CN116948294A - Bimodal polyethylene resin of large-caliber thick-wall low-melting-drop pipe with antibacterial property and preparation method thereof - Google Patents
Bimodal polyethylene resin of large-caliber thick-wall low-melting-drop pipe with antibacterial property and preparation method thereof Download PDFInfo
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- 230000002902 bimodal effect Effects 0.000 title claims abstract description 35
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 29
- 229920013716 polyethylene resin Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000000155 melt Substances 0.000 claims abstract description 12
- 241000191967 Staphylococcus aureus Species 0.000 claims abstract description 10
- 238000007665 sagging Methods 0.000 claims abstract description 10
- 241000588724 Escherichia coli Species 0.000 claims abstract description 9
- 230000001954 sterilising effect Effects 0.000 claims abstract description 9
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010931 gold Substances 0.000 claims abstract description 6
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 30
- -1 polyethylene Polymers 0.000 claims description 27
- 239000004698 Polyethylene Substances 0.000 claims description 24
- 229920000573 polyethylene Polymers 0.000 claims description 24
- 239000004611 light stabiliser Substances 0.000 claims description 22
- 239000003242 anti bacterial agent Substances 0.000 claims description 20
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 229920001903 high density polyethylene Polymers 0.000 claims description 17
- 239000004700 high-density polyethylene Substances 0.000 claims description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 16
- 239000006229 carbon black Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 16
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 14
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 claims description 11
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000004711 α-olefin Substances 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims description 6
- 239000002685 polymerization catalyst Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 241000222122 Candida albicans Species 0.000 description 3
- 229940095731 candida albicans Drugs 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- YXHRTMJUSBVGMX-UHFFFAOYSA-N 4-n-butyl-2-n,4-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2-n-[6-[(2,2,6,6-tetramethylpiperidin-4-yl)amino]hexyl]-1,3,5-triazine-2,4-diamine Chemical compound N=1C=NC(N(CCCCCCNC2CC(C)(C)NC(C)(C)C2)C2CC(C)(C)NC(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)NC(C)(C)C1 YXHRTMJUSBVGMX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides a bimodal polyethylene resin of a large-caliber thick-wall low-melting-drop pipe with antibacterial property and a preparation method thereof. The resin comprises a high molecular weight part and a low molecular weight part, wherein the mass ratio of the low molecular weight part to the high molecular weight part is 2.5:7.5-7.5:2.5; the number average molecular weight Mn is 1000-20000, the weight average molecular weight Mw is 100000-400000, the Mw/Mn is 5-400, the melt flow rate MFRs is 0.1-0.5g/10min, the resin density is 0.930-0.960 g/cm 3 The sterilization rate of the composition to escherichia coli gold and staphylococcus aureus is more than 99 percent. The bimodal polyethylene resin provided by the application has good antibacterial property, improved mechanical property, excellent processing property, excellent strength and anti-sagging property, and is suitable for preparing large-caliber thick-wall low-sagging pipe with antibacterial property.
Description
Technical Field
The application relates to the technical field of polymer pipes, in particular to a bimodal polyethylene pipe resin of a large-caliber thick-wall low-melting-drop pipe with antibacterial performance and a preparation method thereof.
Background
Along with the improvement of the living standard of people, people increasingly pursue comfort of living environment and increasingly pay attention to sanitation management, the antibacterial property of materials has higher requirements, the antibacterial property of the materials plays an important role in creating clean and healthy environment, the development and application of antibacterial plastics play a green barrier for protecting human health trees, the high-density polyethylene (HDPE) pipe has very important significance for improving the living environment of people, reducing the occurrence rate of diseases and protecting the health of people, and the HDPE pipe is used as an important tool for drinking water transportation and has stricter requirements for inhibiting the growth of algae, bacteria or fungi.
Disclosure of Invention
The application aims to provide a bimodal polyethylene resin with antibacterial property for a large-caliber thick-wall low-sagging pipe and a preparation method thereof. The bimodal polyethylene composition prepared by the preparation method has improved mechanical properties, excellent processability, excellent strength and anti-sagging property, is suitable for manufacturing ideal pressure pipes, and is particularly suitable for manufacturing antibacterial large-caliber anti-sagging pipes.
The technical scheme of the application is as follows:
the application provides a bimodal polyethylene resin of a large-caliber thick-wall low-sagging pipe with antibacterial performance, which comprises a high molecular weight part and a low molecular weight part, wherein the mass ratio of the low molecular weight part to the high molecular weight part is 2.5:7.5-7.5:2.5; the number average molecular weight Mn is 1000-20000, the weight average molecular weight Mw is 100000-400000, the Mw/Mn is 5-400, the melt flow rate MFRs is 0.1-0.5g/10min, the resin density is 0.930-0.960 g/cm < 3 >, and the sterilization rate to escherichia coli gold and staphylococcus aureus can reach more than 99%;
further, the mass ratio of the low molecular weight part to the high molecular weight part of the resin is 3:7-7:3; the number average molecular weight Mn is 2000-10000, the weight average molecular weight Mw is 160000-360000, and the Mw/Mn is 16-180; the melt flow rate MFRs is 0.2-0.4 g/10min; the density of the resin is 0.935-0.955 g/cm < 3 >, and the sterilization rate of the resin to escherichia coli gold and staphylococcus aureus can reach more than 99%.
Further, the resin comprises the following raw materials in parts by weight:
100 parts of high-density polyethylene powder, 2-30 parts of high-performance antibacterial agent, 0.01-3 parts of light stabilizer, 0.01-3 parts of ultraviolet absorber, 0.01-3 parts of antioxidant and 1-15 parts of carbon black master batch;
wherein the high density polyethylene has an MFR of 0.1 to 0.5, an olefin of 1-hexene, a mass content of 0.1 to 10, and a molecular weight distribution of 5 to 400.
Further, the resin comprises the following raw materials in parts by weight:
100 parts of high-density polyethylene powder, 5-20 parts of high-performance antibacterial agent, 0.03-0.8 part of light stabilizer, 0.03-1 part of ultraviolet absorber, 0.05-1 part of antioxidant and 2-8 parts of carbon black master batch;
wherein the MFR of the high-density polyethylene is 0.2-0.4, the olefin is 1-hexene, the mass content is 0.5-5, and the molecular weight distribution is 16-180.
In the present application, it is important to properly select the ratio of the low molecular weight fraction and the high molecular weight fraction (also referred to as "partition" between the fractions). If the proportion of the high molecular weight fraction is increased, this results in too low a strength, and if it is too small, this results in undesirable gel formation. The term "Mw/Mn" as used herein refers to the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), which is used to define the breadth of the molecular weight distribution of the polyethylene. "melt flow Rate" (MFR) is an important characterization of bimodal polyethylene for use in the production of pipes. MFR characterizes the flowability of a polymer and, therefore, its processability. The greater the MFR, the less the viscosity of the polymer. MFR is measured at 190℃by different loads and is expressed in g/I0 min. Where the load is indicated as subscript, for example, MFRo is measured at 190℃under a load of 2.16kg in accordance with ISO 1133, and MFRs is measured at 190℃under a load of 5kg in accordance with ISO 1133.
Another important property of the present application is the density of the bimodal polyethylene. For reasons of strength, the density of the resin is 0.930-0.960 g/cm 3 In the high density range, the density measurement is performed according to ISO 1183.
The melt strength is usually expressed by melt tension, which determines the processing characteristics of the material when the pipe is formed, and the high melt tension indicates that the melt has good elongation resistance and sagging resistance, and the melt tension test conditions are as follows: the Rheotens 97 type melt strength tester of GOTTFERT company in Germany is adopted, the die diameter is 2mm, the die temperature is 190 ℃, the gap between the stretching wheels is 0.4mm, and the stretching acceleration is 20mm/s 2 The melt tension at break is characterized as the melt strength. The melt tension of the bimodal polyethylene resin provided by the application reaches 0.4 when the bimodal polyethylene resin breaks50N or more.
A further important property of the resins of the present application is the antimicrobial properties of bimodal polyethylene. Antibacterial properties against E.coli, staphylococcus aureus, and Candida albicans; test was performed according to test method 1 film method of standard GB/T21510-2008, and bacteria for detection: coli ATYCC 25922; staphylococcus aureus ATCC 6538; 5 samples were tested in parallel for each example and comparative example, and the average was taken. Test was performed according to test method 1 film-sticking method of standard GB21551.2-2010, and bacteria for detection: candida albicans ATCC 10231 (Candida albicans); 5 samples were tested in parallel for each example and comparative example, and the average was taken.
The application also provides a preparation method of the bimodal polyethylene resin of the large-caliber thick-wall low-melting-drop pipe with the antibacterial property, which comprises the following steps:
step (1): polymerizing ethylene, hydrogen and comonomer in the presence of a polymerization catalyst by a series reactor method to prepare polyethylene powder; the series reactor consists of a loop reactor and a fluidized bed reactor, wherein a low molecular weight part is obtained by polymerization in the loop reactor, a high molecular weight part is obtained by polymerization in the fluidized bed reactor, and the yield of the two reactors is regulated to regulate the ratio of the high molecular weight part to the low molecular weight part; wherein the ratio of the loop reactor yield to the fluidized bed reactor yield is controlled between 25:75 and 75:25;
step (2): granulating the polyethylene powder prepared in the step (1) by adopting a double-screw extruder, and stably and continuously adding an antibacterial agent, an antioxidant, a light stabilizer, an ultraviolet absorber and a carbon black master batch in the granulating process, wherein the temperature is controlled between 170 ℃ and 260 ℃, so as to prepare the bimodal polyethylene resin of the large-caliber thick-wall low-melting-drop pipe with antibacterial performance.
Further, the molar ratio of ethylene to hydrogen in the step (1) is 8-60mol/Kmol; the comonomer is 1-hexene, and the molar ratio of the comonomer to the ethylene is 25-125mol/Kmol.
Further, the alpha olefin is 1-hexene.
Further, the polymerization catalyst in the step (1) is a Ziegler-Natta catalyst (commercially available) having an activity of 10000 to 20000. The catalyst has moderate activity, can distribute the yield in two reactors, and has excellent hydrogen regulation performance; has good particle morphology to ensure that primary particles formed by supercritical polymerization of the first loop can have good fluidization conditions in the subsequent gas-phase fluidized bed.
Further, the antibacterial agent quaternary ammonium salt, quaternary phosphonium salt, bellirinate or alcohol antibacterial agent in the step (2); the addition amount is 2-30% of the total mass of the polyethylene powder, preferably 5-20%;
further, the antibacterial agent is a mixture of 4-vinylbenzyl tributyl chloride scale and benzyl tributyl chloride scale with the mass ratio of 1:4.
Further, the light stabilizer in the step (2) is a hindered amine light stabilizer 2020, and the addition amount thereof is 0.01 to 3%, preferably 0.03 to 0.8% of the total mass of the polyethylene powder. The light stabilizer is a polymer of the reaction product of N, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine, 2,4, 6-trichloro-1, 3, 5-triazine, N-butyl-1-butylamine, and N-butyl-2, 6-tetramethyl-4-piperidinamine.
Further, the ultraviolet absorber in the step (2) is an ultraviolet absorber UV328, and the addition amount thereof is 0.01-3%, preferably 0.03-0.1% of the total mass of the polyethylene powder. The ultraviolet absorber is 2- (2-hydroxy-3, 5-di-tert-pentylphenyl) benzotriazole.
Further, the antioxidant in the step (2) is a phenolic antioxidant, and the addition amount of the antioxidant is 0.01-3%, preferably 0.05-1% of the total mass of the polyethylene powder. Because the phenolic antioxidant, the ultraviolet absorber and the light stabilizer have good matching effect, the phenolic antioxidant is a novel antioxidant, has good water resistance, hot water extraction and chlorine water extraction, and improves the corrosiveness to seawater.
Further, the phenolic antioxidant is compounded by antioxidant 1010 and antioxidant 168 according to the mass ratio of 1:1-5:1. The antioxidant 1010 is 3- (3, 5-di-tert-butyl-4-hydroxycyclohexyl) propionate, and the antioxidant 168 is (2, 4-di-tert-butylphenol) phosphite.
Further, the carbon black master batch in the step (2) is added in an amount of 1 to 15%, preferably 2 to 8% of the total mass of the polyethylene powder.
The application has the beneficial effects that: the bimodal polyethylene composition has controllable distribution of high molecular weight part and low molecular weight part, reasonable molecular weight distribution, and can be used for manufacturing ideal pressure pipes with good antibacterial property, improved mechanical property, excellent processing property and excellent strength, and is particularly suitable for manufacturing antibacterial large-caliber thick-wall low-melting-drop pipes, and the sterilization rate of the antibacterial high-molecular-weight part and the antibacterial low-melting-drop pipes to escherichia coli gold and staphylococcus aureus can reach more than 99 percent.
Drawings
FIG. 1 is a schematic illustration of the reaction scheme for a bimodal polyethylene resin of the present application;
wherein, R301-prepolymerization reactor; r302-loop reactor; v304-flash vessel; r401-fluidized bed reactor.
Detailed Description
The present application will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present application, but are not intended to limit the application in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present application.
The starting materials used in the examples below are all commercially available. The antibacterial agent used in examples 1-6 was a mixture of 4-vinylbenzyl tributyl chloride and benzyl tributyl chloride scale (LSF-270, blue Peak auxiliary Co., fleenshan); antioxidant 1010 (AT 10, kidney chemical industry) and antioxidant 168 (AT 168, kidney chemical industry); light stabilizers (Chimassorb 2020, basf); ultraviolet absorbers (JYSORB UV328, very chemical-easy); carbon black master batch (GS 9790, suzhou Guojia)
In the following examples, the preparation method of the bimodal polyethylene resin comprises the following specific steps:
step (1), polymerizing ethylene, hydrogen and comonomer (1-hexene) in the presence of a polymerization catalyst by a series reactor method to prepare polyethylene powder, polymerizing in a loop reactor to obtain a low molecular weight part, polymerizing in a fluidized bed reactor to obtain a high molecular weight part, adjusting the yield of the two reactors to adjust the ratio of the high molecular weight part to the low molecular weight part, and a device reaction flow chart is shown in figure 1; light stabilizers
And (2) granulating the polyethylene powder obtained in the step (1) by adopting a double-screw extruder, and stably and continuously adding an antibacterial agent, an antioxidant, a light stabilizer, an ultraviolet absorber and a carbon black master batch in the granulating process, wherein the temperature is controlled at 170-260 ℃, so as to obtain the bimodal polyethylene resin for the pipe. Specific raw materials and proportions are shown in examples 1 to 6.
Example 1
The bimodal polyethylene resin powder comprises 100 parts by weight of high-density polyethylene (prepared from the step 1, MFR:0.30, alpha olefin mass content 0.9 and molecular weight distribution 119.25), 5 parts of an antibacterial agent LSF270,0.05 part of a light stabilizer 2020,0.1 part of an ultraviolet absorber UV328, and 0.2 part of an antioxidant 1010 and an antioxidant 168,5 part of a carbon black master batch in a weight ratio of 2:1.
Example 2
The bimodal polyethylene resin powder comprises 100 parts by weight of high-density polyethylene (prepared in step 1, MFR:0.27, alpha olefin mass content 0.6 and molecular weight distribution 24.29), 8 parts of an antibacterial agent LSF270,0.05 part of a light stabilizer 2020,0.1 parts of an ultraviolet absorber UV328, and 0.2 part of an antioxidant 1010 and an antioxidant 168,5 parts of a carbon black master batch in a weight ratio of 2:1.
Example 3
The bimodal polyethylene resin powder comprises 100 parts by weight of high-density polyethylene (prepared in step 1, MFR:0.23, alpha olefin mass content 0.9 and molecular weight distribution 48.64), 14 parts of an antibacterial agent LSF270,0.05 part of a light stabilizer 2020,0.1 parts of an ultraviolet absorber UV328, and 0.2 part of an antioxidant 1010 and an antioxidant 168,5 parts of a carbon black master batch in a weight ratio of 2:1.
Example 4
The bimodal polyethylene resin powder comprises 100 parts by weight of high-density polyethylene (prepared from the step 1, MFR:0.20, alpha olefin mass content of 3.5 and molecular weight distribution 188.66), 16 parts of an antibacterial agent LSF270,0.05 part of a light stabilizer 2020,0.05 parts of an ultraviolet absorber UV328, and 0.2 part of an antioxidant 1010 and an antioxidant 168,5 parts of a carbon black master batch in a weight ratio of 5:1.
Example 5
The bimodal polyethylene resin powder comprises 100 parts by weight of high-density polyethylene (prepared from the step 1, MFR:0.35, alpha olefin mass content 0.5 and molecular weight distribution 143.35), 18 parts of an antibacterial agent LSF270,1 part of a light stabilizer 2020,0.1 parts of an ultraviolet absorber UV328, and 0.05 part of an antioxidant 1010 and an antioxidant 168,5.5 parts of a carbon black master batch in a weight ratio of 1:1.
Example 6
The bimodal polyethylene resin powder comprises 100 parts by weight of high-density polyethylene (prepared from the step 1, MFR:0.40, alpha olefin mass content 2 and molecular weight distribution 11.22), 20 parts of an antibacterial agent LSF270,0.05 part of a light stabilizer 2020,0.07 part of an ultraviolet absorber UV328, and 0.2 part of an antioxidant 1010 and an antioxidant 168,6 part of a carbon black master batch in a weight ratio of 2:1.
The physical properties of the bimodal polyethylene resin powders obtained in examples 1 to 6 are shown in Table 1.
TABLE 1 results of physical Property test of examples 1 to 6
The results of the antibacterial property test of the bimodal polyethylene resin powders obtained in examples 1 to 6 are shown in Table 2.
TABLE 2 results of antibacterial property tests of examples 1 to 6
| Sample of | Sterilization rate/% (E.coli) | Sterilization rate/% (Staphylococcus aureus) |
| Example 1 | 63.2 | 62.3 |
| Example 2 | 65.5 | 64.3 |
| Example 3 | 86.3 | 84.2 |
| Example 4 | 95.5 | 94.2 |
| Example 5 | 99.9 | 99.9 |
| Example 6 | 99.9 | 99.9 |
The density, molecular weight distribution and melt flow rate of the six bimodal polyethylene resins are all in the designed range, so that the six bimodal polyethylene resins can be ensured to have excellent processing performance; the impact strength is also higher, so that the strength of the pipe is ensured; according to ISO4437:2007, SCG is greater than ISO4437, tested at 80 ℃,0.92 MPa: the long-term performance of the pipe can be met in 500 hours required by 2007 standard; the melt strength of the six examples is more than 0.450N, so that the sagging resistance of the material can be ensured, and the sagging phenomenon of the large-caliber thick-wall pipe in production can be reduced; examples 1 to 6 all have a certain antibacterial property, and especially examples 5 and 6 have a sterilizing rate of more than 99% against Escherichia coli and Staphylococcus aureus, and have a good antibacterial property.
While the preferred embodiments of the present application have been described in detail, the present application is not limited to the embodiments, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present application, and these equivalent modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (15)
1. A bimodal polyethylene resin with antibacterial property for large-caliber thick-wall low-sagging pipe comprises a high molecular weight part and a low molecular weight part, wherein the mass ratio of the low molecular weight part to the high molecular weight part is 2.5:7.5-7.5:2.5; the number average molecular weight Mn is 1000-20000, the weight average molecular weight Mw is 100000-400000, the Mw/Mn is 5-400, the melt flow rate MFRs is 0.1-0.5g/10min, the resin density is 0.930-0.960 g/cm 3 The sterilization rate of the composition to escherichia coli gold and staphylococcus aureus is more than 99 percent.
2. The bimodal polyethylene resin for large caliber thick wall low melt drop tubing having antibacterial properties of claim 1, wherein: the mass ratio of the low molecular weight part to the high molecular weight part of the resin is 3:7-7:3; the number average molecular weight Mn is 2000-10000, the weight average molecular weight Mw is 160000-360000, and the Mw/Mn is 16-180; the melt flow rate MFRs is 0.2-0.4 g/10min; the density of the resin is 0.935-0.955 g/cm 3 The sterilization rate of the composition to escherichia coli gold and staphylococcus aureus is more than 99 percent.
3. The bimodal polyethylene resin for large caliber thick wall low melt drop tubing having antibacterial properties of claim 1, wherein: the resin comprises the following raw materials in parts by weight:
100 parts of high-density polyethylene powder, 2-30 parts of high-performance antibacterial agent, 0.01-3 parts of light stabilizer, 0.01-3 parts of ultraviolet absorber, 0.01-3 parts of antioxidant and 1-15 parts of carbon black master batch;
wherein, the MFR of the high-density polyethylene powder is 0.1-0.5g/10min, the alpha olefin mass content is 0.1-10%, and the molecular weight distribution is 5-400.
4. The bimodal polyethylene resin for large caliber thick wall low melt drop tubing having antibacterial properties of claim 1, wherein: the resin comprises the following raw materials in parts by weight:
100 parts of high-density polyethylene powder, 5-20 parts of high-performance antibacterial agent, 0.03-0.8 part of light stabilizer, 0.03-1 part of ultraviolet absorber, 0.05-1 part of antioxidant and 2-8 parts of carbon black master batch;
wherein the MFR of the high-density polyethylene is 0.2-0.4, the alpha olefin is 1-hexene, the mass content is 0.5-5%, and the molecular weight distribution is 16-180.
5. The method for preparing a bimodal polyethylene resin for a large caliber thick wall low melt drop pipe having antibacterial property according to any one of claims 1 to 4, comprising the steps of:
step (1): polymerizing ethylene, hydrogen and comonomer in the presence of a polymerization catalyst by a series reactor method to prepare polyethylene powder; the series reactor consists of a loop reactor and a fluidized bed reactor, wherein a low molecular weight part is obtained by polymerization in the loop reactor, a high molecular weight part is obtained by polymerization in the fluidized bed reactor, and the yield of the two reactors is regulated to regulate the ratio of the high molecular weight part to the low molecular weight part; wherein the ratio of the loop reactor yield to the fluidized bed reactor yield is controlled between 25:75 and 75:25;
step (2): granulating the polyethylene powder prepared in the step (1) by adopting a double-screw extruder, and stably and continuously adding an antibacterial agent, an antioxidant, a light stabilizer, an ultraviolet absorber and a carbon black master batch in the granulating process, wherein the temperature is controlled between 170 ℃ and 260 ℃, so as to prepare the bimodal polyethylene resin of the large-caliber thick-wall low-melting-drop pipe with antibacterial performance.
6. The method of manufacturing according to claim 5, wherein: the mol ratio of ethylene to hydrogen in the step (1) is 8-60mol/Kmol; the comonomer is 1-hexene, and the molar ratio of the comonomer to the ethylene is 25-125mol/Kmol.
7. The method of manufacturing according to claim 6, wherein: the d olefin is 1-hexene.
8. The method of manufacturing according to claim 5, wherein: the polymerization catalyst in the step (1) is a Ziegler-Natta catalyst, and the activity of the catalyst is 10000-20000.
9. The method of manufacturing according to claim 5, wherein: the antibacterial agent quaternary ammonium salt, quaternary phosphonium salt, bellirine salt or alcohol antibacterial agent in the step (2); the addition amount of the polyethylene powder is 2-30% of the total mass of the polyethylene powder.
10. The method of manufacturing according to claim 9, wherein: the antibacterial agent is 4-vinylbenzyl tributyl scale chloride: the mass ratio of the benzyl tributyl chloride scale is 1:4.
11. The method of manufacturing according to claim 5, wherein: the light stabilizer in the step (2) is hindered amine light stabilizer 2020, and the addition amount of the light stabilizer is 0.01-3% of the total mass of the polyethylene powder.
12. The method of manufacturing according to claim 5, wherein: the ultraviolet absorber in the step (2) is ultraviolet absorber UV328, and the addition amount of the ultraviolet absorber UV328 is 0.01-3% of the total mass of the polyethylene powder.
13. The method of manufacturing according to claim 5, wherein: the antioxidant in the step (2) is a phenolic antioxidant, and the addition amount of the antioxidant is 0.01-3% of the total mass of the polyethylene powder.
14. The method of manufacturing according to claim 13, wherein: the phenolic antioxidant is compounded by antioxidant 1010 and antioxidant 168 according to the mass ratio of 1:1-5:1.
15. The method of manufacturing according to claim 5, wherein: the addition amount of the carbon black master batch in the step (2) is 1-15% of the total mass of the polyethylene powder.
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