CN116948075A - Bimodal polyethylene resin of large-caliber thick-wall low-melting-drop pipe with flame retardant property and preparation method thereof - Google Patents
Bimodal polyethylene resin of large-caliber thick-wall low-melting-drop pipe with flame retardant property and preparation method thereof Download PDFInfo
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- 230000002902 bimodal effect Effects 0.000 title claims abstract description 35
- 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 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000000155 melt Substances 0.000 claims abstract description 12
- 238000007665 sagging Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 29
- 239000004698 Polyethylene Substances 0.000 claims description 23
- -1 polyethylene Polymers 0.000 claims description 23
- 229920000573 polyethylene Polymers 0.000 claims description 23
- 239000004611 light stabiliser Substances 0.000 claims description 21
- 239000003963 antioxidant agent Substances 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 239000006097 ultraviolet radiation absorber 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 15
- 239000004711 α-olefin Substances 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 14
- 229920001903 high density polyethylene Polymers 0.000 claims description 14
- 239000004700 high-density polyethylene Substances 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 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
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 238000012545 processing Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002216 antistatic agent Substances 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
- 238000002485 combustion reaction Methods 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
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 1
- 238000005243 fluidization Methods 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
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application provides a bimodal polyethylene resin of a large-caliber thick-wall low-melting-drop pipe with flame retardance 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 2:8-8:2; the number average molecular weight Mn is 1500-10000, the weight average molecular weight Mw is 150000-450000, the Mw/Mn is 15-300, the melt flow rate MFRs is 0.1-1.5g/10min, the resin density is 0.935-0.955 g/cm3, and the flame retardant property is above V2. The bimodal polyethylene resin provided by the application can be prepared by a reactor formed by connecting a loop reactor and a fluidized bed reactor in series. The bimodal polyethylene resin has good flame retardant 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 flame retardant 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 flame retardant property and a preparation method thereof.
Background
Pipes of polymeric material are often used for a variety of applications, with some applications meeting specific requirements, must be self-extinguishing and the combustion products must not be toxic in addition to the physical and mechanical properties of the typical plastic pipes. The polyolefin material is inflammable, has larger potential safety hazard, has flame retardance by adding the flame retardant, and eliminates the potential safety hazard.
Disclosure of Invention
The application aims to provide a bimodal polyethylene resin with flame retardant 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 large-caliber anti-sagging pipes with flame retardance.
The technical scheme of the application is as follows:
the application provides a bimodal polyethylene resin of a large-caliber thick-wall low-melting-drop pipe with flame retardant property, 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 2:8-8:2; the number average molecular weight Mn is 1500-10000, the weight average molecular weight Mw is 150000-450000, the Mw/Mn is 15-300, the melt flow rate MFRs is 0.1-1.5g/10min, the resin density is 0.935-0.955 g/cm3, and the flame retardant performance is above V2.
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 2000-8000, the weight average molecular weight Mw is 240000-320000, and the Mw/Mn is 30-160; the melt flow rate MFRs is 0.2-1.0 g/10min; the density of the resin is 0.940-0.952 g/cm3, and the flame retardant property is above V1.
Further, the resin comprises the following raw materials in parts by weight:
100 parts of high-density polyethylene powder, 5-30 parts of flame retardant, 0.03-3 parts of light stabilizer, 0.03-3 parts of ultraviolet absorber, 0.03-2 parts of antioxidant and 1-20 parts of carbon black master batch;
wherein, the MFR of the high-density polyethylene powder is 0.1-1.5g/10min, the alpha olefin mass content is 0.1-10%, and the molecular weight distribution is 3-500.
Further, the resin comprises the following raw materials in parts by weight:
100 parts of high-density polyethylene powder, 10-20 parts of flame retardant, 0.04-1 part of light stabilizer, 0.04-1 part of ultraviolet absorber, 0.04-1 part of antioxidant and 5-10 parts of carbon black master batch;
wherein the MFR of the high-density polyethylene is 0.2-1.0, the alpha olefin mass content is 0.5-5%, and the molecular weight distribution is 10-200.
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. The MFR is measured at 190℃by different loads and is expressed in g/l0 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. The density of the resin is 0.945 to 0.960g/cm due to the strength 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 more than 0.450N when the bimodal polyethylene resin breaks.
A further important property of the resins of the application is the flame retardancy of bimodal polyethylene. The vertical flame retardant property test was performed according to the UL-94 standard, and the sample size was 127 mm. Times.12 mm. Times.3.2 mm; the flame retardant level is gradually increased from HB, V-2, V-1 to V-0; HB: the lowest flame retardant rating in the UL94 standard. It is required that for samples 3 to 13 mm thick, the burn rate is less than 40 mm per minute; a sample less than 3 mm thick, a burn rate of less than 70 mm per minute; or extinguished before the 100 mm mark. V-2: after two 10 second burn tests on the samples, the flame extinguished within 60 seconds. The cotton wool below 30cm can be ignited. V-1: after two 10 second burn tests on the samples, the flame extinguished within 60 seconds. The cotton wool below 30cm cannot be ignited. V-0: after two 10 second burn tests on the samples, the flame extinguished within 10 seconds.
The application also provides a preparation method of the bimodal polyethylene resin of the large-caliber thick-wall low-melting-drop pipe with the flame retardant 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 30:70 and 70:30;
step (2): granulating the polyethylene powder prepared in the step (1) by adopting a double-screw extruder, and stably and continuously adding a flame retardant, an antioxidant, a light stabilizer, an ultraviolet absorbent 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 flame retardant property.
Further, the molar ratio of ethylene to hydrogen in the step (1) is 15-35mol/Kmol; the comonomer is alpha olefin, and the molar ratio of the comonomer to the ethylene is 50-125mol/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 13000 to 15000. 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 flame retardant in the step (2) is zinc borate flame retardant, preferably 4ZnO.B 2 O 3 ·H 2 O is added in an amount of 5 to 30% by weight, preferably 10 to 20% by weight, based on the total mass of the polyethylene powder.
Further, the light stabilizer in the step (2) is a hindered amine light stabilizer 2020, and the addition amount thereof is 0.03 to 3%, preferably 0.04 to 1% 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 0.03-3%, preferably 0.04-1% 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 0.03-2%, preferably 0.04-1% 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 20% by weight, preferably 5 to 10% by weight, based on 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 antistatic performance, improved mechanical property, excellent processing performance and excellent strength, and is particularly suitable for manufacturing flame-retardant large-caliber thick-wall low-sagging pipe materials.
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 flame retardant used in examples 1-6 is a zinc borate flame retardant, preferably 4ZnO.B2O3.H2O (HT-207, jinan Hongtail New Material Co., ltd.); 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 (alpha olefin) 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, and regulating the yield of the two reactors to regulate the ratio of the high molecular weight part to the low molecular weight part, wherein a device reaction flow chart is shown in figure 1;
and (2) granulating the polyethylene powder obtained in the step (1) by adopting a double-screw extruder, and stably and continuously adding an antistatic agent, an antioxidant, a light stabilizer, an ultraviolet absorbent 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:0.28, alpha olefin mass content 0.9 and molecular weight distribution 119.89), 10 parts of flame retardant, 0.06 part of light stabilizer 2020,0.2 parts of ultraviolet absorber UV328, 0.3 part of antioxidant 1010 and antioxidant 168,6 parts of 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 from the step 1, MFR:0.26, alpha olefin mass content 0.6 and molecular weight distribution 25.34), 12 parts of flame retardant, 0.06 part of light stabilizer 2020,0.2 parts of ultraviolet absorber UV328, 0.3 part of antioxidant 1010 and 168,6 parts of antioxidant 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 from the step 1, MFR:0.24, alpha olefin mass content 0.9 and molecular weight distribution 51.26), 14 parts of flame retardant, 0.06 part of light stabilizer 2020,0.2 parts of ultraviolet absorber UV328, 0.3 part of antioxidant 1010 and 168,6 parts of antioxidant 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:0.19, alpha olefin mass content of 3.5 and molecular weight distribution 188.46), 16 parts of flame retardant, 0.06 part of light stabilizer 2020,0.2 parts of ultraviolet absorber UV328, 0.3 part of antioxidant 1010 and antioxidant 168,6 parts of carbon black master batch in a weight ratio of 2:1.
Example 5
The bimodal polyethylene resin powder comprises 100 parts by weight of high-density polyethylene (prepared from the step 1, MFR:0.50, alpha olefin mass content 0.5 and molecular weight distribution 149.88), 18 parts of flame retardant, 0.06 part of light stabilizer 2020,0.2 parts of ultraviolet absorber UV328, 0.3 part of antioxidant 1010 and antioxidant 168,6 parts of carbon black master batch in a weight ratio of 2:1.
Example 6
The bimodal polyethylene resin powder comprises 100 parts by weight of high-density polyethylene (prepared from the step 1, MFR:0.90, alpha olefin mass content 2 and molecular weight distribution 11.24), 20 parts of flame retardant, 0.06 part of light stabilizer 2020,0.2 parts of ultraviolet absorber UV328, 0.3 part of antioxidant 1010 and 168,6 parts of antioxidant 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 test results for examples 1-6
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 had flame retardant properties above V2 and had good flame retardancy.
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 (14)
1. A bimodal polyethylene resin with flame retardant 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 2:8-8:2; the number average molecular weight Mn is 1500-10000, the weight average molecular weight Mw is 150000-450000, the Mw/Mn is 15-300, the melt flow rate MFRs is 0.1-1.5g/10min, the resin density is 0.935-0.955 g/cm3, and the flame retardant property is above V2.
2. The bimodal polyethylene resin with flame retardant properties for large caliber thick wall low melt drop tubing 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 2000-8000, the weight average molecular weight Mw is 240000-320000, and the Mw/Mn is 30-160; the melt flow rate MFRs is 0.2-1.0 g/10min; the density of the resin is 0.940-0.952 g/cm 3’ The flame retardant property can reach more than V1.
3. The bimodal polyethylene resin with flame retardant properties for large caliber thick wall low melt drop tubing of claim 1, wherein: the resin comprises the following raw materials in parts by weight:
100 parts of high-density polyethylene powder, 5-30 parts of flame retardant, 0.03-3 parts of light stabilizer, 0.03-3 parts of ultraviolet absorber, 0.03-2 parts of antioxidant and 1-20 parts of carbon black master batch;
wherein, the MFR of the high-density polyethylene powder is 0.1-1.5g/10min, the alpha olefin mass content is 0.1-10%, and the molecular weight distribution is 15-300.
4. The bimodal polyethylene resin with flame retardant properties for large caliber thick wall low melt drop tubing of claim 1, wherein: the resin comprises the following raw materials in parts by weight:
100 parts of high-density polyethylene powder, 10-20 parts of flame retardant, 0.04-1 part of light stabilizer, 0.04-1.5 parts of ultraviolet absorber, 0.04-1.0 part of antioxidant and 5-10 parts of carbon black master batch;
wherein the high density polyethylene has an MFR of 0.2-1.0, an alpha olefin mass content of 0.5-5% and a molecular weight distribution of 30-160.
5. The method for preparing the bimodal polyethylene resin of the large-caliber thick-wall low-sagging pipe with flame retardant property according to any one of claims 1 to 4, comprising 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 20:80 and 80:20;
step (2): granulating the polyethylene powder prepared in the step (1) by adopting a double-screw extruder, and stably and continuously adding a flame retardant, an antioxidant, a light stabilizer, an ultraviolet absorbent 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 flame retardant property.
6. The method of manufacturing according to claim 5, wherein: the mol ratio of ethylene to hydrogen in the step (1) is 15-35mol/Kmol; the comonomer is alpha olefin, and the molar ratio of the comonomer to the ethylene is 50-125mol/Kmol.
7. The method of manufacturing according to claim 6, wherein: the alpha 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 13000-15000.
9. The method of manufacturing according to claim 5, wherein: the flame retardant in the step (2) is zinc borate, and the addition amount of the flame retardant is 5-30% of the total mass of the polyethylene powder.
10. 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 0.03-3% of the total mass of the polyethylene powder.
11. 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 0.03-3% of the total mass of the polyethylene powder.
12. 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 0.03-2% of the total mass of the polyethylene powder.
13. 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.
14. The method of manufacturing according to claim 5, wherein: the addition amount of the carbon black master batch in the step (2) is 1-20% of the total mass of the polyethylene powder.
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| CN202210401614.5A CN116948075A (en) | 2022-04-15 | 2022-04-15 | Bimodal polyethylene resin of large-caliber thick-wall low-melting-drop pipe with flame retardant property and preparation method thereof |
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| CN202210401614.5A CN116948075A (en) | 2022-04-15 | 2022-04-15 | Bimodal polyethylene resin of large-caliber thick-wall low-melting-drop pipe with flame retardant property and preparation method thereof |
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