Dynamic covalent cross-linking material for enhancing polyethylene performance and preparation method and application thereof

A covalent cross-linking and dynamic cross-linking technology, applied in the field of polymer materials, can solve the problems of increasing the processing difficulty of cross-linked polyethylene materials, restricting the recycling and reuse of cross-linked polyethylene, and achieving excellent creep resistance. , The effect of polyethylene performance improvement and good operability

Active Publication Date: 2021-02-12
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The stable chemical structure significantly increases the processing difficulty of cross-linked polyethylene materials, and greatly limits the recycling and reprocessing of cross-linked polyethylene

Method used

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  • Dynamic covalent cross-linking material for enhancing polyethylene performance and preparation method and application thereof
  • Dynamic covalent cross-linking material for enhancing polyethylene performance and preparation method and application thereof
  • Dynamic covalent cross-linking material for enhancing polyethylene performance and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] The synthesis of embodiment 1 borate-containing polycyclooctene PCOE-B

[0039]

[0040] Take a 250 mL round bottom flask, add 4.40 g of cyclooctene, 1.66 g of cyclooctene borate monomer (compound 1), 100 mL of anhydrous dichloromethane, and stir at room temperature. 8.5 mg of Grubbs second-generation catalyst (Grubbs G2) was dissolved in 5 mL of dichloromethane and added to the monomer solution. After reacting at room temperature for 6 hours, 10 μL of vinyl n-butyl ether was added to terminate the reaction. The reaction liquid was dropped into anhydrous methanol to precipitate the polymer, and after vacuum drying at 40° C. for 12 hours, 5.56 g of the product was obtained, with a yield of 92%.

Embodiment 2

[0041] The synthesis of embodiment 2 borate-containing polyethylene PE-B

[0042]

[0043] Take a 150mL thick-walled explosion-proof pressure-resistant bottle, weigh cyclooctene copolymer PCOE-B (0.22g), and dissolve it with 10mL o-xylene. Add p-toluenesulfonyl hydrazide (1.86g, 10mmol), 2,6-di-tert-butyl-4-methylphenol (17.6mg, 0.08mmol), triethylamine (1.01g, 10mmol), tighten the bottle mouth to The bottle was sealed and heated to 120°C for 12 hours. After the reaction, the reaction solution was added dropwise into 100 mL of anhydrous methanol to precipitate a polymer, and vacuum-dried at 60° C. for 12 hours to obtain 0.22 g of the product, with a yield of 100%.

[0044] The second part of the synthesis of dynamically cross-linked polyethylene

Embodiment 3

[0045] The synthesis of embodiment 3 linking agent

[0046]

[0047] Synthesis of 1,6-hexanediboronic acid (2): Take a clean 250mL three-necked round-bottom flask, a spherical condenser, a 100mL constant pressure dropping funnel, apply vacuum silicone grease to the contact part of the grinding port, and inject nitrogen gas after the instrument is assembled. Reactants, solvents, etc. were all added under nitrogen atmosphere. 1,6-Dibromohexane (7.32g, 30.00mmol) was dissolved in 60mL of anhydrous tetrahydrofuran and transferred to a constant pressure dropping funnel, and 2.16g (90.00mmol) of magnesium powder was weighed and added to the flask. Open the constant pressure dropping funnel, drop about 10mL of 1,6-dibromohexane solution into the round bottom flask, heat rapidly to reflux the solvent. Add the remaining 1,6-dibromohexane solution dropwise. During the process, keep the solvent in a slightly boiling state. After the dropwise addition, continue to heat and reflux for ...

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Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a dynamic covalent cross-linking material for enhancing polyethylene performance and a preparation method and application thereof. The dynamic covalent cross-linking material is prepared from linear polyethylene with a borate group and a borate cross-linking agent through a borate exchange reaction,wherein the borate cross-linking agent is prepared from polybasic boric acid molecules and 1, 2-diol molecules or 1, 3-diol molecules through a dehydration condensation reaction; according to the dynamic covalent cross-linking polyethylene material, conversion and recombination of a polymer network can be realized through reversible exchange reaction among different borate groups. The dynamic covalent cross-linking polyethylene is added into commercial thermoplastic polyethylene to synthesize a polyethylene/dynamic cross-linked polyethylene composite polymer material; the mechanical properties (such as tensile strength and Young's modulus), creep resistance, solvent resistance, heat resistance and the like of the composite polymer material are remarkably enhanced, and the composite polymer material can be used for repeated processing, repeated shaping and 3D printing.

Description

technical field [0001] The invention belongs to the technical field of polymer materials, and in particular relates to a dynamic covalent cross-linked polyethylene material and its preparation method and application. Background technique [0002] Polyethylene (PE) is one of the most widely produced and used general-purpose plastics in the world. As of 2019, the global annual output of polyethylene has exceeded 100 million tons, and it is widely used in film, packaging, pipe, insulation and other fields, and plays an extremely important role in human production and life. [0003] However, polyethylene products usually have poor heat resistance, and they are prone to creep in high temperature environments, resulting in irreversible deformation of the product. Therefore, polyethylene materials can only be used at lower temperatures (for example, below 80°C), which limits the use range of polyethylene materials (Chem.Rev.1957,57,665-742; J.Mater.Sci.1994 ,294-323; Patent No.: ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08J3/24C08L65/00C08K5/55C08G61/12C08L23/06
CPCC08J3/24C08G61/123C08J3/246C08G2261/12C08G2261/3322C08G2261/418C08G2261/3342C08G2261/724C08G2261/76C08J2365/00C08K5/55C08J2323/06C08J2465/00
Inventor 陈茂王宗涛
Owner FUDAN UNIV
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