Peking addition auxiliary research institute, the product model of antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition auxiliary research institute, the product model of GW-944), and 0.2kg of oleamide, pouring into a stirrer, stirring for 15min, and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Comparative example 3
Weighing 80kg of linear low density polyethylene (with the brand number of DFDA7042), 13kg of maleic anhydride grafted high density polyethylene, 7kg of ethylene-vinyl acetate copolymer, 2.5kg of color master (manufactured by Dinghai plastic chemical Co., Ltd., Dongguan city, the product model of Dinghai 81030), 0.16kg of antioxidant (manufactured by Beijing addition agent research institute, the product model of antioxidant PKB-225), 0.2kg of light stabilizer (manufactured by Beijing addition agent research institute, the product model of GW-944), 0.2kg of oleamide, pouring into a stirrer, stirring for 15min, and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Comparative example 4
Weighing 70kg of linear low density polyethylene (with the brand number of DFDA7042), 10kg of metallocene linear polyethylene (with the brand number of QX5983), 35kg of maleic anhydride grafted high density polyethylene, 7kg of ethylene-vinyl acetate copolymer, 2.5kg of color masterbatch (Dinghai plastic chemical Co., Ltd., Toguan city, the product model of Dinghai 81030), 0.16kg of antioxidant (Beijing addition agent institute, the product model of antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition agent institute, the product model of GW-944), 0.2kg of oleamide and pouring into a stirrer, stirring for 15min and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Comparative example 5
Weighing 70kg of linear low density polyethylene (with the brand number of DFDA7042), 10kg of metallocene linear polyethylene (with the brand number of QX5983), 8kg of maleic anhydride grafted high density polyethylene, 7kg of ethylene-vinyl acetate copolymer, 2.5kg of color masterbatch (Dinghai plastic chemical Co., Ltd., Toguan city, the product model of Dinghai 81030), 0.16kg of antioxidant (Beijing addition agent institute, the product model of antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition agent institute, the product model of GW-944), 0.2kg of oleamide and pouring into a stirrer, stirring for 15min and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Comparative example 6
Weighing 70kg of linear low density polyethylene (with the brand number of DFDA7042), 10kg of metallocene linear polyethylene (with the brand number of QX5983), 13kg of maleic anhydride grafted high density polyethylene, 2kg of ethylene-octene copolymer, 2.5kg of color masterbatch (Dinghai plastic chemical Co., Ltd., Toguan city, the product model of Dinghai 81030), 0.16kg of antioxidant (Beijing addition agent institute, the product model of antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition agent institute, the product model of GW-944), 0.2kg of oleamide, pouring into a stirrer, stirring for 15min, and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Comparative example 7
Weighing 70kg of linear low density polyethylene (with the brand number of DFDA7042), 10kg of metallocene linear polyethylene (with the brand number of QX5983), 13kg of maleic anhydride grafted high density polyethylene, 20kg of ethylene-octene copolymer, 2.5kg of color masterbatch (Dinghai plastic chemical Co., Ltd., Toguan city, the product model of Dinghai 81030), 0.16kg of antioxidant (Beijing addition agent institute, the product model of antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition agent institute, the product model of GW-944), 0.2kg of oleamide, pouring into a stirrer, stirring for 15min, and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Comparative example 8
Weighing 70kg of maleic anhydride grafted linear low-density polyethylene, 10kg of metallocene linear polyethylene (the trade name is QX5983), 13kg of high-density polyethylene, 7kg of ethylene-octene copolymer, 2.5kg of color master (Dinghai plastic chemical Co., Ltd., Toguan, product model is Dinghai 81030), 0.16kg of antioxidant (Beijing addition agent institute, product model is antioxidant PKB-225), 0.2kg of light stabilizer (Beijing addition agent institute, product model is GW-944), 0.2kg of oleamide and pouring into a stirrer, stirring for 15min and uniformly mixing;
pouring the mixed master batch into a hopper of a single-screw extruder, extruding and granulating by using the single-screw extruder to obtain modified polyethylene; wherein the temperature setting parameters of the single screw extruder are as follows: 130 ℃; and a second stage: 130 ℃; a third stage: 140 ℃; fourth to seventh stages: 130-140 ℃; an eighth stage: 135 ℃ is adopted.
Application example 1
The polyethylenes prepared in examples 1 to 3 and comparative examples 1 to 7 were respectively ground into modified polyethylene powders by a pulverizer as powder coatings.
And (2) sequentially washing and drying the hot-dip galvanized metal substrate, preheating for 15min at 150 ℃ to obtain preheating pieces, respectively soaking the preheating pieces in the powder coating, vibrating to remove residual powder, putting the plastic-dipped pieces into a curing chamber, curing for 10min at 130 ℃, and forming a modified polyethylene coating (with the thickness of 400-600 mu m) on the surface of the hot-dip galvanized metal substrate.
Test example 1
Carrying out tensile property test on the modified polyethylene coating prepared in the example 1 according to a GB/T1040 plastic tensile property test method; carrying out adhesion test on the modified polyethylene coating prepared in the example 1 according to a GB/T9286-88 plastic adhesion performance test method; the test results are shown in table 1, and compared with comparative examples 1-7, the tensile strength of the coating formed on the surface of the hot-dip galvanized metal substrate by using the modified polyethylene provided by the invention as the powder coating is 13.3-13.8 MPa, and the adhesive force is 0 grade or 1 grade, so that the modified polyethylene has excellent tensile strength and adhesive force.
TABLE 1 results of performance test of powder coatings obtained in examples 1 to 3 and comparative examples 1 to 7
| Serial number | Tensile Strength (MPa) | Adhesion force |
| Example 1 | 13.5 | Level 0 |
| Example 2 | 13.3 | Level 0 |
| Example 3 | 13.8 | Level 1 |
| Example 4 | 13.3 | Level 0 |
| Example 5 | 13.7 | Level 0 |
| Comparative example 1 | 12.2 | Grade 3 |
| Comparative example 2 | 13.1 | 4 stage |
| Comparative example 3 | 12.1 | Level 0 |
| Comparative example 4 | 12.6 | Level 0 |
| Comparative example 5 | 13.2 | 4 stage |
| Comparative example 6 | 13.2 | 4 stage |
| Comparative example 7 | 12.5 | Level 0 |
| Comparative example 8 | 11.7 | Level 1 |
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. The modified polyethylene is characterized by comprising the following components in parts by mass:
2. the modified polyethylene of claim 1, wherein the linear low density polyethylene is available under the trade designation DFDA7042, TJZS-2650, LLDPE3224, DNDA8320, M1840, M2320, YLF-1802, and LLO220 KJ.
3. The modified polyethylene of claim 1 wherein the metallocene linear polyethylene is of the brand name QX5983, Sp1071C, 5815, BPD3801, Sp2040 and M3581 UV.
4. The modified polyethylene of claim 1, wherein the thermoplastic elastomer is one or more of a polyester elastomer, a polyolefin elastomer, an acrylate elastomer, and an ethylene-vinyl acetate copolymer elastomer.
5. The modified polyethylene of claim 1 wherein the additives comprise antioxidants, light stabilizers and lubricants.
6. The modified polyethylene of claim 5, wherein the mass ratio of the antioxidant to the light stabilizer to the lubricant is 1 (1-2) to (1-2).
7. A method for preparing a modified polyethylene according to any one of claims 1 to 6, comprising the steps of:
mixing, melt extruding and granulating linear low-density polyethylene, metallocene linear polyethylene, maleic anhydride grafted high-density polyethylene, thermoplastic elastomer, color master batch and additive to obtain the modified polyethylene.
8. The method for preparing according to claim 7, wherein the extrusion is carried out in a single screw extruder whose body is divided into eight sections;
the temperature of the first section is 110-140 ℃, the temperature of the second section is 120-150 ℃, the temperature of the third section is 130-160 ℃, the temperature of the fourth-seventh sections is 120-160 ℃ independently, and the temperature of the eighth section is 120-150 ℃.
9. The preparation method according to claim 7, wherein the mixing time is 10-15 min, the mixing is performed under stirring conditions, and the rotation speed of the stirring is 40-60 r/min.
10. Use of the modified polyethylene according to any one of claims 1 to 6 or the modified polyethylene obtained by the production method according to any one of claims 7 to 9 as a powder coating.
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