CN109134986B - Dual-crosslinking self-repairing epoxidized natural rubber and preparation method and application thereof - Google Patents
Dual-crosslinking self-repairing epoxidized natural rubber and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of rubber, and discloses double-crosslinking self-repairing epoxidized natural rubber as well as a preparation method and application thereof. The self-repairing epoxidized natural rubber is mainly prepared from the following components in parts by weight: 100 parts of epoxidized natural rubber, 3-35 parts of vulcanization assistant, 0.1-10 parts of sulfur, 0.1-10 parts of disulfide bond-containing cross-linking agent and 0.1-10 parts of reaction catalyst. The disulfide bond-containing crosslinking agent is more than one of 2,2 ' -dithiodibenzoic acid, 4 ' -diaminodiphenyl disulfide, 2 ' -diaminodiphenyl disulfide, 3 ' -dithiodipropionic acid and 4,4 ' -dithiodibutanoic acid. The invention also discloses a preparation method of the self-repairing epoxidized natural rubber. The self-repairing epoxidized natural rubber disclosed by the invention can realize high self-repairing rate when being damaged, has better mechanical strength and is beneficial to prolonging the service life of rubber products.
Description
Technical Field
The invention belongs to the field of functional rubber, and particularly relates to double-crosslinked self-repairing epoxidized natural rubber as well as a preparation method and application thereof.
Background
Rubber has irreplaceable importance in the fields of seals, tires and shock absorbers, but practical application thereof is seriously hindered due to the problems of resource waste, environmental pollution and the like caused by difficult effective recycling. In addition, rubber materials suffer from bottlenecks in expanding their applications to the field of advanced smart materials. If a self-repairing system is introduced into a rubber molecular chain network through reasonable design, the rubber material has both strength and self-repairing functionality, the service life of a rubber product can be greatly prolonged, and the organic combination of rubber material functionalization and sustainable development concept is realized.
Raw rubber with low strength and low modulus usually has no practical value, and better comprehensive performance can be obtained by proper crosslinking, and the rubber is not favored by researchers in the self-repairing field due to poor structural designability and lack of molecular chain fluidity after crosslinking. Therefore, most self-healing systems are specifically designed and synthesized. The currently reported technology for self-repairing rubber mainly depends on the addition of microcapsules containing a repairing agent and the construction of a non-covalent bond cross-linked network to realize a self-repairing function (see patents CN103467791, CN104014288 and CN107987188A), but the stable dispersion and compatibility of the microcapsules in a rubber matrix are greatly examined by rubber processing procedures, while the non-covalent bond cross-linked network mainly depends on the introduction of hydrogen bonds, ionic bonds, metal coordination bonds and the like into a system to construct a bond reversible cross-linked network, and compared with the covalent bond cross-linked network, the acting force is weak, the structural stability of most products is poor, creep is easy to generate, and the mechanical property is insufficient.
In addition, there is also a report on a technology for realizing a rubber self-repairing function by constructing a reversible covalent cross-linking network (see patent CN104610587A and literature (Xiang H P, Qian H J, Lu Z Y, et al crack healing and repairing of a vulcanized rubber by sintering the recycling of the molecular chain and cross-linking networks [ J ] Green Chemistry,2015,17(8):4315-4325.), but generally the cross-linking density of the system is low, so as to ensure a certain molecular chain fluidity to realize self-repairing, and a large amount of reversible bond-containing small molecular substances are required to make up for the deficiency of reversible bond content in a low cross-linking network structure, so that the problem of difficult compromise between mechanical strength and self-repairing performance is faced, the material strength is only 3-4, and only about 80% of original repairing performance can be recovered after repairing under MPa. The lower mechanical properties limit its practical application.
Disclosure of Invention
The invention aims to provide a double-crosslinking self-repairing epoxidized natural rubber and a preparation method thereof aiming at the defects of the prior art. The invention selects a rubber matrix with a plurality of functional groups on a molecular chain to construct a double-crosslinked network system, the crosslinked network is dynamically reversible, and multiple reversible functions can be introduced through a plurality of functional sites, so that the mechanical strength and the self-repairing performance of the material can be effectively balanced.
The preparation process of the self-repairing rubber provided by the invention is simple and easy to operate, and the obtained material has both strength and high repairing efficiency, is beneficial to prolonging the service life of rubber products and conforms to the concept of sustainable development.
Another object of the present invention is to provide the use of the above double cross-linked self-healing epoxidized natural rubber. The double cross-linked self-repairing epoxidized natural rubber is applied to the fields of military equipment, electronic products, automobiles, airplanes and building materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
a double cross-linked self-repairing epoxidized natural rubber is mainly prepared from the following components in parts by weight:
100 parts of epoxidized natural rubber, 3-35 parts of vulcanization assistant, 0.1-10 parts of sulfur, 0.1-10 parts of disulfide bond-containing cross-linking agent and 0.1-10 parts of reaction catalyst. The disulfide-containing cross-linking agent contains-COOH and/or-NH2。
The disulfide bond-containing cross-linking agent is more than one of 2,2 ' -dithiodibenzoic acid, 4 ' -diaminodiphenyl disulfide, 2 ' -diaminodiphenyl disulfide, 3 ' -dithiodipropionic acid and 4,4 ' -dithiodibutanoic acid;
the reaction catalyst is more than one of 1, 2-dimethyl imidazole, 1-methyl imidazole, 4-methyl imidazole and 1-ethyl imidazole;
the rubber matrix is epoxidized natural rubber, and the epoxidation degree is 25-75%.
The vulcanizing assistant is a conventional vulcanizing assistant and comprises the following components in parts by weight: 0.5-5 parts of a neutralizing agent, 1-5 parts of zinc oxide, 0.5-5 parts of stearic acid, 0.5-5 parts of an accelerator, 0.5-5 parts of an anti-aging agent and 0-10 parts of a plasticizer.
The neutralizing agent is alkali substances such as basic magnesium carbonate, sodium carbonate and basic zinc carbonate; the accelerator is at least one of N-tertiary butyl-2-benzothiazole sulfonamide, accelerator CZ, accelerator NOBS, accelerator DM, accelerator M and the like; the anti-aging agent is at least one of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, anti-aging agent 4010NA, anti-aging agent D, anti-aging agent DNP and the like; the plasticizer is at least one of dioctyl phthalate, dioctyl sebacate DOS, dibutyl sebacate DBS, dibutyl phthalate DBP and the like.
The preparation method of the double-crosslinking self-repairing epoxidized natural rubber comprises the following steps:
s1: uniformly mixing 100 parts by weight of epoxidized natural rubber, 3-35 parts by weight of a vulcanization assistant, 0.1-10 parts by weight of sulfur, 0.1-10 parts by weight of a disulfide bond-containing cross-linking agent and 0.1-10 parts by weight of a reaction catalyst at 40-150 ℃ to prepare a rubber compound;
s2: and (2) standing the mixed rubber obtained in the step (1), turning and refining the mixed rubber to obtain pieces, and vulcanizing to obtain the double cross-linked self-repairing epoxidized natural rubber.
The vulcanization condition is that the temperature is 150-200 ℃ and the vulcanization condition is 80-150 kgf/cm2Vulcanizing under the condition; the vulcanization time is 5-40 minutes. The standing time is 8-16 hours.
The self-repairing principle of the double-crosslinking self-repairing epoxidized natural rubber is as follows: the molecular chain of the epoxidized natural rubber adopted by the invention has double active sites of carbon-carbon double bonds and epoxy groups, and the sulfur acts on the double active sites to adjust the vulcanization process to form a first re-crosslinking network mainly comprising disulfide bonds and polysulfide bonds; a diacid containing disulfide bonds and a diamine crosslinking agent act on epoxy group sites, a second double crosslinking network based on disulfide bonds is introduced, a large number of dynamic disulfide bonds are distributed in a rubber system due to the existence of the double crosslinking network, and a certain amount of hydroxyl is generated after ring-opening reaction of the epoxy groups to form reversible hydrogen bonding action with polar groups in the system. When the rubber sections are in full contact with each other, the disulfide bonds can perform exchange reaction at a certain temperature, and the hydrogen bond effect also has thermal reversibility, so that the network structure at the sections is untied, and therefore, molecular chain diffusion, reconnection entanglement and crosslinking can be performed, a new dynamic network structure is further formed to reunite the sections together, the section repair is completed, and the self-repair of the rubber is realized.
The self-repairing method of the double-crosslinking self-repairing epoxidized natural rubber comprises the step of fully contacting the sections of the double-crosslinking self-repairing epoxidized natural rubber under the heating condition in the air atmosphere to finish repairing. The heating temperature is 60-120 ℃; the repairing time is 0.5-24 h.
After the self-repairing of the double-crosslinked self-repairing epoxidized natural rubber provided by the invention, the strength of the self-repaired epoxidized natural rubber can reach 8-9 MPa, and the repairing efficiency is as high as 98%.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, the double cross-linked network self-repairing system is constructed by using the epoxidized natural rubber containing the bifunctional group, the cross-linked network is dynamically reversible, and the disulfide bond and hydrogen bond double reversible bonds are introduced through double cross-linked sites, so that the prepared elastomer has sufficient strength and higher self-repairing efficiency, and the defects that the existing rubber self-repairing technology cannot give consideration to both the mechanical property and the self-repairing efficiency of the material are overcome;
(2) the invention adopts the conventional rubber processing technology for processing, and the preparation technology is simple and reliable;
(3) the epoxidized natural rubber prepared by the invention has a self-repairing function, and a repairing agent is not required to be added during repairing, so that the service life of industrial vulcanized rubber can be effectively prolonged, and the problems of resource waste and the like in the rubber industry can be solved.
Drawings
FIG. 1 is a schematic diagram of the repairing mechanism of the double cross-linked self-repairing epoxidized natural rubber of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the reagents and processing aids used in the examples were purchased from commercial sources and were not purified prior to use. The repairing mechanism of the double-crosslinking self-repairing epoxidized natural rubber is schematically shown in figure 1.
The repair efficiency (. eta.) is defined as the tensile strength (. sigma.) after repairhealed) Tensile strength (σ) as receivedvirgin) The ratio of (A) to (B) is as follows:
in the formula sigmahealed-tensile strength of the sample after repair; sigmavirgin-tensile strength as received.
The parts used in examples 1 to 11 and comparative examples 1 to 2 are parts by weight.
Example 1
Plasticating 100 parts of epoxidized natural rubber with the epoxidation degree of 25 percent on an open mill for 3 minutes at 50 ℃, coating a roll, adding 0.5 part of basic magnesium carbonate, 3 parts of zinc oxide, 3 parts of stearic acid, 0.5 part of N-tert-butyl-2-benzothiazole sulfonamide, 1 part of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 10 parts of dioctyl phthalate, 1 part of sulfur, 1 part of 2, 2' -dithiodibenzoic acid and 1 part of 1, 2-dimethyl imidazole, and uniformly mixing to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2And (4) vulcanizing to obtain a 2mm sheet to obtain the double-crosslinked self-repairing epoxidized natural rubber. After standing for 24h at room temperature, the mechanical properties of the material were determined by tensile testing. And after the original shape of the material is sheared off, the two sections are fully contacted, and after the material is repaired for 24 hours at 120 ℃, the mechanical property of the material is tested again to obtain the stress-strain curves of the original shape and the repaired sample. The schematic diagram of the repair mechanism of the double-crosslinked self-repairing epoxidized natural rubber of the present invention is shown in fig. 1. In the figure, S-is a disulfide bond cross-linked network structure formed after double vulcanization of sulfur and a disulfide bond cross-linking agent.
Example 2
Plasticating 100 parts of epoxidized natural rubber with the epoxidation degree of 40 percent on an open mill for 3 minutes at 50 ℃, coating rollers, adding 3 parts of basic magnesium carbonate, 3 parts of zinc oxide, 1 part of stearic acid, 0.5 part of N-tert-butyl-2-benzothiazole sulfonamide, 3 parts of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 8 parts of dioctyl phthalate, 1 part of sulfur, 2 parts of 3, 3' -dithiodipropionic acid and 2 parts of 1-methylimidazole, and uniformly mixing to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2And (4) vulcanizing to obtain a 2mm sheet to obtain the double-crosslinked self-repairing epoxidized natural rubber. After the mixture is stood for 24 hours at room temperature,the mechanical properties of the material were determined by tensile testing. And after the original shape of the material is sheared off, the two sections are fully contacted, the mechanical property of the material is tested again after the material is repaired for 20 hours at 110 ℃, and the stress-strain curves of the original shape and the repaired sample are obtained.
Example 3
Plasticating 100 parts of epoxidized natural rubber with the epoxidation degree of 50 percent on an open mill for 3 minutes at 50 ℃, coating a roll, adding 2 parts of basic magnesium carbonate, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of N-tert-butyl-2-benzothiazole sulfonamide, 3 parts of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 5 parts of dioctyl phthalate, 1 part of sulfur, 3.2 parts of 4, 4' -dithiodibutyrate and 2 parts of 1, 2-dimethyl imidazole, and uniformly mixing to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2And (4) vulcanizing to obtain a 2mm sheet to obtain the double-crosslinked self-repairing epoxidized natural rubber. After standing for 24h at room temperature, the mechanical properties of the material were determined by tensile testing. And after the original shape of the material is sheared off, the two sections are fully contacted, and after the material is repaired for 24 hours at 120 ℃, the mechanical property of the material is tested again to obtain the stress-strain curves of the original shape and the repaired sample.
Example 4
Plasticating 100 parts of epoxidized natural rubber with the epoxidation degree of 40 percent on an open mill for 3 minutes at 50 ℃, coating a roll, adding 1 part of basic magnesium carbonate, 5 parts of zinc oxide, 1 part of stearic acid, 0.5 part of N-tertiary butyl-2-benzothiazole sulfonamide, 3 parts of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 1 part of dioctyl phthalate, 0.5 part of sulfur, 0.8 part of 3, 3' -dithiodipropionic acid and 0.5 part of 1, 2-dimethyl imidazole, and uniformly mixing to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2And (4) vulcanizing to obtain a 2mm sheet to obtain the double-crosslinked self-repairing epoxidized natural rubber. After standing for 24h at room temperature, the mechanical properties of the material were determined by tensile testing. And after the original shape of the material is sheared off, fully contacting the two sections, repairing at 120 ℃ for 12 hours, and testing the mechanical property of the material again to obtain the stress-strain curves of the original shape and the repaired sample.
Example 5
At 50 deg.CAccording to the weight portion, 100 portions of epoxidized natural rubber with the epoxidation degree of 50 percent are plasticated on an open mill for 3 minutes, 2 portions of basic magnesium carbonate, 5 portions of zinc oxide, 1 portion of stearic acid, 0.5 portion of N-tertiary butyl-2-benzothiazole sulfenamide, 1 portion of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 3 portions of dioctyl phthalate, 0.8 portion of sulfur, 0.8 portion of 3, 3' -dithiodipropionic acid and 1 portion of 1, 2-dimethyl imidazole are added after roller wrapping, and the mixture is evenly mixed to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2And (4) vulcanizing to obtain a 2mm sheet to obtain the double-crosslinked self-repairing epoxidized natural rubber. After standing for 24h at room temperature, the mechanical properties of the material were determined by tensile testing. And after the original shape of the material is sheared off, the two sections are fully contacted, and after the material is repaired for 24 hours at 120 ℃, the mechanical property of the material is tested again to obtain the stress-strain curves of the original shape and the repaired sample.
Example 6
Plasticating 100 parts of epoxidized natural rubber with the epoxidation degree of 50 percent on an open mill for 3 minutes at 50 ℃, coating a roll, adding 5 parts of basic magnesium carbonate, 5 parts of zinc oxide, 3 parts of stearic acid, 2 parts of N-tert-butyl-2-benzothiazole sulfonamide, 4 parts of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 2 parts of dioctyl phthalate, 1.5 parts of sulfur, 0.8 part of 2, 2' -dithiodibenzoic acid and 2 parts of 1, 2-dimethyl imidazole, and uniformly mixing to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2And (4) vulcanizing to obtain a 2mm sheet to obtain the double-crosslinked self-repairing epoxidized natural rubber. After standing for 24h at room temperature, the mechanical properties of the material were determined by tensile testing. And after the original shape of the material is sheared off, the two sections are fully contacted, and after the material is repaired for 24 hours at 120 ℃, the mechanical property of the material is tested again to obtain the stress-strain curves of the original shape and the repaired sample.
Example 7
Plasticating 100 parts of epoxidized natural rubber with the epoxidation degree of 50 percent on an open mill for 3 minutes at 50 ℃, coating rollers, and then adding 2 parts of basic magnesium carbonate, 5 parts of zinc oxide, 1 part of stearic acid, 0.8 part of N-tertiary butyl-2-benzothiazole sulfonamide, 1 part of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer and 1 part of dioctyl phthalate3 parts of ester, 0.5 part of sulfur, 0.8 part of 2,2 '-dithiodibenzoic acid, 0.8 part of 3, 3' -dithiodipropionic acid and 1 part of 1, 2-dimethyl imidazole are uniformly mixed to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2And (4) vulcanizing to obtain a 2mm sheet to obtain the double-crosslinked self-repairing epoxidized natural rubber. After standing for 24h at room temperature, the mechanical properties of the material were determined by tensile testing. And after the original shape of the material is sheared off, the two sections are fully contacted, and after the material is repaired for 24 hours at 120 ℃, the mechanical property of the material is tested again to obtain the stress-strain curves of the original shape and the repaired sample.
Example 8
Plasticating 100 parts of epoxidized natural rubber with the epoxidation degree of 50 percent on an open mill for 3 minutes at 50 ℃, coating a roll, adding 2 parts of basic magnesium carbonate, 5 parts of zinc oxide, 1 part of stearic acid, 0.5 part of N-tert-butyl-2-benzothiazole sulfonamide, 1 part of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 3 parts of dioctyl phthalate, 0.8 part of sulfur, 1.6 parts of 2, 2' -dithiodibenzoic acid, 0.8 part of 3, 3-dithiodipropionic acid and 1 part of 1, 2-dimethyl imidazole, and uniformly mixing to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2And (4) vulcanizing to obtain a 2mm sheet to obtain the double-crosslinked self-repairing epoxidized natural rubber. After standing for 24h at room temperature, the mechanical properties of the material were determined by tensile testing. And after the original shape of the material is sheared off, the two sections are fully contacted, and after the material is repaired for 24 hours at the temperature of 110 ℃, the mechanical property of the material is tested again to obtain the stress-strain curves of the original shape and the repaired sample.
Example 9
Plasticating 100 parts of epoxidized natural rubber with the epoxidation degree of 50 percent on an open mill for 3 minutes at 50 ℃, coating a roll, adding 2 parts of basic magnesium carbonate, 3 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of N-tert-butyl-2-benzothiazole sulfonamide, 1 part of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 3 parts of dioctyl phthalate, 2 parts of sulfur, 3.2 parts of 3, 3' -dithiopropionic acid and 2 parts of 1, 2-dimethyl imidazole, and uniformly mixing to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2The lower part is vulcanized into a 2mm sheet to obtain double cross-linking self-repairingEpoxidized natural rubber. After standing for 24h at room temperature, the mechanical properties of the material were determined by tensile testing. And after the original shape of the material is sheared off, the two sections are fully contacted, and after the material is repaired for 24 hours at 120 ℃, the mechanical property of the material is tested again to obtain the stress-strain curves of the original shape and the repaired sample.
Example 10
Plasticating 100 parts by weight of epoxidized natural rubber with the epoxidation degree of 50 percent on an open mill for 3 minutes at 50 ℃, coating a roll, adding 5 parts by weight of basic magnesium carbonate, 4 parts by weight of zinc oxide, 3 parts by weight of stearic acid, 2 parts by weight of N-tert-butyl-2-benzothiazole sulfonamide, 2 parts by weight of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 8 parts by weight of dioctyl phthalate, 0.3 part by weight of sulfur, 1.6 parts by weight of 2,2 '-dithiodibenzoic acid, 0.4 part by weight of 2, 2' -diaminodiphenyl disulfide and 1 part by weight of 1, 2-dimethyl imidazole, and uniformly mixing to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2And (4) vulcanizing to obtain a 2mm sheet to obtain the double-crosslinked self-repairing epoxidized natural rubber. After standing for 24h at room temperature, the mechanical properties of the material were determined by tensile testing. And after the original shape of the material is sheared off, the two sections are fully contacted, and after the material is repaired for 24 hours at 120 ℃, the mechanical property of the material is tested again to obtain the stress-strain curves of the original shape and the repaired sample.
Example 11
Plasticating 100 parts by weight of epoxidized natural rubber with the epoxidation degree of 50 percent on an open mill for 3 minutes at 50 ℃, coating rollers, adding 3 parts by weight of basic magnesium carbonate, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of N-tert-butyl-2-benzothiazole sulfonamide, 5 parts by weight of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 10 parts by weight of dioctyl phthalate, 1 part by weight of sulfur, 0.8 part by weight of 2,2 '-dithiodibenzoic acid, 0.8 part by weight of 4, 4' -diaminodiphenyl disulfide and 2 parts by weight of 1, 2-dimethylimidazole, and uniformly mixing to prepare a mixed rubber; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2And (4) vulcanizing to obtain a 2mm sheet to obtain the double-crosslinked self-repairing epoxidized natural rubber. After standing for 24h at room temperature, the mechanical properties of the material were determined by tensile testing. Shearing the original shape of the material, fully contacting the two sections, repairing at 120 ℃ for 24h, and testing the mechanical property of the material again to obtain the original materialStress-strain curves for the samples and the repaired samples.
Comparative example 1
Plasticating 100 parts by weight of epoxidized natural rubber with the epoxidation degree of 50 percent on an open mill for 3 minutes at 50 ℃, coating rollers, adding 3 parts by weight of basic magnesium carbonate, 3 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of triallyl isocyanurate, 3 parts by weight of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 8 parts by weight of dibutyl phthalate, 1 part by weight of dicumyl peroxide, 2 parts by weight of 4, 4' -dicarboxydiphenyl ether and 0.5 part by weight of 1, 2-dimethylimidazole, and uniformly mixing to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2Vulcanizing to form a 2mm sheet, standing at room temperature for 24h, and measuring the mechanical property of the material by a tensile test. And after the original shape of the material is sheared off, the two sections are fully contacted, and after the material is repaired for 24 hours at 120 ℃, the mechanical property of the material is tested again to obtain the stress-strain curves of the original shape and the repaired sample.
Comparative example 2
Plasticating 100 parts of epoxidized natural rubber with the epoxidation degree of 50 percent on an open mill for 3 minutes at 50 ℃, coating a roll, adding 5 parts of basic magnesium carbonate, 5 parts of zinc oxide, 1 part of stearic acid, 1.5 parts of N-tert-butyl-2-benzothiazole sulfonamide, 1 part of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, 2 parts of dioctyl phthalate, 0.5 part of sulfur, 2 parts of 4, 4' -succinic acid and 1 part of 1, 2-dimethyl imidazole, and uniformly mixing to prepare a rubber compound; after standing at room temperature for 8 hours, the mixture was heated at 155 ℃ under a pressure of 100kgf/cm2Vulcanizing to form a 2mm sheet, standing at room temperature for 24h, and measuring the mechanical property of the material by a tensile test. And after the original shape of the material is sheared off, the two sections are fully contacted, and after the material is repaired for 24 hours at 120 ℃, the mechanical property of the material is tested again to obtain the stress-strain curves of the original shape and the repaired sample.
The tensile test is adopted to carry out quantitative characterization on the repairing performance of the elastomers in the examples 1-11 and the comparative examples 1-2: and (3) performing a tensile test on a Z010 type electronic universal tester of Zwick company, wherein the tensile rate is 500mm/min, butting two sections after the sample is sheared to ensure that the sections are fully contacted, repairing for 24h at 120 ℃, standing for 24h at room temperature, and stretching the repaired sample again to obtain a stress-strain curve of the repaired sample. The test results are shown in table 1.
TABLE 1 self-healing Performance Table for elastomers in examples and comparative examples
As can be seen from Table 1, the double cross-linked self-healing epoxidized natural rubber of the present invention has excellent strength and self-healing properties.
The vulcanizing assistant in the double-crosslinking self-repairing epoxidized natural rubber is a common assistant, the basic magnesium carbonate is a neutralizer, is used for neutralizing residual acid in the epoxidized natural rubber and reducing the side reaction degree of an epoxy group ring-opening reaction, and can be replaced by other alkaline substances such as sodium carbonate, basic zinc carbonate and the like; zinc oxide and stearic acid are used as active agents for improving the vulcanization efficiency and the aging resistance of the rubber material; n-tertiary butyl-2-benzothiazole sulfonamide is an accelerator NS, is used for shortening the vulcanization time and improving the utilization rate of sulfur, and can be replaced by an accelerator CZ, an accelerator NOBS, an accelerator DM, an accelerator M and the like; the 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer is an anti-aging agent RD, is used for delaying the aging rate of rubber so as to prolong the service life of the rubber, and can be replaced by the anti-aging agent 4010, the anti-aging agent 4010NA, the anti-aging agent D, the anti-aging agent DNP and the like; dioctyl phthalate is used as a plasticizer DOP, is used for reducing intermolecular acting force of rubber, enhancing chain segment movement capacity, reducing glass transition temperature and improving the processability of the rubber, and can be replaced by dioctyl sebacate DOS, dibutyl sebacate DBS, dibutyl phthalate DBP and the like.
Claims (8)
1. A double-crosslinking self-repairing epoxidized natural rubber is characterized in that: the paint is prepared from the following components in parts by weight:
100 parts of epoxidized natural rubber, 3-35 parts of vulcanization assistant, 0.1-2 parts of sulfur, 0.1-10 parts of disulfide bond-containing cross-linking agent and 0.1-10 parts of reaction catalyst; the disulfide-containing cross-linking agent contains-COOH and/or-NH2(ii) a The disulfide bond-containing crosslinking agentIs more than one of 2,2 ' -dithiodibenzoic acid, 4 ' -diaminodiphenyl disulfide, 2 ' -diaminodiphenyl disulfide, 3 ' -dithiodipropionic acid and 4,4 ' -dithiodibutanoic acid;
the vulcanization auxiliary agent comprises the following components in parts by weight: 0.5-5 parts of a neutralizing agent, 1-5 parts of zinc oxide, 0.5-5 parts of stearic acid, 0.5-5 parts of an accelerator, 0.5-5 parts of an anti-aging agent and 0-10 parts of a plasticizer;
the preparation method of the double-crosslinking self-repairing epoxidized natural rubber comprises the following steps:
s1: uniformly mixing 100 parts by weight of epoxidized natural rubber, 3-35 parts by weight of a vulcanization assistant, 0.1-2 parts by weight of sulfur, 0.1-10 parts by weight of a disulfide bond-containing cross-linking agent and 0.1-10 parts by weight of a reaction catalyst at 40-150 ℃ to prepare a rubber compound;
s2: standing the rubber compound obtained in the step S1 for 8-16 hours, and then keeping the temperature at 150-200 ℃ and 80-150 kgf/cm2And vulcanizing under the condition to obtain the double-crosslinking self-repairing epoxidized natural rubber.
2. The double cross-linked self-healing epoxidized natural rubber of claim 1, wherein: the reaction catalyst is more than one of 1, 2-dimethyl imidazole, 1-methyl imidazole, 4-methyl imidazole and 1-ethyl imidazole.
3. The double cross-linked self-healing epoxidized natural rubber of claim 1, wherein: the epoxidation degree of the epoxidized natural rubber is 25-75%.
4. The preparation method of the double-crosslinked self-repairing epoxidized natural rubber according to any one of claims 1 to 3, characterized by comprising the following steps: the method comprises the following steps:
s1: uniformly mixing 100 parts by weight of epoxidized natural rubber, 3-35 parts by weight of a vulcanization assistant, 0.1-2 parts by weight of sulfur, 0.1-10 parts by weight of a disulfide bond-containing cross-linking agent and 0.1-10 parts by weight of a reaction catalyst at 40-150 ℃ to prepare a rubber compound;
s2: and (4) standing the mixed rubber obtained in the step S1 for a period of time, and vulcanizing to obtain the double-crosslinked self-repairing epoxidized natural rubber.
5. The preparation method of the double-crosslinked self-repairing epoxidized natural rubber according to claim 4, characterized by comprising the following steps: the vulcanization condition is that the temperature is 150-200 ℃ and the vulcanization condition is 80-150 kgf/cm2Vulcanizing under the condition; the standing time is 8-16 hours.
6. The application of the double-crosslinked self-repairing epoxidized natural rubber according to any one of claims 1 to 3 in the fields of military equipment, electronic products, automobiles, airplanes and building materials.
7. The self-repairing method of the double-crosslinked self-repairing epoxidized natural rubber according to any one of claims 1 to 3, characterized in that: in the air atmosphere, the cross sections of the double-crosslinking self-repairing epoxidized natural rubber are fully contacted under the heating condition, and the self-repairing of the rubber is completed.
8. The self-repairing method of the double-crosslinked self-repairing epoxidized natural rubber according to claim 7, characterized in that: the heating temperature is 60-120 ℃, and the self-repairing time is 0.5-24 h.
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| WO2002083786A1 (en) * | 2001-04-11 | 2002-10-24 | Cheong Seok Hong | Shape memory rubber composition |
| WO2010128007A1 (en) * | 2009-05-06 | 2010-11-11 | Technische Universiteit Eindhoven | Self-healing polymers |
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| WO2002083786A1 (en) * | 2001-04-11 | 2002-10-24 | Cheong Seok Hong | Shape memory rubber composition |
| WO2010128007A1 (en) * | 2009-05-06 | 2010-11-11 | Technische Universiteit Eindhoven | Self-healing polymers |
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