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Double-crosslinking self-repairing epoxidized natural rubber and preparation method and application thereof

A natural rubber and double cross-linking technology, which is applied in the field of double cross-linking self-repairing epoxidized natural rubber and its preparation, can solve the problems of low mechanical properties, low cross-linking density, weak force, etc., and achieve high repair efficiency, The preparation process is simple to operate and the effect of prolonging the service life

Active Publication Date: 2019-01-04
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Currently reported technologies for rubber self-repair mainly rely on the addition of repair agent-containing microcapsules and the construction of non-covalent bond cross-linked networks to achieve self-repair function (see patents CN103467791, CN104014288, patent application CN107987188A), but the microcapsules in the rubber matrix The stable dispersion and compatibility in rubber are faced with great challenges due to the rubber processing procedures, while the non-covalent bond crosslinking network mainly relies on the introduction of hydrogen bonds, ionic bonds, metal coordination bonds, etc. into the system to form Bond reversible crosslinking network, compared with covalent bond crosslinking network, its force is weak, most of the products have poor structural stability, prone to creep and insufficient mechanical properties
[0004] In addition, there are also reports to realize the technology of rubber self-healing function by constructing a reversible covalent crosslinking network (see patent CN104610587A and literature (Xiang H P, Qian H J, Lu Z Y, et al. Crack healing and reclaiming of vulcanized rubber by triggering the rearrangement of inherentsulfur crosslinked networks[J].Green Chemistry,2015,17(8):4315-4325.)), but usually the crosslinking density of the system is low, so as to ensure a certain molecular chain mobility to achieve self-repair, and it needs A large number of small molecules containing reversible bonds are added to make up for the lack of reversible bond content in the network structure with low crosslinking degree. Therefore, it is often difficult to balance the mechanical strength and self-repairing performance. The material strength is only 3-4MPa, and only Can restore about 80% of the original performance
Low mechanical properties limit its practical application

Method used

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  • Double-crosslinking self-repairing epoxidized natural rubber and preparation method and application thereof
  • Double-crosslinking self-repairing epoxidized natural rubber and preparation method and application thereof
  • Double-crosslinking self-repairing epoxidized natural rubber and preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] At 50°C, in parts by weight, masticate 100 parts of epoxidized natural rubber with an epoxidation degree of 25% on an open mill for 3 minutes, add 0.5 parts of basic magnesium carbonate and 3 parts of zinc oxide after wrapping , 3 parts of stearic acid, 0.5 parts of N-tert-butyl-2-benzothiazole sulfenamide, 1 part of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, phthalate Mix 10 parts of dioctyl formate, 1 part of sulfur, 1 part of 2,2′-dithiodibenzoic acid, and 1 part of 1,2-dimethylimidazole to make a mixed rubber; stand at room temperature for 8 hours Afterwards, at 155°C, pressure 100kgf / cm 2 vulcanized into a 2mm sheet to obtain double cross-linked self-healing epoxidized natural rubber. After standing at room temperature for 24 h, the mechanical properties of the material were measured by tensile test. After the material is cut as it is, the two sections are fully contacted, and after repairing at 120°C for 24 hours, the mechanical properties of the material are...

Embodiment 2

[0036] At 50°C, in parts by weight, masticate 100 parts of epoxidized natural rubber with an epoxidation degree of 40% on an open mill for 3 minutes, add 3 parts of basic magnesium carbonate and 3 parts of zinc oxide after wrapping , 1 part of stearic acid, 0.5 parts of N-tert-butyl-2-benzothiazole sulfenamide, 3 parts of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, phthalate 8 parts of dioctyl formate, 1 part of sulfur, 2 parts of 3,3′-dithiodipropionic acid, and 2 parts of 1-methylimidazole were mixed evenly to obtain a mixed rubber; after standing at room temperature for 8 hours, the 155℃, pressure 100kgf / cm 2 vulcanized into a 2mm sheet to obtain double cross-linked self-healing epoxidized natural rubber. After standing at room temperature for 24 h, the mechanical properties of the material were measured by tensile test. After the material is cut as it is, the two sections are fully contacted, and after repairing at 110°C for 20 hours, the mechanical properties of the mat...

Embodiment 3

[0038] At 50°C, in parts by weight, masticate 100 parts of epoxidized natural rubber with an epoxidation degree of 50% on an open mill for 3 minutes, add 2 parts of basic magnesium carbonate and 5 parts of zinc oxide after wrapping , 2 parts of stearic acid, 2 parts of N-tert-butyl-2-benzothiazole sulfenamide, 3 parts of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, phthalate Mix 5 parts of dioctyl formate, 1 part of sulfur, 3.2 parts of 4,4′-dithiodibutyric acid, and 2 parts of 1,2-dimethylimidazole to make a mixed rubber; let stand at room temperature for 8 hours Afterwards, at 155°C, pressure 100kgf / cm 2 vulcanized into a 2mm sheet to obtain double cross-linked self-healing epoxidized natural rubber. After standing at room temperature for 24 h, the mechanical properties of the material were measured by tensile test. After the material is cut as it is, the two sections are fully contacted, and after repairing at 120°C for 24 hours, the mechanical properties of the material...

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Abstract

The invention belongs to the technical field of rubber, and discloses double-crosslinking self-repairing epoxidized natural rubber and a preparation method and application thereof. The self-repairingepoxidized natural rubber is mainly prepared from, by weight, 100 parts of epoxidized natural rubber, 3-35 parts of a vulcanizing agent, 0.1-10 parts of sulphur, 0.1-10 parts of a cross-linking agentcontaining disulfide bonds and 0.1-10 parts of a reaction catalyst. The cross-linking agent containing the disulfide bonds is one or more of 2,2'-dithiodibenzoic acid, 4,4'-dithiodianiline, 2,2'-dithiodianiline, 3,3'-dithiodipropionic acid and 4,4'-dithiodibutyric acid. The invention further discloses a preparation method of the double-crosslinking self-repairing epoxidized natural rubber. The double-crosslinking self-repairing epoxidized natural rubber can achieve the high self-repairing rate when being subject to damage, has better mechanical strength, and is conductive to prolonging the service life of rubber products.

Description

technical field [0001] The invention belongs to the field of functional rubber, and in particular relates to a double-crosslinked self-repairing epoxidized natural rubber and a preparation method and application thereof. Background technique [0002] Rubber is of irreplaceable importance in the fields of seals, tires and shock absorbers, but its practical application has been severely hindered due to problems such as waste of resources and environmental pollution caused by the difficulty of effective recycling. In addition, rubber materials encounter bottlenecks when expanding their applications to the field of advanced smart materials. If a self-healing system can be introduced into the rubber molecular chain network through reasonable design, so that the rubber material has both strength and self-healing functionality, the service life of rubber products can be greatly extended, and the functionalization and sustainable development of rubber materials can be realized. An ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08L15/00C08J3/24
CPCC08J3/24C08J2315/00
Inventor 卢珣程波杨一林秦锐周佳辉
Owner SOUTH CHINA UNIV OF TECH
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