WO2025055233A1 - Regenerated high-density polyethylene for marine fishing net and preparation method therefor - Google Patents
Regenerated high-density polyethylene for marine fishing net and preparation method therefor Download PDFInfo
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- WO2025055233A1 WO2025055233A1 PCT/CN2024/072464 CN2024072464W WO2025055233A1 WO 2025055233 A1 WO2025055233 A1 WO 2025055233A1 CN 2024072464 W CN2024072464 W CN 2024072464W WO 2025055233 A1 WO2025055233 A1 WO 2025055233A1
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- WIPO (PCT)
- Prior art keywords
- polyurethane elastomer
- density polyethylene
- terminal hydroxyl
- antioxidant
- polybutadiene
- Prior art date
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- 229920001903 high density polyethylene Polymers 0.000 title claims abstract description 68
- 239000004700 high-density polyethylene Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 140
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 124
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 124
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 67
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 66
- 239000000314 lubricant Substances 0.000 claims abstract description 24
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004698 Polyethylene Substances 0.000 claims abstract description 20
- 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 abstract description 20
- -1 polyethylene Polymers 0.000 claims abstract description 20
- 229920000573 polyethylene Polymers 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000012948 isocyanate Substances 0.000 claims abstract description 15
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 239000006229 carbon black Substances 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 120
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- 239000000178 monomer Substances 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 48
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 39
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 27
- 229920001451 polypropylene glycol Polymers 0.000 claims description 22
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 18
- 238000005292 vacuum distillation Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 238000013329 compounding Methods 0.000 claims description 11
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 11
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 10
- 239000008116 calcium stearate Substances 0.000 claims description 10
- 235000013539 calcium stearate Nutrition 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 abstract description 25
- 230000002787 reinforcement Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 230000003712 anti-aging effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 230000006698 induction Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930193351 phorone Natural products 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 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
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the invention relates to the technical field of high-density polyethylene, in particular to recycled high-density polyethylene for marine fishing nets and a preparation method thereof.
- HDPE recycled material is also called high-density polyethylene recycled material. It is made by recycling HDPE nozzle materials and HDPE products, and then washing, dehydrating, crushing, and granulating them in a granulator.
- high-density polyethylene recycled material is poor, and due to multiple processing, the aging performance of the material will also be affected, and it cannot meet our needs in actual use.
- This scheme discloses a recycled high-density polyethylene for marine fishing nets and a preparation method thereof to solve this technical problem.
- the object of the present invention is to provide a recycled high-density polyethylene for marine fishing nets and a preparation method thereof, so as to solve the problems raised in the above-mentioned background technology.
- the present invention provides the following technical solutions:
- the reaction produces a polyurethane elastomer A; when the alcohol monomer is a terminal hydroxyl polybutadiene with a molecular weight of 1600 to 1800, the reaction produces a polyurethane elastomer B; when the alcohol monomer is a terminal hydroxyl polybutadiene with a molecular weight of 2000 to 2500, the reaction produces a polyurethane elastomer C;
- Recycled high-density polyethylene, high-density polyethylene, carbon black, a compatibilizer, a lubricant, a compounded polyurethane elastomer, and a compounded antioxidant are mixed and melt-extruded to obtain the polyethylene.
- the melting temperature is 175°C.
- step (1) the molar ratio of terminal hydroxyl polybutadiene with a molecular weight of 1000-1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1: (0.03-0.04): (2.8-3.0): (2.8-2.9).
- the mass ratio of the polyurethane elastomer A, the polyurethane elastomer B and the polyurethane elastomer C is 2:(1-1.5):(0.6-0.8).
- step (3) the contents of each component are: by mass, 90-95 parts of recycled high-density polyethylene, 5-8 parts of high-density polyethylene, 1-2 parts of carbon black, 10-12 parts of compatibilizer, 1-1.5 parts of lubricant, 8-10 parts of compounded polyurethane elastomer, and 1-2 parts of compounded antioxidant.
- the compatibilizer is maleic anhydride grafted polyethylene; the lubricant is calcium stearate; and the compound antioxidant is a mixture of a terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010, with a mass ratio of (4-5):1.
- the specific preparation steps of the terminal hydroxyl polybutadiene modified antioxidant are: take modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene, mix them, stir them evenly, add isophorone diisocyanate under nitrogen environment, react at 40-45°C for 4-5h, then heat to 70-75°C, add 2,2'-thiobis(4-methyl-6-tert-butylphenol), keep warm and react for 5-6h, collect the product after the reaction, and vacuum dry to obtain the terminal hydroxyl polybutadiene modified antioxidant.
- the molar ratio of the modified terminal hydroxyl polybutadiene and isophorone diisocyanate is (2-3):1; the amount of dibutyltin dilaurate is 1-1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) and isophorone diisocyanate is (2.5-3):1.
- step (2) the mass ratio of the alcohol monomer to polyoxypropylene glycol is (9-10):1, and the amount of dibutyltin dilaurate is 0.1-0.15wt% of the alcohol monomer; the R value in the system, i.e., the molar ratio of isocyanate to hydroxyl group is (1-1.2).
- a more optimized solution is the polyethylene prepared by the method for preparing recycled high-density polyethylene for marine fishing nets according to any of the above items.
- the invention discloses a recycled high-density polyethylene for marine fishing nets and a preparation method thereof.
- the recycled high-density polyethylene, high-density polyethylene, carbon black, a compatibilizer, a lubricant, a compounded polyurethane elastomer and a compounded antioxidant are mixed and melt-extruded to obtain the high-density polyethylene for fishing nets.
- a polyurethane elastomer is added to enhance it, and the polyurethane elastomer is prepared by reacting terminal hydroxyl polybutadiene and isocyanate.
- the polyurethane elastomer has higher compatibility with the system and better enhancement effect.
- the scheme also prepares different polyurethane elastomers according to the different molecular weights of terminal hydroxyl polybutadiene, and compound them to form a compound polyurethane elastomer; the scheme first epoxidizes the hydroxyl groups at both ends of the terminal hydroxyl polybutadiene with a molecular weight of 1000-1500 and then hydrolyzes them to open the ring to generate a multi-hydroxyl-terminated polybutadiene.
- the multi-hydroxyl-terminated polybutadiene is selected to improve the cross-linking of the polyurethane elastomer, thereby improving the reinforcement effect of the polyurethane elastomer A; and the terminal hydroxyl polybutadiene with a molecular weight of 1600-1800 and the terminal hydroxyl polybutadiene with a molecular weight of 2000-2500 used subsequently have a large molecular weight. If they are epoxidized and then opened, it will affect the reinforcement of the system. Therefore, they are only reacted with isocyanate to obtain polyurethane elastomer B and polyurethane elastomer C; the compounded elastomer obtained by compounding can reinforce polyethylene to the greatest extent.
- the solution uses polyhydroxy-terminated polybutadiene and isocyanate pre-polymerization and then grafts the antioxidant 2,2'-thiobis(4-methyl-6-tert-butylphenol) to generate a long-chain antioxidant.
- the antioxidant is compounded with antioxidant 1010 to effectively improve the anti-aging performance of the product; on the other hand, the migration resistance of the antioxidant in the system is greatly reduced, the anti-aging performance of the product is maintained for a long time, and the comprehensive practicality is higher.
- the invention discloses a recycled high-density polyethylene for marine fishing nets and a preparation method thereof.
- the overall formula of the scheme is suitable, and the process parameters of each step are appropriate.
- the prepared polyethylene not only has excellent mechanical properties and high strength, but also has excellent anti-aging performance and high practicality.
- hydroxyl-terminated polybutadiene 1 has a number average molecular weight of 1500 g/mol and a hydroxyl value of 1.5 mmol/g
- hydroxyl-terminated polybutadiene 2 has a number average molecular weight of 1800 g/mol and a hydroxyl value of 1.44 mmol/g
- hydroxyl-terminated polybutadiene 3 has a number average molecular weight of 1800 g/mol and a hydroxyl value of 1.44 mmol/g.
- Embodiment 1 A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
- the molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
- the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
- the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
- terminal hydroxyl polybutadiene modified antioxidant modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 40°C for 5 hours, the temperature is then raised to 70°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
- the molar ratio of the modified terminal hydroxyl polybutadiene to isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to isophorone diisocyanate is 3:1.
- the compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
- Embodiment 2 A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
- the molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
- the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
- the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
- terminal hydroxyl polybutadiene modified antioxidant modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 5.5 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
- the molar ratio of the modified terminal hydroxyl polybutadiene to isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to isophorone diisocyanate is 3:1.
- the compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
- Embodiment 3 A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
- the molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
- the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
- the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
- terminal hydroxyl polybutadiene modified antioxidant modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
- the molar ratio of the modified terminal hydroxyl polybutadiene to isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to isophorone diisocyanate is 3:1.
- the compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
- Comparative Example 1 Example 3 was used as the control group. In Comparative Example 1, the terminal hydroxyl polybutadiene 1 was not modified. Only the terminal hydroxyl polybutadiene 1 was used to prepare the polyurethane elastomer A and the terminal hydroxyl polybutadiene-modified antioxidant, and the other steps remained unchanged.
- the polyurethane elastomer A is obtained by reaction;
- the reaction produces polyurethane elastomer B;
- the reaction produces polyurethane elastomer C.
- the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
- terminal hydroxyl polybutadiene modified antioxidant terminal hydroxyl polybutadiene 1, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
- the molar ratio of the terminal hydroxyl polybutadiene 1 and isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) and isophorone diisocyanate is 3:1.
- the compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
- Comparative Example 2 Example 3 was used as the control group. In Comparative Example 2, only conventional antioxidant 1010 was used, and its dosage was increased, while the other steps remained unchanged.
- the filtrate is collected by suction filtration, the pH is adjusted to neutral with sulfuric acid, toluene and water are removed by vacuum distillation to obtain epoxy-terminated polybutadiene glycidyl ether; the epoxy-terminated polybutadiene glycidyl ether obtained by the reaction, 50 mL of deionized water, and 3 drops of concentrated sulfuric acid are mixed, hydrolyzed at 25° C. for 3 h, washed with water until neutral, and water is removed by vacuum distillation at 90° C. to obtain modified hydroxy-terminated polybutadiene Diene.
- the molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
- the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
- the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
- the compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
- Comparative Example 3 Example 3 was used as the control group. In Comparative Example 3, no hydroxy-terminated polybutadiene 3 was introduced, and the other steps remained unchanged.
- the molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
- the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B.
- the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
- terminal hydroxyl polybutadiene modified antioxidant modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
- the molar ratio of the modified terminal hydroxyl polybutadiene to isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to isophorone diisocyanate is 3:1.
- the compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
- Comparative Example 4 Taking Example 3 as the control group, the proportion of terminal hydroxyl polybutadiene 3 was increased in Comparative Example 4, and the other steps remained unchanged.
- the molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
- the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
- the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
- terminal hydroxyl polybutadiene modified antioxidant modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
- the molar ratio of the modified terminal hydroxyl polybutadiene to isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to isophorone diisocyanate is 3:1.
- the compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
- Comparative Example 5 Example 3 was used as the control group. In Comparative Example 5, hydroxy-terminated polybutadiene 2 and hydroxy-terminated polybutadiene 3 were not introduced, and only hydroxy-terminated polybutadiene 1 was added, and the other steps remained unchanged.
- the molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
- polyurethane elastomer A is obtained by reaction.
- terminal hydroxyl polybutadiene modified antioxidant modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
- the compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
- Anti-migration performance of antioxidants Take the polyethylene prepared in Examples 1 to 3 and Comparative Examples 1 to 5, and injection mold them at an injection molding temperature of 180°C to obtain a sheet sample with a size of 15 cm ⁇ 15 cm ⁇ 1 cm. Immerse it in 30 mL of anhydrous ethanol, place it in a 50°C water bath for 48 hours, take it out and vacuum dry it at 40°C for 12 hours, and re-measure the 200°C oxidation induction period.
- the invention discloses a recycled high-density polyethylene for marine fishing nets and a preparation method thereof.
- the overall formula of the scheme is suitable.
- the process parameters of each step are appropriate, and the prepared polyethylene not only has excellent mechanical properties and high strength, but also excellent anti-aging properties and high practicality.
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Abstract
Description
本发明涉及高密度聚乙烯技术领域，具体为一种海洋渔网用再生高密度聚乙烯及其制备方法。The invention relates to the technical field of high-density polyethylene, in particular to recycled high-density polyethylene for marine fishing nets and a preparation method thereof.
HDPE再生料又叫高密度聚乙烯再生料，它是通过回收的HDPE水口料、HDPE制品的再次利用，经过清洗、除水后，再破碎后，经过造粒机，造粒而成。但高密度聚乙烯再生料的物理性能较差，且由于多次加工，材料的老化性能也会收到影响，实际使用时无法满足我们的需求。HDPE recycled material is also called high-density polyethylene recycled material. It is made by recycling HDPE nozzle materials and HDPE products, and then washing, dehydrating, crushing, and granulating them in a granulator. However, the physical properties of high-density polyethylene recycled material are poor, and due to multiple processing, the aging performance of the material will also be affected, and it cannot meet our needs in actual use.
因此，如何提高再生高密度聚乙烯的综合力学性能和抗老化性能，这是我们亟待解决的技术问题，本方案公开了一种海洋渔网用再生高密度聚乙烯及其制备方法，以解决该技术问题。Therefore, how to improve the comprehensive mechanical properties and anti-aging properties of recycled high-density polyethylene is a technical problem that we urgently need to solve. This scheme discloses a recycled high-density polyethylene for marine fishing nets and a preparation method thereof to solve this technical problem.
发明内容Summary of the invention
本发明的目的在于提供一种海洋渔网用再生高密度聚乙烯及其制备方法，以解决上述背景技术中提出的问题。The object of the present invention is to provide a recycled high-density polyethylene for marine fishing nets and a preparation method thereof, so as to solve the problems raised in the above-mentioned background technology.
为了解决上述技术问题，本发明提供如下技术方案：In order to solve the above technical problems, the present invention provides the following technical solutions:
一种海洋渔网用再生高密度聚乙烯及其制备方法，包括以下步骤：A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
(1)将分子量为1000～1500的端羟基聚丁二烯和甲苯混合，搅拌至溶解，加入四丁基溴化铵和固体氢氧化钠，加热升温至40～45℃，加入环氧氯丙烷，55～60℃水浴下反应1.5～2.5h，抽滤收集滤液，硫酸调节pH至中性，减压蒸馏除去甲苯和水，得到环氧基封端聚丁二烯缩水甘油醚；将环氧基封端聚丁二烯缩水甘油醚、去离子水、浓硫酸混合，25～30℃水解3h，水洗至中性，得到改性端羟基聚丁二烯；(1) Mixing terminal hydroxyl polybutadiene with a molecular weight of 1000 to 1500 and toluene, stirring until dissolved, adding tetrabutylammonium bromide and solid sodium hydroxide, heating to 40 to 45° C., adding epichlorohydrin, reacting in a water bath at 55 to 60° C. for 1.5 to 2.5 hours, collecting the filtrate by suction, adjusting the pH to neutral with sulfuric acid, and removing toluene and water by vacuum distillation to obtain epoxy-terminated polybutadiene glycidyl ether; mixing epoxy-terminated polybutadiene glycidyl ether, deionized water, and concentrated sulfuric acid, hydrolyzing at 25 to 30° C. for 3 hours, and washing with water until neutral to obtain modified terminal hydroxyl polybutadiene;
(2)将醇单体与聚氧化丙烯二醇混合，搅拌均匀，加热升温至80～85℃，加入二月桂酸二丁基锡，搅拌20～30min，再加入异佛尔酮二异氰酸酯，浇注至模具中，抽真空20～30min，45～50℃下固化7～10天，得到聚氨酯弹性体； (2) mixing the alcohol monomer and polyoxypropylene glycol, stirring evenly, heating to 80-85° C., adding dibutyltin dilaurate, stirring for 20-30 minutes, then adding isophorone diisocyanate, pouring into a mold, evacuating for 20-30 minutes, and curing at 45-50° C. for 7-10 days to obtain a polyurethane elastomer;
当醇单体为改性端羟基聚丁二烯时，反应制得聚氨酯弹性体A；当醇单体为分子量为1600～1800的端羟基聚丁二烯时，反应制得聚氨酯弹性体B；当醇单体为分子量为2000～2500的端羟基聚丁二烯时，反应制得聚氨酯弹性体C；When the alcohol monomer is a modified terminal hydroxyl polybutadiene, the reaction produces a polyurethane elastomer A; when the alcohol monomer is a terminal hydroxyl polybutadiene with a molecular weight of 1600 to 1800, the reaction produces a polyurethane elastomer B; when the alcohol monomer is a terminal hydroxyl polybutadiene with a molecular weight of 2000 to 2500, the reaction produces a polyurethane elastomer C;
(3)将聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C复配混合，得到复配聚氨酯弹性体；(3) compounding and mixing polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C to obtain a compounded polyurethane elastomer;
取再生高密度聚乙烯、高密度聚乙烯、炭黑、相容剂、润滑剂、复配聚氨酯弹性体、复配抗氧剂混合，熔融挤出，得到所述聚乙烯。熔融温度为175℃。Recycled high-density polyethylene, high-density polyethylene, carbon black, a compatibilizer, a lubricant, a compounded polyurethane elastomer, and a compounded antioxidant are mixed and melt-extruded to obtain the polyethylene. The melting temperature is 175°C.
较优化的方案，步骤(1)中，分子量为1000～1500的端羟基聚丁二烯、四丁基溴化铵、固体氢氧化钠、环氧氯丙烷的摩尔比为1：(0.03～0.04)：(2.8～3.0)：(2.8～2.9)。In a more optimized solution, in step (1), the molar ratio of terminal hydroxyl polybutadiene with a molecular weight of 1000-1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1: (0.03-0.04): (2.8-3.0): (2.8-2.9).
较优化的方案，步骤(3)复配聚氨酯弹性体中，所述聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C质量比为2：(1～1.5)：(0.6～0.8)。According to a more optimized solution, in the step (3) of compounding the polyurethane elastomer, the mass ratio of the polyurethane elastomer A, the polyurethane elastomer B and the polyurethane elastomer C is 2:(1-1.5):(0.6-0.8).
较优化的方案，步骤(3)中，各组分含量为：以质量份数计，再生高密度聚乙烯90～95份、高密度聚乙烯5～8份、炭黑1～2份、相容剂10～12份、润滑剂1～1.5份、复配聚氨酯弹性体8～10份、复配抗氧剂1～2份。In a more optimized solution, in step (3), the contents of each component are: by mass, 90-95 parts of recycled high-density polyethylene, 5-8 parts of high-density polyethylene, 1-2 parts of carbon black, 10-12 parts of compatibilizer, 1-1.5 parts of lubricant, 8-10 parts of compounded polyurethane elastomer, and 1-2 parts of compounded antioxidant.
较优化的方案，所述相容剂为马来酸酐接枝聚乙烯；所述润滑剂为硬脂酸钙；所述复配抗氧剂为端羟基聚丁二烯改性抗氧剂、抗氧剂1010混合，质量比为(4～5)：1。In a more optimized solution, the compatibilizer is maleic anhydride grafted polyethylene; the lubricant is calcium stearate; and the compound antioxidant is a mixture of a terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010, with a mass ratio of (4-5):1.
较优化的方案，所述端羟基聚丁二烯改性抗氧剂具体制备步骤为：取改性端羟基聚丁二烯、二月桂酸二丁基锡和甲苯混合，搅拌均匀，氮气环境下加入异佛尔酮二异氰酸酯，40～45℃下反应4～5h，再升温至70～75℃，加入2,2’-硫代双(4-甲基-6-叔丁基苯酚)，保温反应5～6h，反应结束后收集产物，真空干燥，得到端羟基聚丁二烯改性抗氧剂。A more optimized scheme, the specific preparation steps of the terminal hydroxyl polybutadiene modified antioxidant are: take modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene, mix them, stir them evenly, add isophorone diisocyanate under nitrogen environment, react at 40-45°C for 4-5h, then heat to 70-75°C, add 2,2'-thiobis(4-methyl-6-tert-butylphenol), keep warm and react for 5-6h, collect the product after the reaction, and vacuum dry to obtain the terminal hydroxyl polybutadiene modified antioxidant.
较优化的方案，所述改性端羟基聚丁二烯、异佛尔酮二异氰酸酯的摩尔比为(2～3)：1；所述二月桂酸二丁基锡用量为异佛尔酮二异氰酸酯的1～1.5wt％；所述2,2’-硫代双(4-甲基-6-叔丁基苯酚)、异佛尔酮二异氰酸酯的摩尔比为(2.5～3)：1。In a more optimized solution, the molar ratio of the modified terminal hydroxyl polybutadiene and isophorone diisocyanate is (2-3):1; the amount of dibutyltin dilaurate is 1-1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) and isophorone diisocyanate is (2.5-3):1.
较优化的方案，步骤(2)中，所述醇单体、聚氧化丙烯二醇的质量比为(9～10)：1，所述二月桂酸二丁基锡用量为醇单体的0.1～0.15wt％；体系中R值，即异氰酸酯、羟基摩尔比为(1～1.2)。In a more optimized solution, in step (2), the mass ratio of the alcohol monomer to polyoxypropylene glycol is (9-10):1, and the amount of dibutyltin dilaurate is 0.1-0.15wt% of the alcohol monomer; the R value in the system, i.e., the molar ratio of isocyanate to hydroxyl group is (1-1.2).
较优化的方案，根据以上任意一项所述的一种海洋渔网用再生高密度聚乙烯的制备方法制备的聚乙烯。 A more optimized solution is the polyethylene prepared by the method for preparing recycled high-density polyethylene for marine fishing nets according to any of the above items.
与现有技术相比，本发明所达到的有益效果是：Compared with the prior art, the beneficial effects achieved by the present invention are:
本发明公开了一种海洋渔网用再生高密度聚乙烯及其制备方法，方案以再生高密度聚乙烯、高密度聚乙烯、炭黑、相容剂、润滑剂、复配聚氨酯弹性体、复配抗氧剂混合，熔融挤出后得到渔网用高密度聚乙烯；本方案中，为提高聚乙烯的强度和综合力学性能，方案添加了聚氨酯弹性体对其进行增强，且聚氨酯弹性体以端羟基聚丁二烯、异氰酸酯反应制得，相比于常规聚氨酯弹性体，其与体系相容性更高，增强效果更优异。The invention discloses a recycled high-density polyethylene for marine fishing nets and a preparation method thereof. The recycled high-density polyethylene, high-density polyethylene, carbon black, a compatibilizer, a lubricant, a compounded polyurethane elastomer and a compounded antioxidant are mixed and melt-extruded to obtain the high-density polyethylene for fishing nets. In the present invention, in order to improve the strength and comprehensive mechanical properties of polyethylene, a polyurethane elastomer is added to enhance it, and the polyurethane elastomer is prepared by reacting terminal hydroxyl polybutadiene and isocyanate. Compared with conventional polyurethane elastomers, the polyurethane elastomer has higher compatibility with the system and better enhancement effect.
在此基础上，方案还根据端羟基聚丁二烯的分子量不同，以制得不同的聚氨酯弹性体，并将其复配形成复配聚氨酯弹性体；方案先将分子量为1000～1500的端羟基聚丁二烯两端羟基环氧化后水解开环，以生成多羟基封端的聚丁二烯，由于此时选择的端羟基聚丁二烯分子量较低，因而选择制得多羟基封端的聚丁二烯，以提高聚氨酯弹性体的交联，从而提高聚氨酯弹性体A的增强效果；而后续采用的分子量为1600～1800的端羟基聚丁二烯、分子量为2000～2500的端羟基聚丁二烯，其分子量较大，若对其环氧化后开环反而会影响体系增强，故而仅将其与异氰酸酯反应制得聚氨酯弹性体B、聚氨酯弹性体C；复配得到的复配弹性体能够最大程度对聚乙烯进行增强。On this basis, the scheme also prepares different polyurethane elastomers according to the different molecular weights of terminal hydroxyl polybutadiene, and compound them to form a compound polyurethane elastomer; the scheme first epoxidizes the hydroxyl groups at both ends of the terminal hydroxyl polybutadiene with a molecular weight of 1000-1500 and then hydrolyzes them to open the ring to generate a multi-hydroxyl-terminated polybutadiene. Since the terminal hydroxyl polybutadiene selected at this time has a low molecular weight, the multi-hydroxyl-terminated polybutadiene is selected to improve the cross-linking of the polyurethane elastomer, thereby improving the reinforcement effect of the polyurethane elastomer A; and the terminal hydroxyl polybutadiene with a molecular weight of 1600-1800 and the terminal hydroxyl polybutadiene with a molecular weight of 2000-2500 used subsequently have a large molecular weight. If they are epoxidized and then opened, it will affect the reinforcement of the system. Therefore, they are only reacted with isocyanate to obtain polyurethane elastomer B and polyurethane elastomer C; the compounded elastomer obtained by compounding can reinforce polyethylene to the greatest extent.
与此同时，为提高产品的抗老化性能，方案利用多羟基封端的聚丁二烯与异氰酸酯预聚后接枝抗氧剂2,2’-硫代双(4-甲基-6-叔丁基苯酚)，从而生成长链抗氧剂，一方面，该抗氧剂与抗氧剂1010复配，能够有效提高产品的抗老化性能；另一方面，体系中的抗氧剂的耐迁移性大大降低，产品的抗老化性能长久保持，综合实用性更高。At the same time, in order to improve the anti-aging performance of the product, the solution uses polyhydroxy-terminated polybutadiene and isocyanate pre-polymerization and then grafts the antioxidant 2,2'-thiobis(4-methyl-6-tert-butylphenol) to generate a long-chain antioxidant. On the one hand, the antioxidant is compounded with antioxidant 1010 to effectively improve the anti-aging performance of the product; on the other hand, the migration resistance of the antioxidant in the system is greatly reduced, the anti-aging performance of the product is maintained for a long time, and the comprehensive practicality is higher.
本发明公开了一种海洋渔网用再生高密度聚乙烯及其制备方法，方案整体配方适宜，各步骤工艺参数得当，制备得到的聚乙烯不仅具有优异的力学性能，强度高，且抗老化性能优异，具有较高的实用性。The invention discloses a recycled high-density polyethylene for marine fishing nets and a preparation method thereof. The overall formula of the scheme is suitable, and the process parameters of each step are appropriate. The prepared polyethylene not only has excellent mechanical properties and high strength, but also has excellent anti-aging performance and high practicality.
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
以下实施例中，端羟基聚丁二烯1：数均分子量为1500g/mol，羟值为1.5mmol/g；端羟基聚丁二烯2：数均分子量为1800g/mol，羟值为1.44mmol/g；端羟基聚丁二烯3：数均 分子量为2400g/mol，羟值为0.67mmol/g；以上均由洛阳黎明化工研究院提供；再生高密度聚乙烯为塑料瓶盖、牛奶瓶盖回收，切断清洗烘干后获得，熔融指数(MFI，190℃/5Kg)为5.8g/10min，雄县天海塑料制品厂提供；聚氧化丙烯二醇(N210)，Mn＝1000，烟台万华聚氨酯股份有限公司提供；高密度聚乙烯5000S，中国石油大庆石化分公司提供；马来酸酐接枝聚乙烯：马来酸酐接枝低密度聚乙烯，MV206，MAH接枝率为1％，上海日之升新技术发展有限公司提供。In the following examples, hydroxyl-terminated polybutadiene 1 has a number average molecular weight of 1500 g/mol and a hydroxyl value of 1.5 mmol/g; hydroxyl-terminated polybutadiene 2 has a number average molecular weight of 1800 g/mol and a hydroxyl value of 1.44 mmol/g; and hydroxyl-terminated polybutadiene 3 has a number average molecular weight of 1800 g/mol and a hydroxyl value of 1.44 mmol/g. The molecular weight is 2400g/mol, and the hydroxyl value is 0.67mmol/g; all of the above are provided by Luoyang Liming Chemical Research Institute; recycled high-density polyethylene is recycled from plastic bottle caps and milk bottle caps, obtained after cutting, cleaning and drying, with a melt index (MFI, 190℃/5Kg) of 5.8g/10min, provided by Xiongxian Tianhai Plastic Products Factory; polyoxypropylene glycol (N210), Mn=1000, provided by Yantai Wanhua Polyurethane Co., Ltd.; high-density polyethylene 5000S, provided by PetroChina Daqing Petrochemical Branch; maleic anhydride grafted polyethylene: maleic anhydride grafted low-density polyethylene, MV206, MAH grafting rate is 1%, provided by Shanghai Rizhisheng New Technology Development Co., Ltd.
实施例1：一种海洋渔网用再生高密度聚乙烯及其制备方法，包括以下步骤：Embodiment 1: A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
(1)将0.01mol分子量为1500的端羟基聚丁二烯1和10mL甲苯混合，搅拌至溶解，加入四丁基溴化铵和固体氢氧化钠，加热升温至40℃，加入环氧氯丙烷，55℃水浴下反应2.5h，抽滤收集滤液，硫酸调节pH至中性，减压蒸馏除去甲苯和水，得到环氧基封端聚丁二烯缩水甘油醚；将反应得到的环氧基封端聚丁二烯缩水甘油醚、50mL去离子水、3滴浓硫酸混合，25℃水解3h，水洗至中性，90℃下减压蒸馏除水，得到改性端羟基聚丁二烯。(1) 0.01 mol of hydroxy-terminated polybutadiene 1 with a molecular weight of 1500 and 10 mL of toluene are mixed, stirred until dissolved, tetrabutylammonium bromide and solid sodium hydroxide are added, heated to 40°C, epichlorohydrin is added, reacted in a water bath at 55°C for 2.5 h, the filtrate is collected by suction, the pH is adjusted to neutral with sulfuric acid, toluene and water are removed by vacuum distillation to obtain epoxy-terminated polybutadiene glycidyl ether; the epoxy-terminated polybutadiene glycidyl ether obtained by the reaction, 50 mL of deionized water, and 3 drops of concentrated sulfuric acid are mixed, hydrolyzed at 25°C for 3 h, washed with water until neutral, and water is removed by vacuum distillation at 90°C to obtain modified hydroxy-terminated polybutadiene.
分子量为1500的端羟基聚丁二烯1、四丁基溴化铵、固体氢氧化钠、环氧氯丙烷的摩尔比为1：0.03：3.0：2.9。The molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
(2)将醇单体与聚氧化丙烯二醇混合，搅拌均匀，加热升温至80℃，加入二月桂酸二丁基锡，搅拌30min，再加入异佛尔酮二异氰酸酯，浇注至模具中，抽真空30min，45℃下固化7天，得到聚氨酯弹性体。(2) The alcohol monomer and polyoxypropylene glycol are mixed, stirred evenly, heated to 80° C., dibutyltin dilaurate is added, stirred for 30 minutes, and then isophorone diisocyanate is added, poured into a mold, vacuumed for 30 minutes, and cured at 45° C. for 7 days to obtain a polyurethane elastomer.
当醇单体为改性端羟基聚丁二烯时，反应制得聚氨酯弹性体A；当醇单体为分子量为1800的端羟基聚丁二烯2时，反应制得聚氨酯弹性体B；当醇单体为分子量为2400的端羟基聚丁二烯3时，反应制得聚氨酯弹性体C。When the alcohol monomer is modified terminal hydroxyl polybutadiene, the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
以上聚氨酯弹性体制备时，所述醇单体、聚氧化丙烯二醇的质量比为9.5：1，所述二月桂酸二丁基锡用量为醇单体的0.15wt％；体系中R值，即体系中异氰酸酯、羟基摩尔比为1.2。When preparing the above polyurethane elastomer, the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
(3)制备端羟基聚丁二烯改性抗氧剂：取改性端羟基聚丁二烯、二月桂酸二丁基锡和甲苯混合，搅拌均匀，氮气环境下加入异佛尔酮二异氰酸酯，40℃下反应5h，再升温至70℃，加入2,2’-硫代双(4-甲基-6-叔丁基苯酚)，保温反应6h，反应结束后收集产物，真空干燥，得到端羟基聚丁二烯改性抗氧剂。 (3) Preparation of terminal hydroxyl polybutadiene modified antioxidant: modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 40°C for 5 hours, the temperature is then raised to 70°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
所述改性端羟基聚丁二烯、异佛尔酮二异氰酸酯的摩尔比为2：1；所述二月桂酸二丁基锡用量为异佛尔酮二异氰酸酯的1.5wt％；所述2,2’-硫代双(4-甲基-6-叔丁基苯酚)、异佛尔酮二异氰酸酯的摩尔比为3：1。The molar ratio of the modified terminal hydroxyl polybutadiene to isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to isophorone diisocyanate is 3:1.
(4)将聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C复配混合，得到复配聚氨酯弹性体；所述聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C质量比为2：1：0.6。将端羟基聚丁二烯改性抗氧剂、抗氧剂1010混合，得到复配抗氧剂；所述端羟基聚丁二烯改性抗氧剂、抗氧剂1010质量比为5：1。(4) Compounding polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C to obtain a compound polyurethane elastomer; the mass ratio of polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C is 2:1:0.6. Mixing terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 to obtain a compound antioxidant; the mass ratio of terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 is 5:1.
以质量份数计，取90份再生高密度聚乙烯、8份高密度聚乙烯、2份炭黑、12份相容剂、1.5份润滑剂、8份复配聚氨酯弹性体、1.5份复配抗氧剂混合，熔融挤出，得到所述聚乙烯。所述相容剂为马来酸酐接枝聚乙烯；所述润滑剂为硬脂酸钙。90 parts of recycled high-density polyethylene, 8 parts of high-density polyethylene, 2 parts of carbon black, 12 parts of compatibilizer, 1.5 parts of lubricant, 8 parts of compounded polyurethane elastomer, and 1.5 parts of compounded antioxidant are mixed and melt-extruded to obtain the polyethylene. The compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
实施例2：一种海洋渔网用再生高密度聚乙烯及其制备方法，包括以下步骤：Embodiment 2: A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
(1)将0.01mol分子量为1500的端羟基聚丁二烯1和10mL甲苯混合，搅拌至溶解，加入四丁基溴化铵和固体氢氧化钠，加热升温至45℃，加入环氧氯丙烷，58℃水浴下反应2h，抽滤收集滤液，硫酸调节pH至中性，减压蒸馏除去甲苯和水，得到环氧基封端聚丁二烯缩水甘油醚；将反应得到的环氧基封端聚丁二烯缩水甘油醚、50mL去离子水、3滴浓硫酸混合，25℃水解3h，水洗至中性，90℃下减压蒸馏除水，得到改性端羟基聚丁二烯。(1) 0.01 mol of hydroxy-terminated polybutadiene 1 with a molecular weight of 1500 and 10 mL of toluene are mixed, stirred until dissolved, tetrabutylammonium bromide and solid sodium hydroxide are added, heated to 45°C, epichlorohydrin is added, reacted in a water bath at 58°C for 2 h, the filtrate is collected by suction, the pH is adjusted to neutral with sulfuric acid, toluene and water are removed by vacuum distillation to obtain epoxy-terminated polybutadiene glycidyl ether; the epoxy-terminated polybutadiene glycidyl ether obtained by the reaction, 50 mL of deionized water, and 3 drops of concentrated sulfuric acid are mixed, hydrolyzed at 25°C for 3 h, washed with water until neutral, and water is removed by vacuum distillation at 90°C to obtain modified hydroxy-terminated polybutadiene.
分子量为1500的端羟基聚丁二烯1、四丁基溴化铵、固体氢氧化钠、环氧氯丙烷的摩尔比为1：0.03：3.0：2.9。The molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
(2)将醇单体与聚氧化丙烯二醇混合，搅拌均匀，加热升温至85℃，加入二月桂酸二丁基锡，搅拌25min，再加入异佛尔酮二异氰酸酯，浇注至模具中，抽真空30min，50℃下固化7天，得到聚氨酯弹性体。(2) The alcohol monomer and polyoxypropylene glycol are mixed, stirred evenly, heated to 85° C., dibutyltin dilaurate is added, stirred for 25 minutes, and then isophorone diisocyanate is added, poured into a mold, vacuumed for 30 minutes, and cured at 50° C. for 7 days to obtain a polyurethane elastomer.
当醇单体为改性端羟基聚丁二烯时，反应制得聚氨酯弹性体A；当醇单体为分子量为1800的端羟基聚丁二烯2时，反应制得聚氨酯弹性体B；当醇单体为分子量为2400的端羟基聚丁二烯3时，反应制得聚氨酯弹性体C。When the alcohol monomer is modified terminal hydroxyl polybutadiene, the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
以上聚氨酯弹性体制备时，所述醇单体、聚氧化丙烯二醇的质量比为9.5：1，所述二月桂酸二丁基锡用量为醇单体的0.15wt％；体系中R值，即体系中异氰酸酯、羟基摩尔比 为1.2。When preparing the above polyurethane elastomer, the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
(3)制备端羟基聚丁二烯改性抗氧剂：取改性端羟基聚丁二烯、二月桂酸二丁基锡和甲苯混合，搅拌均匀，氮气环境下加入异佛尔酮二异氰酸酯，45℃下反应4.5h，再升温至75℃，加入2,2’-硫代双(4-甲基-6-叔丁基苯酚)，保温反应5.5h，反应结束后收集产物，真空干燥，得到端羟基聚丁二烯改性抗氧剂。(3) Preparation of terminal hydroxyl polybutadiene modified antioxidant: modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 5.5 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
所述改性端羟基聚丁二烯、异佛尔酮二异氰酸酯的摩尔比为2：1；所述二月桂酸二丁基锡用量为异佛尔酮二异氰酸酯的1.5wt％；所述2,2’-硫代双(4-甲基-6-叔丁基苯酚)、异佛尔酮二异氰酸酯的摩尔比为3：1。The molar ratio of the modified terminal hydroxyl polybutadiene to isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to isophorone diisocyanate is 3:1.
(4)将聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C复配混合，得到复配聚氨酯弹性体；所述聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C质量比为2：1：0.6。将端羟基聚丁二烯改性抗氧剂、抗氧剂1010混合，得到复配抗氧剂；所述端羟基聚丁二烯改性抗氧剂、抗氧剂1010质量比为5：1。(4) Compounding polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C to obtain a compound polyurethane elastomer; the mass ratio of polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C is 2:1:0.6. Mixing terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 to obtain a compound antioxidant; the mass ratio of terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 is 5:1.
以质量份数计，取90份再生高密度聚乙烯、8份高密度聚乙烯、2份炭黑、12份相容剂、1.5份润滑剂、9份复配聚氨酯弹性体、1.5份复配抗氧剂混合，熔融挤出，得到所述聚乙烯。所述相容剂为马来酸酐接枝聚乙烯；所述润滑剂为硬脂酸钙。90 parts of recycled high-density polyethylene, 8 parts of high-density polyethylene, 2 parts of carbon black, 12 parts of compatibilizer, 1.5 parts of lubricant, 9 parts of compounded polyurethane elastomer, and 1.5 parts of compounded antioxidant are mixed and melt-extruded to obtain the polyethylene. The compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
实施例3：一种海洋渔网用再生高密度聚乙烯及其制备方法，包括以下步骤：Embodiment 3: A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
(1)将0.01mol分子量为1500的端羟基聚丁二烯1和10mL甲苯混合，搅拌至溶解，加入四丁基溴化铵和固体氢氧化钠，加热升温至45℃，加入环氧氯丙烷，60℃水浴下反应1.5h，抽滤收集滤液，硫酸调节pH至中性，减压蒸馏除去甲苯和水，得到环氧基封端聚丁二烯缩水甘油醚；将反应得到的环氧基封端聚丁二烯缩水甘油醚、50mL去离子水、3滴浓硫酸混合，25℃水解3h，水洗至中性，90℃下减压蒸馏除水，得到改性端羟基聚丁二烯。(1) 0.01 mol of hydroxy-terminated polybutadiene 1 with a molecular weight of 1500 and 10 mL of toluene are mixed, stirred until dissolved, tetrabutylammonium bromide and solid sodium hydroxide are added, heated to 45°C, epichlorohydrin is added, reacted in a water bath at 60°C for 1.5 h, the filtrate is collected by suction, the pH is adjusted to neutral with sulfuric acid, toluene and water are removed by vacuum distillation to obtain epoxy-terminated polybutadiene glycidyl ether; the epoxy-terminated polybutadiene glycidyl ether obtained by the reaction, 50 mL of deionized water, and 3 drops of concentrated sulfuric acid are mixed, hydrolyzed at 25°C for 3 h, washed with water until neutral, and water is removed by vacuum distillation at 90°C to obtain modified hydroxy-terminated polybutadiene.
分子量为1500的端羟基聚丁二烯1、四丁基溴化铵、固体氢氧化钠、环氧氯丙烷的摩尔比为1：0.03：3.0：2.9。The molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
(2)将醇单体与聚氧化丙烯二醇混合，搅拌均匀，加热升温至85℃，加入二月桂酸二丁基锡，搅拌30min，再加入异佛尔酮二异氰酸酯，浇注至模具中，抽真空30min，50℃下固化7天，得到聚氨酯弹性体。 (2) The alcohol monomer and polyoxypropylene glycol are mixed, stirred evenly, heated to 85° C., dibutyltin dilaurate is added, stirred for 30 minutes, and then isophorone diisocyanate is added, poured into a mold, vacuumed for 30 minutes, and cured at 50° C. for 7 days to obtain a polyurethane elastomer.
当醇单体为改性端羟基聚丁二烯时，反应制得聚氨酯弹性体A；当醇单体为分子量为1800的端羟基聚丁二烯2时，反应制得聚氨酯弹性体B；当醇单体为分子量为2400的端羟基聚丁二烯3时，反应制得聚氨酯弹性体C。When the alcohol monomer is modified terminal hydroxyl polybutadiene, the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
以上聚氨酯弹性体制备时，所述醇单体、聚氧化丙烯二醇的质量比为9.5：1，所述二月桂酸二丁基锡用量为醇单体的0.15wt％；体系中R值，即体系中异氰酸酯、羟基摩尔比为1.2。When preparing the above polyurethane elastomer, the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
(3)制备端羟基聚丁二烯改性抗氧剂：取改性端羟基聚丁二烯、二月桂酸二丁基锡和甲苯混合，搅拌均匀，氮气环境下加入异佛尔酮二异氰酸酯，45℃下反应4.5h，再升温至75℃，加入2,2’-硫代双(4-甲基-6-叔丁基苯酚)，保温反应6h，反应结束后收集产物，真空干燥，得到端羟基聚丁二烯改性抗氧剂。(3) Preparation of terminal hydroxyl polybutadiene modified antioxidant: modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
所述改性端羟基聚丁二烯、异佛尔酮二异氰酸酯的摩尔比为2：1；所述二月桂酸二丁基锡用量为异佛尔酮二异氰酸酯的1.5wt％；所述2,2’-硫代双(4-甲基-6-叔丁基苯酚)、异佛尔酮二异氰酸酯的摩尔比为3：1。The molar ratio of the modified terminal hydroxyl polybutadiene to isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to isophorone diisocyanate is 3:1.
(4)将聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C复配混合，得到复配聚氨酯弹性体；所述聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C质量比为2：1：0.6。将端羟基聚丁二烯改性抗氧剂、抗氧剂1010混合，得到复配抗氧剂；所述端羟基聚丁二烯改性抗氧剂、抗氧剂1010质量比为5：1。(4) Compounding polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C to obtain a compound polyurethane elastomer; the mass ratio of polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C is 2:1:0.6. Mixing terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 to obtain a compound antioxidant; the mass ratio of terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 is 5:1.
以质量份数计，取90份再生高密度聚乙烯、8份高密度聚乙烯、2份炭黑、12份相容剂、1.5份润滑剂、10份复配聚氨酯弹性体、1.5份复配抗氧剂混合，熔融挤出，得到所述聚乙烯。所述相容剂为马来酸酐接枝聚乙烯；所述润滑剂为硬脂酸钙。90 parts of recycled high-density polyethylene, 8 parts of high-density polyethylene, 2 parts of carbon black, 12 parts of compatibilizer, 1.5 parts of lubricant, 10 parts of compounded polyurethane elastomer, and 1.5 parts of compounded antioxidant are mixed by mass, and melt extruded to obtain the polyethylene. The compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
对比例1：以实施例3为对照组，对比例1中并未对端羟基聚丁二烯1改性，仅采用端羟基聚丁二烯1制备聚氨酯弹性体A和端羟基聚丁二烯改性抗氧剂，其余步骤不变。Comparative Example 1: Example 3 was used as the control group. In Comparative Example 1, the terminal hydroxyl polybutadiene 1 was not modified. Only the terminal hydroxyl polybutadiene 1 was used to prepare the polyurethane elastomer A and the terminal hydroxyl polybutadiene-modified antioxidant, and the other steps remained unchanged.
一种海洋渔网用再生高密度聚乙烯及其制备方法，包括以下步骤：A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
(1)将醇单体与聚氧化丙烯二醇混合，搅拌均匀，加热升温至85℃，加入二月桂酸二丁基锡，搅拌30min，再加入异佛尔酮二异氰酸酯，浇注至模具中，抽真空30min，50℃下固化7天，得到聚氨酯弹性体。(1) The alcohol monomer and polyoxypropylene glycol are mixed, stirred evenly, heated to 85° C., dibutyltin dilaurate is added, stirred for 30 minutes, and then isophorone diisocyanate is added, poured into a mold, vacuumed for 30 minutes, and cured at 50° C. for 7 days to obtain a polyurethane elastomer.
当醇单体为分子量为1500的端羟基聚丁二烯1时，反应制得聚氨酯弹性体A；当醇 单体为分子量为1800的端羟基聚丁二烯2时，反应制得聚氨酯弹性体B；当醇单体为分子量为2400的端羟基聚丁二烯3时，反应制得聚氨酯弹性体C。When the alcohol monomer is a hydroxy-terminated polybutadiene 1 with a molecular weight of 1500, the polyurethane elastomer A is obtained by reaction; When the monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
以上聚氨酯弹性体制备时，所述醇单体、聚氧化丙烯二醇的质量比为9.5：1，所述二月桂酸二丁基锡用量为醇单体的0.15wt％；体系中R值，即体系中异氰酸酯、羟基摩尔比为1.2。When preparing the above polyurethane elastomer, the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
(2)制备端羟基聚丁二烯改性抗氧剂：取端羟基聚丁二烯1、二月桂酸二丁基锡和甲苯混合，搅拌均匀，氮气环境下加入异佛尔酮二异氰酸酯，45℃下反应4.5h，再升温至75℃，加入2,2’-硫代双(4-甲基-6-叔丁基苯酚)，保温反应6h，反应结束后收集产物，真空干燥，得到端羟基聚丁二烯改性抗氧剂。(2) Preparation of terminal hydroxyl polybutadiene modified antioxidant: terminal hydroxyl polybutadiene 1, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
所述端羟基聚丁二烯1、异佛尔酮二异氰酸酯的摩尔比为2：1；所述二月桂酸二丁基锡用量为异佛尔酮二异氰酸酯的1.5wt％；所述2,2’-硫代双(4-甲基-6-叔丁基苯酚)、异佛尔酮二异氰酸酯的摩尔比为3：1。The molar ratio of the terminal hydroxyl polybutadiene 1 and isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) and isophorone diisocyanate is 3:1.
(3)将聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C复配混合，得到复配聚氨酯弹性体；所述聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C质量比为2：1：0.6。将端羟基聚丁二烯改性抗氧剂、抗氧剂1010混合，得到复配抗氧剂；所述端羟基聚丁二烯改性抗氧剂、抗氧剂1010质量比为5：1。(3) Compounding polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C to obtain a compound polyurethane elastomer; the mass ratio of the polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C is 2:1:0.6. Mixing a terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 to obtain a compound antioxidant; the mass ratio of the terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 is 5:1.
以质量份数计，取90份再生高密度聚乙烯、8份高密度聚乙烯、2份炭黑、12份相容剂、1.5份润滑剂、10份复配聚氨酯弹性体、1.5份复配抗氧剂混合，熔融挤出，得到所述聚乙烯。所述相容剂为马来酸酐接枝聚乙烯；所述润滑剂为硬脂酸钙。90 parts of recycled high-density polyethylene, 8 parts of high-density polyethylene, 2 parts of carbon black, 12 parts of compatibilizer, 1.5 parts of lubricant, 10 parts of compounded polyurethane elastomer, and 1.5 parts of compounded antioxidant are mixed by mass, and melt extruded to obtain the polyethylene. The compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
对比例2：以实施例3为对照组，对比例2中仅采用常规抗氧剂1010，并增加其用量，其余步骤不变。Comparative Example 2: Example 3 was used as the control group. In Comparative Example 2, only conventional antioxidant 1010 was used, and its dosage was increased, while the other steps remained unchanged.
一种海洋渔网用再生高密度聚乙烯及其制备方法，包括以下步骤：A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
(1)将0.01mol分子量为1500的端羟基聚丁二烯1和10mL甲苯混合，搅拌至溶解，加入四丁基溴化铵和固体氢氧化钠，加热升温至45℃，加入环氧氯丙烷，60℃水浴下反应1.5h，抽滤收集滤液，硫酸调节pH至中性，减压蒸馏除去甲苯和水，得到环氧基封端聚丁二烯缩水甘油醚；将反应得到的环氧基封端聚丁二烯缩水甘油醚、50mL去离子水、3滴浓硫酸混合，25℃水解3h，水洗至中性，90℃下减压蒸馏除水，得到改性端羟基聚丁 二烯。(1) 0.01 mol of hydroxy-terminated polybutadiene 1 with a molecular weight of 1500 and 10 mL of toluene are mixed, stirred until dissolved, tetrabutylammonium bromide and solid sodium hydroxide are added, heated to 45° C., epichlorohydrin is added, reacted in a water bath at 60° C. for 1.5 h, the filtrate is collected by suction filtration, the pH is adjusted to neutral with sulfuric acid, toluene and water are removed by vacuum distillation to obtain epoxy-terminated polybutadiene glycidyl ether; the epoxy-terminated polybutadiene glycidyl ether obtained by the reaction, 50 mL of deionized water, and 3 drops of concentrated sulfuric acid are mixed, hydrolyzed at 25° C. for 3 h, washed with water until neutral, and water is removed by vacuum distillation at 90° C. to obtain modified hydroxy-terminated polybutadiene Diene.
分子量为1500的端羟基聚丁二烯1、四丁基溴化铵、固体氢氧化钠、环氧氯丙烷的摩尔比为1：0.03：3.0：2.9。The molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
(2)将醇单体与聚氧化丙烯二醇混合，搅拌均匀，加热升温至85℃，加入二月桂酸二丁基锡，搅拌30min，再加入异佛尔酮二异氰酸酯，浇注至模具中，抽真空30min，50℃下固化7天，得到聚氨酯弹性体。(2) The alcohol monomer and polyoxypropylene glycol are mixed, stirred evenly, heated to 85° C., dibutyltin dilaurate is added, stirred for 30 minutes, and then isophorone diisocyanate is added, poured into a mold, vacuumed for 30 minutes, and cured at 50° C. for 7 days to obtain a polyurethane elastomer.
当醇单体为改性端羟基聚丁二烯时，反应制得聚氨酯弹性体A；当醇单体为分子量为1800的端羟基聚丁二烯2时，反应制得聚氨酯弹性体B；当醇单体为分子量为2400的端羟基聚丁二烯3时，反应制得聚氨酯弹性体C。When the alcohol monomer is modified terminal hydroxyl polybutadiene, the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
以上聚氨酯弹性体制备时，所述醇单体、聚氧化丙烯二醇的质量比为9.5：1，所述二月桂酸二丁基锡用量为醇单体的0.15wt％；体系中R值，即体系中异氰酸酯、羟基摩尔比为1.2。When preparing the above polyurethane elastomer, the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
(3)将聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C复配混合，得到复配聚氨酯弹性体；所述聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C质量比为2：1：0.6。(3) Compounding and mixing polyurethane elastomer A, polyurethane elastomer B and polyurethane elastomer C to obtain a compounded polyurethane elastomer; the mass ratio of the polyurethane elastomer A, polyurethane elastomer B and polyurethane elastomer C is 2:1:0.6.
以质量份数计，取90份再生高密度聚乙烯、8份高密度聚乙烯、2份炭黑、12份相容剂、1.5份润滑剂、10份复配聚氨酯弹性体、3.5份抗氧剂1010混合，熔融挤出，得到所述聚乙烯。所述相容剂为马来酸酐接枝聚乙烯；所述润滑剂为硬脂酸钙。90 parts of recycled high-density polyethylene, 8 parts of high-density polyethylene, 2 parts of carbon black, 12 parts of compatibilizer, 1.5 parts of lubricant, 10 parts of compounded polyurethane elastomer, and 3.5 parts of antioxidant 1010 are mixed and melt-extruded to obtain the polyethylene. The compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
对比例3：以实施例3为对照组，对比例3中并未引入端羟基聚丁二烯3，其余步骤不变。Comparative Example 3: Example 3 was used as the control group. In Comparative Example 3, no hydroxy-terminated polybutadiene 3 was introduced, and the other steps remained unchanged.
一种海洋渔网用再生高密度聚乙烯及其制备方法，包括以下步骤：A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
(1)将0.01mol分子量为1500的端羟基聚丁二烯1和10mL甲苯混合，搅拌至溶解，加入四丁基溴化铵和固体氢氧化钠，加热升温至45℃，加入环氧氯丙烷，60℃水浴下反应1.5h，抽滤收集滤液，硫酸调节pH至中性，减压蒸馏除去甲苯和水，得到环氧基封端聚丁二烯缩水甘油醚；将反应得到的环氧基封端聚丁二烯缩水甘油醚、50mL去离子水、3滴浓硫酸混合，25℃水解3h，水洗至中性，90℃下减压蒸馏除水，得到改性端羟基聚丁二烯。 (1) 0.01 mol of hydroxy-terminated polybutadiene 1 with a molecular weight of 1500 and 10 mL of toluene are mixed, stirred until dissolved, tetrabutylammonium bromide and solid sodium hydroxide are added, heated to 45°C, epichlorohydrin is added, reacted in a water bath at 60°C for 1.5 h, the filtrate is collected by suction, the pH is adjusted to neutral with sulfuric acid, toluene and water are removed by vacuum distillation to obtain epoxy-terminated polybutadiene glycidyl ether; the epoxy-terminated polybutadiene glycidyl ether obtained by the reaction, 50 mL of deionized water, and 3 drops of concentrated sulfuric acid are mixed, hydrolyzed at 25°C for 3 h, washed with water until neutral, and water is removed by vacuum distillation at 90°C to obtain modified hydroxy-terminated polybutadiene.
分子量为1500的端羟基聚丁二烯1、四丁基溴化铵、固体氢氧化钠、环氧氯丙烷的摩尔比为1：0.03：3.0：2.9。The molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
(2)将醇单体与聚氧化丙烯二醇混合，搅拌均匀，加热升温至85℃，加入二月桂酸二丁基锡，搅拌30min，再加入异佛尔酮二异氰酸酯，浇注至模具中，抽真空30min，50℃下固化7天，得到聚氨酯弹性体。(2) The alcohol monomer and polyoxypropylene glycol are mixed, stirred evenly, heated to 85° C., dibutyltin dilaurate is added, stirred for 30 minutes, and then isophorone diisocyanate is added, poured into a mold, vacuumed for 30 minutes, and cured at 50° C. for 7 days to obtain a polyurethane elastomer.
当醇单体为改性端羟基聚丁二烯时，反应制得聚氨酯弹性体A；当醇单体为分子量为1800的端羟基聚丁二烯2时，反应制得聚氨酯弹性体B。When the alcohol monomer is modified terminal hydroxyl polybutadiene, the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B.
以上聚氨酯弹性体制备时，所述醇单体、聚氧化丙烯二醇的质量比为9.5：1，所述二月桂酸二丁基锡用量为醇单体的0.15wt％；体系中R值，即体系中异氰酸酯、羟基摩尔比为1.2。When preparing the above polyurethane elastomer, the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
(3)制备端羟基聚丁二烯改性抗氧剂：取改性端羟基聚丁二烯、二月桂酸二丁基锡和甲苯混合，搅拌均匀，氮气环境下加入异佛尔酮二异氰酸酯，45℃下反应4.5h，再升温至75℃，加入2,2’-硫代双(4-甲基-6-叔丁基苯酚)，保温反应6h，反应结束后收集产物，真空干燥，得到端羟基聚丁二烯改性抗氧剂。(3) Preparation of terminal hydroxyl polybutadiene modified antioxidant: modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
所述改性端羟基聚丁二烯、异佛尔酮二异氰酸酯的摩尔比为2：1；所述二月桂酸二丁基锡用量为异佛尔酮二异氰酸酯的1.5wt％；所述2,2’-硫代双(4-甲基-6-叔丁基苯酚)、异佛尔酮二异氰酸酯的摩尔比为3：1。The molar ratio of the modified terminal hydroxyl polybutadiene to isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to isophorone diisocyanate is 3:1.
(4)将聚氨酯弹性体A、聚氨酯弹性体B复配混合，得到复配聚氨酯弹性体；所述聚氨酯弹性体A、聚氨酯弹性体B质量比为2：1。将端羟基聚丁二烯改性抗氧剂、抗氧剂1010混合，得到复配抗氧剂；所述端羟基聚丁二烯改性抗氧剂、抗氧剂1010质量比为5：1。(4) Compounding polyurethane elastomer A and polyurethane elastomer B to obtain a compounded polyurethane elastomer; the mass ratio of the polyurethane elastomer A to the polyurethane elastomer B is 2:1. Mixing a terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 to obtain a compounded antioxidant; the mass ratio of the terminal hydroxyl polybutadiene modified antioxidant to the antioxidant 1010 is 5:1.
以质量份数计，取90份再生高密度聚乙烯、8份高密度聚乙烯、2份炭黑、12份相容剂、1.5份润滑剂、10份复配聚氨酯弹性体、1.5份复配抗氧剂混合，熔融挤出，得到所述聚乙烯。所述相容剂为马来酸酐接枝聚乙烯；所述润滑剂为硬脂酸钙。90 parts of recycled high-density polyethylene, 8 parts of high-density polyethylene, 2 parts of carbon black, 12 parts of compatibilizer, 1.5 parts of lubricant, 10 parts of compounded polyurethane elastomer, and 1.5 parts of compounded antioxidant are mixed by mass, and melt extruded to obtain the polyethylene. The compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
对比例4：以实施例3为对照组，对比例4中增加端羟基聚丁二烯3的占比值，其余步骤不变。Comparative Example 4: Taking Example 3 as the control group, the proportion of terminal hydroxyl polybutadiene 3 was increased in Comparative Example 4, and the other steps remained unchanged.
一种海洋渔网用再生高密度聚乙烯及其制备方法，包括以下步骤： A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
(1)将0.01mol分子量为1500的端羟基聚丁二烯1和10mL甲苯混合，搅拌至溶解，加入四丁基溴化铵和固体氢氧化钠，加热升温至45℃，加入环氧氯丙烷，60℃水浴下反应1.5h，抽滤收集滤液，硫酸调节pH至中性，减压蒸馏除去甲苯和水，得到环氧基封端聚丁二烯缩水甘油醚；将反应得到的环氧基封端聚丁二烯缩水甘油醚、50mL去离子水、3滴浓硫酸混合，25℃水解3h，水洗至中性，90℃下减压蒸馏除水，得到改性端羟基聚丁二烯。(1) 0.01 mol of hydroxy-terminated polybutadiene 1 with a molecular weight of 1500 and 10 mL of toluene are mixed, stirred until dissolved, tetrabutylammonium bromide and solid sodium hydroxide are added, heated to 45°C, epichlorohydrin is added, reacted in a water bath at 60°C for 1.5 h, the filtrate is collected by suction, the pH is adjusted to neutral with sulfuric acid, toluene and water are removed by vacuum distillation to obtain epoxy-terminated polybutadiene glycidyl ether; the epoxy-terminated polybutadiene glycidyl ether obtained by the reaction, 50 mL of deionized water, and 3 drops of concentrated sulfuric acid are mixed, hydrolyzed at 25°C for 3 h, washed with water until neutral, and water is removed by vacuum distillation at 90°C to obtain modified hydroxy-terminated polybutadiene.
分子量为1500的端羟基聚丁二烯1、四丁基溴化铵、固体氢氧化钠、环氧氯丙烷的摩尔比为1：0.03：3.0：2.9。The molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
(2)将醇单体与聚氧化丙烯二醇混合，搅拌均匀，加热升温至85℃，加入二月桂酸二丁基锡，搅拌30min，再加入异佛尔酮二异氰酸酯，浇注至模具中，抽真空30min，50℃下固化7天，得到聚氨酯弹性体。(2) The alcohol monomer and polyoxypropylene glycol are mixed, stirred evenly, heated to 85° C., dibutyltin dilaurate is added, stirred for 30 minutes, and then isophorone diisocyanate is added, poured into a mold, vacuumed for 30 minutes, and cured at 50° C. for 7 days to obtain a polyurethane elastomer.
当醇单体为改性端羟基聚丁二烯时，反应制得聚氨酯弹性体A；当醇单体为分子量为1800的端羟基聚丁二烯2时，反应制得聚氨酯弹性体B；当醇单体为分子量为2400的端羟基聚丁二烯3时，反应制得聚氨酯弹性体C。When the alcohol monomer is modified terminal hydroxyl polybutadiene, the reaction produces polyurethane elastomer A; when the alcohol monomer is terminal hydroxyl polybutadiene 2 with a molecular weight of 1800, the reaction produces polyurethane elastomer B; when the alcohol monomer is terminal hydroxyl polybutadiene 3 with a molecular weight of 2400, the reaction produces polyurethane elastomer C.
以上聚氨酯弹性体制备时，所述醇单体、聚氧化丙烯二醇的质量比为9.5：1，所述二月桂酸二丁基锡用量为醇单体的0.15wt％；体系中R值，即体系中异氰酸酯、羟基摩尔比为1.2。When preparing the above polyurethane elastomer, the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
(3)制备端羟基聚丁二烯改性抗氧剂：取改性端羟基聚丁二烯、二月桂酸二丁基锡和甲苯混合，搅拌均匀，氮气环境下加入异佛尔酮二异氰酸酯，45℃下反应4.5h，再升温至75℃，加入2,2’-硫代双(4-甲基-6-叔丁基苯酚)，保温反应6h，反应结束后收集产物，真空干燥，得到端羟基聚丁二烯改性抗氧剂。(3) Preparation of terminal hydroxyl polybutadiene modified antioxidant: modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
所述改性端羟基聚丁二烯、异佛尔酮二异氰酸酯的摩尔比为2：1；所述二月桂酸二丁基锡用量为异佛尔酮二异氰酸酯的1.5wt％；所述2,2’-硫代双(4-甲基-6-叔丁基苯酚)、异佛尔酮二异氰酸酯的摩尔比为3：1。The molar ratio of the modified terminal hydroxyl polybutadiene to isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; and the molar ratio of 2,2'-thiobis(4-methyl-6-tert-butylphenol) to isophorone diisocyanate is 3:1.
(4)将聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C复配混合，得到复配聚氨酯弹性体；所述聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C质量比为2：1：1.2。将端羟基聚丁二烯改性抗氧剂、抗氧剂1010混合，得到复配抗氧剂；所述端羟基聚丁二烯改性抗氧剂、抗氧剂1010质量比为5：1。 (4) Compounding polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C to obtain a compounded polyurethane elastomer; the mass ratio of the polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C is 2:1:1.2. Mixing a terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 to obtain a compounded antioxidant; the mass ratio of the terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 is 5:1.
以质量份数计，取90份再生高密度聚乙烯、8份高密度聚乙烯、2份炭黑、12份相容剂、1.5份润滑剂、10份复配聚氨酯弹性体、1.5份复配抗氧剂混合，熔融挤出，得到所述聚乙烯。所述相容剂为马来酸酐接枝聚乙烯；所述润滑剂为硬脂酸钙。90 parts of recycled high-density polyethylene, 8 parts of high-density polyethylene, 2 parts of carbon black, 12 parts of compatibilizer, 1.5 parts of lubricant, 10 parts of compounded polyurethane elastomer, and 1.5 parts of compounded antioxidant are mixed by mass, and melt extruded to obtain the polyethylene. The compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
对比例5：以实施例3为对照组，对比例5中并未引入端羟基聚丁二烯2、端羟基聚丁二烯3，仅加入端羟基聚丁二烯1，其余步骤不变。Comparative Example 5: Example 3 was used as the control group. In Comparative Example 5, hydroxy-terminated polybutadiene 2 and hydroxy-terminated polybutadiene 3 were not introduced, and only hydroxy-terminated polybutadiene 1 was added, and the other steps remained unchanged.
一种海洋渔网用再生高密度聚乙烯及其制备方法，包括以下步骤：A recycled high-density polyethylene for marine fishing nets and a preparation method thereof, comprising the following steps:
(1)将0.01mol分子量为1500的端羟基聚丁二烯1和10mL甲苯混合，搅拌至溶解，加入四丁基溴化铵和固体氢氧化钠，加热升温至45℃，加入环氧氯丙烷，60℃水浴下反应1.5h，抽滤收集滤液，硫酸调节pH至中性，减压蒸馏除去甲苯和水，得到环氧基封端聚丁二烯缩水甘油醚；将反应得到的环氧基封端聚丁二烯缩水甘油醚、50mL去离子水、3滴浓硫酸混合，25℃水解3h，水洗至中性，90℃下减压蒸馏除水，得到改性端羟基聚丁二烯。(1) 0.01 mol of hydroxy-terminated polybutadiene 1 with a molecular weight of 1500 and 10 mL of toluene are mixed, stirred until dissolved, tetrabutylammonium bromide and solid sodium hydroxide are added, heated to 45°C, epichlorohydrin is added, reacted in a water bath at 60°C for 1.5 h, the filtrate is collected by suction, the pH is adjusted to neutral with sulfuric acid, toluene and water are removed by vacuum distillation to obtain epoxy-terminated polybutadiene glycidyl ether; the epoxy-terminated polybutadiene glycidyl ether obtained by the reaction, 50 mL of deionized water, and 3 drops of concentrated sulfuric acid are mixed, hydrolyzed at 25°C for 3 h, washed with water until neutral, and water is removed by vacuum distillation at 90°C to obtain modified hydroxy-terminated polybutadiene.
分子量为1500的端羟基聚丁二烯1、四丁基溴化铵、固体氢氧化钠、环氧氯丙烷的摩尔比为1：0.03：3.0：2.9。The molar ratio of terminal hydroxyl polybutadiene 1 with a molecular weight of 1500, tetrabutylammonium bromide, solid sodium hydroxide and epichlorohydrin is 1:0.03:3.0:2.9.
(2)将醇单体与聚氧化丙烯二醇混合，搅拌均匀，加热升温至85℃，加入二月桂酸二丁基锡，搅拌30min，再加入异佛尔酮二异氰酸酯，浇注至模具中，抽真空30min，50℃下固化7天，得到聚氨酯弹性体。(2) The alcohol monomer and polyoxypropylene glycol are mixed, stirred evenly, heated to 85° C., dibutyltin dilaurate is added, stirred for 30 minutes, and then isophorone diisocyanate is added, poured into a mold, vacuumed for 30 minutes, and cured at 50° C. for 7 days to obtain a polyurethane elastomer.
当醇单体为改性端羟基聚丁二烯时，反应制得聚氨酯弹性体A。When the alcohol monomer is modified terminal hydroxyl polybutadiene, polyurethane elastomer A is obtained by reaction.
以上聚氨酯弹性体制备时，所述醇单体、聚氧化丙烯二醇的质量比为9.5：1，所述二月桂酸二丁基锡用量为醇单体的0.15wt％；体系中R值，即体系中异氰酸酯、羟基摩尔比为1.2。When preparing the above polyurethane elastomer, the mass ratio of the alcohol monomer to polyoxypropylene glycol is 9.5:1, and the amount of dibutyltin dilaurate is 0.15wt% of the alcohol monomer; the R value in the system, that is, the molar ratio of isocyanate to hydroxyl in the system is 1.2.
(3)制备端羟基聚丁二烯改性抗氧剂：取改性端羟基聚丁二烯、二月桂酸二丁基锡和甲苯混合，搅拌均匀，氮气环境下加入异佛尔酮二异氰酸酯，45℃下反应4.5h，再升温至75℃，加入2,2’-硫代双(4-甲基-6-叔丁基苯酚)，保温反应6h，反应结束后收集产物，真空干燥，得到端羟基聚丁二烯改性抗氧剂。(3) Preparation of terminal hydroxyl polybutadiene modified antioxidant: modified terminal hydroxyl polybutadiene, dibutyltin dilaurate and toluene are mixed and stirred evenly, isophorone diisocyanate is added under nitrogen environment, the reaction is carried out at 45°C for 4.5 hours, the temperature is then raised to 75°C, 2,2'-thiobis(4-methyl-6-tert-butylphenol) is added, and the reaction is kept warm for 6 hours. After the reaction is completed, the product is collected and vacuum dried to obtain the terminal hydroxyl polybutadiene modified antioxidant.
所述改性端羟基聚丁二烯、异佛尔酮二异氰酸酯的摩尔比为2：1；所述二月桂酸二丁基锡用量为异佛尔酮二异氰酸酯的1.5wt％；所述2,2’-硫代双(4-甲基-6-叔丁基苯酚)、异 佛尔酮二异氰酸酯的摩尔比为3：1。The molar ratio of the modified terminal hydroxyl polybutadiene and isophorone diisocyanate is 2:1; the amount of dibutyltin dilaurate is 1.5wt% of isophorone diisocyanate; the 2,2'-thiobis(4-methyl-6-tert-butylphenol), isophorone diisocyanate and dibutyltin dilaurate are 1.5wt% of isophorone diisocyanate. The molar ratio of phorone diisocyanate is 3:1.
(4)将端羟基聚丁二烯改性抗氧剂、抗氧剂1010混合，得到复配抗氧剂；所述端羟基聚丁二烯改性抗氧剂、抗氧剂1010质量比为5：1。(4) Mixing the terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 to obtain a compound antioxidant; the mass ratio of the terminal hydroxyl polybutadiene modified antioxidant and antioxidant 1010 is 5:1.
以质量份数计，取90份再生高密度聚乙烯、8份高密度聚乙烯、2份炭黑、12份相容剂、1.5份润滑剂、10份聚氨酯弹性体A、1.5份复配抗氧剂混合，熔融挤出，得到所述聚乙烯。所述相容剂为马来酸酐接枝聚乙烯；所述润滑剂为硬脂酸钙。90 parts of recycled high-density polyethylene, 8 parts of high-density polyethylene, 2 parts of carbon black, 12 parts of compatibilizer, 1.5 parts of lubricant, 10 parts of polyurethane elastomer A, and 1.5 parts of compound antioxidant are mixed by mass, and melt extruded to obtain the polyethylene. The compatibilizer is maleic anhydride grafted polyethylene; and the lubricant is calcium stearate.
检测实验：Detection experiment:
拉伸强度：取实施例1～3、对比例1～5制备的聚乙烯，注塑成型，制得哑铃状样品，注塑温度为180℃；参照GB/T1040-2006公开的方法测试拉伸强度，拉伸速率为50mm/min，标距为25mm。Tensile strength: The polyethylene prepared in Examples 1 to 3 and Comparative Examples 1 to 5 was injection molded to obtain dumbbell-shaped samples at an injection molding temperature of 180°C. The tensile strength was tested according to the method disclosed in GB/T1040-2006 at a stretching rate of 50 mm/min and a gauge length of 25 mm.
200℃氧化诱导期：参照GB/T19466.6-2009公开的方法测试氧化诱导期，升温速率为20℃/min，升温至200℃，记录200℃氧化诱导期。200°C oxidation induction period: refer to the method disclosed in GB/T19466.6-2009 to test the oxidation induction period, with a heating rate of 20°C/min, heating to 200°C, and recording the 200°C oxidation induction period.
抗氧剂的耐迁移性能：取实施例1～3、对比例1～5制备的聚乙烯，注塑成型，注塑温度为180℃，制得片状试样，尺寸为15cm×15cm×1cm，置于30mL无水乙醇中浸泡，50℃水浴下放置48h，取出后40℃下真空干燥12h，重新测200℃氧化诱导期。
Anti-migration performance of antioxidants: Take the polyethylene prepared in Examples 1 to 3 and Comparative Examples 1 to 5, and injection mold them at an injection molding temperature of 180°C to obtain a sheet sample with a size of 15 cm×15 cm×1 cm. Immerse it in 30 mL of anhydrous ethanol, place it in a 50°C water bath for 48 hours, take it out and vacuum dry it at 40°C for 12 hours, and re-measure the 200°C oxidation induction period.
结论：根据以上数据可知，方案通过调整对端羟基聚丁二烯1进行改性，以此制备聚氨酯弹性体A，再利用聚氨酯弹性体A、聚氨酯弹性体B、聚氨酯弹性体C复配实现聚乙烯增强；同时采用复配抗氧剂保证产品抗老化性能。Conclusion: According to the above data, the scheme modifies the terminal hydroxyl polybutadiene 1 to prepare polyurethane elastomer A, and then uses polyurethane elastomer A, polyurethane elastomer B, and polyurethane elastomer C to achieve polyethylene reinforcement; at the same time, a compound antioxidant is used to ensure the anti-aging performance of the product.
本发明公开了一种海洋渔网用再生高密度聚乙烯及其制备方法，方案整体配方适宜， 各步骤工艺参数得当，制备得到的聚乙烯不仅具有优异的力学性能，强度高，且抗老化性能优异，具有较高的实用性。The invention discloses a recycled high-density polyethylene for marine fishing nets and a preparation method thereof. The overall formula of the scheme is suitable. The process parameters of each step are appropriate, and the prepared polyethylene not only has excellent mechanical properties and high strength, but also excellent anti-aging properties and high practicality.
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
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