CN110577709A - High-mechanical-property self-repairing halogenated butyl rubber material and preparation method thereof - Google Patents
High-mechanical-property self-repairing halogenated butyl rubber material and preparation method thereof Download PDFInfo
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- C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
Abstract
The invention discloses a high-mechanical-property self-repairing halogenated butyl rubber material and a preparation method thereof. The preparation method comprises the steps of obtaining uniform blending rubber by a solution blending method or a mechanical blending method through a pyridine derivative, brominated or/and chlorinated butyl rubber and other auxiliaries, and carrying out high-temperature vulcanization molding. According to the high-mechanical-property self-repairing halogenated butyl rubber material provided by the invention, the high-strength ion aggregate gives the halogenated butyl rubber material high mechanical property, and the ion aggregate is subjected to self-repairing by high-temperature dissociation.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to a high-mechanical-property self-repairing halogenated butyl rubber material and a preparation method thereof.
Background
The rubber is used as a reversible polymer with low modulus and large deformation, and has wide application in the fields of daily life, military industry and the like. The existing rubber products are usually vulcanized by adopting irreversible covalent bonds, which causes that the self-repairing and recycling of materials are difficult after the materials are damaged, and the waste, incineration or landfill treatment causes serious black pollution. Therefore, the search for a new material capable of replacing the traditional rubber becomes a hot spot of competitive research of countries in the world. The self-repairing rubber material can heal and recover the mechanical property when being stressed and damaged, has the characteristics of reprocessing and recycling, and is a new material with wide development prospect. However, the self-repairing material always has a contradiction between self-repairing efficiency and high performance, and mechanical properties of the self-repairing material are sacrificed to a certain extent when the self-repairing efficiency is improved, so that the application of the self-repairing material in industry is limited. At present, aiming at the high performance of elastic materials, dynamic sacrificial bonds are introduced mainly through a complex molecular structure design, for example, Pengyi and the like adopt acrylic monomers with long alkyl chains and a pair of monomers with opposite charges, and precipitate products are slowly formed through a dynamic controllable polymerization mode, so that the prepared materials have high strength and high self-repairing efficiency. (Yan Pen, Lijuan ZHao, ChangyueYang, et al.J.Mater.chem.A,2018,6(39): 19066-19074.). Yue Lai and the like adopt a special 'phase-locked' structural design to fix dynamic disulfide bonds in polyurethane in a hard segment, the strength of the disulfide bonds is ensured at room temperature, no exchange reaction occurs, the hard segment is untied at a certain temperature, the disulfide bonds are subjected to exchange reaction, and the prepared material has high strength and high self-repairing efficiency. (Yue Lai, Xiao Kuang, Ping Zhu, et al Advance materials.2018,30(38):1802556 (3-8)). However, there are few simple and practical methods for achieving high performance and high self-repairing efficiency of commercial halogenated butyl rubber, and therefore, in order to meet the requirements for high performance and high self-repairing efficiency of commercial halogenated butyl rubber materials, it is necessary to develop a novel, practically usable and simple crosslinking system.
Disclosure of Invention
Aiming at the technical current situation and the defects of high strength and self-repairing of rubber materials, the first purpose of the invention is to provide a butyl rubber material with high strength and self-repairing; the second purpose of the invention is to provide a simple method for preparing a butyl rubber material with high strength and self-repairing performance, so as to overcome the problem that the mechanical performance and the self-repairing efficiency are contradictory to each other in the improvement of the performance of the butyl rubber material in the prior art.
The basic idea of the invention is that a nucleophilic substitution reaction is carried out between the pyridine derivatives and halogenated butyl rubber to form dynamic ionic cross-linked bonds, so that the rubber material is endowed with high mechanical properties and self-repairing properties. The basic idea for preparing the high-mechanical-property and self-repairing rubber material is to perform nucleophilic substitution reaction on the pyridine derivatives and halogen atoms on brominated or/and chlorinated butyl rubber to form pyridine ring positive charges and free halogen anions grafted on a rubber main chain, so that a plurality of pairs of positive and negative charges are gathered together to form a high-strength ion cross-linked network, and the rubber material is endowed with high mechanical property. In addition, the ion cross-linked network (or ion aggregate) is dissociated at high temperature, the mobility of molecular chains is increased, and the damaged parts of the rubber material are repaired, so that the mechanical property of the material is recovered.
The high-mechanical-property self-repairing halogenated butyl rubber material provided by the invention is characterized in that a pyridine derivative is used as a cross-linking agent, and is uniformly dispersed in a brominated butyl rubber or/and chlorinated butyl rubber matrix by a solution blending method or a mechanical blending method to form a dynamic ionic cross-linked bond, so that the high mechanical property and the self-repairing property are endowed to the halogenated butyl rubber material. The high-mechanical-property self-repairing halogenated butyl rubber material comprises 100 parts by mass of brominated butyl rubber or/and chlorinated butyl rubber and 0.5-10 parts by mass of pyridine derivatives. Preferably, the pyridine derivative is 1.0 to 10.0 parts by mass.
In the above aspect of the present invention, in order to promote the better exertion of the crosslinking effect of the pyridine derivative, it is preferable that the rubber material contains not more than 10 parts by mass of a metal oxide; preferably, not more than 5 parts by mass of the metal oxide. The metal oxide is preferably selected from magnesium oxide, zinc oxide, lead oxide, and the like.
In the technical scheme of the invention, in order to prevent the reduction of rubber performance caused by the escape of halogen elements and the aging of rubber molecular chains in the high-temperature ionic crosslinking process of halogenated butyl rubber, the rubber material also comprises not more than 10 parts by mass of a rubber anti-aging agent; preferably, not more than 5 parts by mass of a rubber antioxidant. The rubber antioxidant can be selected from antioxidant 4010NA, antioxidant D, antioxidant TAP, antioxidant NBC, etc.
In the technical scheme of the invention, in order to meet the specific application of the halogenated butyl rubber and reinforce the mechanical property of the halogenated butyl rubber, the rubber material can also comprise not more than 80 parts by mass of reinforcing filler. Preferably, not more than 60 parts by mass of reinforcing filler; the reinforcing filler can be carbon black, white carbon black and the like.
In the above technical solution of the present invention, the pyridine derivative preferably has at least one pyridine derivative selected from the group consisting of an alkyl group, an amino group, a phenyl group, an N, N- (dialkyl) amino group, an amide, a carboxyl group, an epoxy group, and an aldehyde group as a substituent on the pyridine ring.
The high-mechanical-property self-repairing halogenated butyl rubber material can be prepared by one of the following methods:
(1) Solution blending method: according to the formula, brominated butyl rubber or/and chlorinated butyl rubber are dissolved in a solvent, then other components at least comprising pyridine derivatives are added into the solution to form a uniform and stable dispersion system, the solvent is removed, and the halogenated butyl rubber material with high mechanical property is obtained after vulcanization at 100-160 ℃;
(2) Mechanical blending method: according to the formula, the brominated butyl rubber or/and chlorinated butyl rubber and other components at least comprising pyridine derivatives are added into an internal mixer or an open mill for mixing, the mixed rubber obtained after uniform mixing is vulcanized at 100-160 ℃, and the high-mechanical-property self-repairing halogenated butyl rubber material is obtained.
in the above technical solution of the present invention, the solvent may be selected from tetrahydrofuran or dichloromethane.
the high-mechanical-property self-repairing halogenated butyl rubber material provided by the invention utilizes the nucleophilic substitution reaction of the pyridine derivatives and halogen atoms on the rubber main chain to form dynamic ionic cross-linked bonds, and utilizes the electron withdrawing/supplying characteristics of substituents on the pyridine derivatives and the steric effect of different groups to regulate and control the bonding strength of ionic aggregates, so that the mechanical property, the self-repairing temperature and the self-repairing efficiency of the material can be regulated in a wide range. The metal oxide plays roles of promoting and assisting crosslinking, and the anti-aging agent can prevent the brominated or/and chlorinated butyl rubber from losing halogen elements and aging rubber molecular chains in the high-temperature ion crosslinking process to cause the reduction of rubber performance.
The mechanical property of the high-mechanical-property self-repairing halogenated butyl rubber material provided by the invention is tested by a method specified in GB/T529-1999, the tensile strength of brominated or/and chlorinated butyl rubber is 16-24 MPa, the elongation at break is 500-1600%, and the permanent deformation is 5-18%. The characterization of the self-repairing efficiency is that according to an original sample with a specified size, the original sample is spliced together after being completely cut off by using scissors, the sample is repaired for 1-6 hours at the temperature of 80-110 ℃, the tensile strength and the elongation at break after the repair are tested, the repairing efficiency (%) is (the mechanical property after the repair of the rubber/the original mechanical property of the rubber) multiplied by 100, and the self-repairing efficiency of the obtained brominated or/and chlorinated butyl rubber is 40-95%. The test results show that different pyridine derivatives are used independently and multiple pyridine derivatives are used together, so that the tensile strength and the self-repairing efficiency of the halogenated butyl rubber material are greatly influenced, the 3-and 5-positions of the pyridine ring contain functional groups with larger alkyl groups, the self-repairing performance of the halogenated butyl rubber is promoted, the mechanical properties of the halogenated butyl rubber are influenced by carboxyl, amino, aldehyde and the like on the 4-position of the pyridine ring, but the steric hindrance of the groups on the 3-and 5-positions of the pyridine ring is increased within a certain range, so that the influence on the mechanical properties is small, the improvement of the self-repairing efficiency is facilitated, and the high mechanical properties and the high self-repairing efficiency of the halogenated butyl rubber are ensured; the sizes of the radii of bromine atoms and chlorine atoms on halogenated butyl rubber and the strength of electronegativity are different, and the strength of positive and negative charge ion pairs formed after nucleophilic substitution reaction with pyridine derivatives influences the ionic crosslinking strength and the self-repairing efficiency of rubber materials; the mechanical property of the halogenated butyl rubber material is slightly influenced by adding the metal oxide and the anti-aging agent, but when too much metal oxide is added, once the vulcanization temperature is further increased, the metal oxide participates in the reaction to form covalent crosslinking to a certain degree, and the tensile property and the self-repairing property of the material are influenced; the addition of the reinforcing filler is beneficial to the improvement of the elastic modulus and the stretching strength of the halogenated butyl rubber material, contributes little to the tensile strength of the material, and simultaneously reduces the self-repairing efficiency of the material.
The inventor finds that in the research of the high-mechanical-property self-repairing halogenated butyl rubber material, unimolecular pyridine and halogenated butyl rubber can only form 3-5 MPa of tensile strength and have no great commercial use value, and pyridine derivatives with groups such as alkyl, amino, phenyl, N- (dialkyl alkyl) amino, amide, carboxyl, epoxy, aldehyde and the like introduced to the 3,4 and 5 positions of a pyridine ring and the halogenated butyl rubber can realize the unification of high performance and high self-repairing efficiency of the halogenated butyl rubber material. The groups introduced at the 3,4,5 positions of the pyridine ring may be the same group or different groups. The inventor has completed the invention based on the above findings, and the pyridine derivatives are blended into halogenated butyl rubber, and the halogenated butyl rubber material with high mechanical properties is prepared by high-temperature compression molding.
According to the high-mechanical-property self-repairing halogenated butyl rubber material provided by the invention, the pyridine derivatives and brominated or/and chlorinated butyl rubber are blended by a solution blending method or a mechanical blending method, the pyridine derivatives uniformly dispersed in a rubber matrix and halogen atoms on a halogenated butyl rubber main chain generate nucleophilic substitution reaction to form a high-strength ion cross-linked network, and at a certain temperature, ion aggregates are difficult to dissociate, so that the high mechanical property of the rubber material is ensured; when the material is damaged, the rubber material can be placed at a higher temperature, and the damaged part of the rubber material is repaired by utilizing the ionic aggregates to be heated and slowly dissociated and reassembled, so that the service life of the rubber material is prolonged. The method not only avoids complex molecular structure design, but also does not need complicated preparation procedures, and more importantly, the method solves the unification of high mechanical property and higher self-repairing efficiency of the current commercial halogenated butyl rubber. The high-mechanical-property self-repairing halogenated butyl rubber material provided by the invention has the advantages of high mechanical strength, high self-repairing efficiency, low production cost, simple preparation process, no environmental pollution and easiness in realizing large-scale industrial production.
Drawings
FIG. 1 is a molecular structure diagram of pyridine derivatives, wherein R is1And R2Alkyl groups such as hydrogen, methyl, ethyl, and tert-butyl; t-alkyl, phenyl, amino, N- (dialkyl) amino, amide, carboxyl, epoxy, aldehyde.
FIG. 2 shows the prepared high mechanical property self-repairing brominated butyl rubber material, wherein (a) is without filler and (b) is with filler.
FIG. 3 is a stress-strain curve of brominated butyl rubber materials of example 1 and comparative example 1, wherein # 1 represents a sulfur-crosslinked brominated butyl rubber material and # 2 represents a pyridine derivative ionically-crosslinked brominated butyl rubber material. As can be seen from the figure, the pyridine derivative cross-linked brominated butyl rubber material of the invention has obviously better tensile strength and elongation at break than pure sulfur cross-linked brominated butyl rubber material.
FIG. 4 is a bar graph of the self-healing efficiency of brominated butyl rubber materials of example 1 and comparative example 1, where 1#Represents a sulfur-crosslinked brominated butyl rubber material, 2#Represents a brominated butyl rubber material ionically crosslinked with a pyridine derivative. As can be seen from the figure, the pyridine derivatives of the present inventionThe self-repairing efficiency of the biological cross-linked brominated butyl rubber material is obviously higher than that of a pure sulfur cross-linked brominated butyl rubber material.
FIG. 5 is a bar graph of the tensile strength and self-healing efficiency of the brominated butyl rubber materials of example 8 and comparative example 2, where 1#Brominated butyl rubber material cross-linked with a pyridine derivative having a large steric hindrance, 2#Represents the brominated butyl rubber material crosslinked with the pyridine derivative having a small steric hindrance in comparative example 2. As can be seen from the figure, the steric hindrance on the pyridine ring has a certain influence on the tensile strength of the brominated butyl rubber material, and has a small influence on the self-repairing performance of the rubber.
Detailed Description
The present invention will now be described specifically by way of examples. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
Example 1
A mechanical blending method is adopted, and 2.5g of (3-methyl-4-amino) pyridine, 2.5g of 4-carboxypyridine and 100g of brominated butyl rubber are blended, are thinly passed through an open mill and are molded at 135 ℃ in a compression molding mode. The tensile strength of the prepared sheet is 20.5MPa, the elastic modulus is 1.7MPa, the elongation at break is 1510%, and the self-repairing efficiency at 100 ℃ is 91%.
Example 2
By adopting a solution blending method, firstly 10g of brominated butyl rubber is dissolved in 100ml of tetrahydrofuran solution, then 0.25g of (3-methyl-4-amino) pyridine and 0.25g of 4-carboxypyridine are added and uniformly stirred, then 0.2g of magnesium oxide, 0.3g of zinc oxide, 0.3g of anti-aging agent and other auxiliary agents are added and stirred for 1 hour, then the mixture is poured into a polytetrafluoroethylene mold, and after the solvent is completely volatilized, the mixture is placed into an oven to be vulcanized at 135 ℃. The tensile strength of the prepared film material is 20.4MPa, the elastic modulus is 1.6MPa, the elongation at break is 1350%, and the self-repairing efficiency at 100 ℃ is 91%.
Example 3
A mechanical blending method is adopted, firstly 2.5g of (3-methyl-4-amino) pyridine, 2.5g of 4-carboxypyridine and 100g of brominated butyl rubber are blended, then 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent and other auxiliary agents are added and mixed uniformly, and the mixture is subjected to compression molding at 135 ℃ after being thinned on an open mill. The prepared sheet has the tensile strength of 21MPa, the elastic modulus of 1.8MPa, the elongation at break of 1460 percent and the self-repairing efficiency of 87 percent at 100 ℃.
Example 4
Firstly, 0.25g of (3-methyl-4-amino) pyridine, 0.25g of 4-carboxypyridine and 100g of brominated butyl rubber are blended by adopting a mechanical blending method, then, 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent and other auxiliary agents are added and mixed uniformly, and the mixture is subjected to compression molding at 135 ℃ after being thinned on an open mill. The tensile strength of the prepared sheet is 13.6MPa, the elastic modulus is 1.8MPa, the elongation at break is 1250%, and the self-repairing efficiency at 100 ℃ is 95%.
Example 5
A mechanical blending method is adopted, firstly 2.5g of (3-methyl-4-amino) pyridine, 2.5g of 4-carboxypyridine and 100g of chlorinated butyl rubber are blended, then 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent and other auxiliary agents are added and mixed uniformly, and the mixture is subjected to compression molding at 135 ℃ after being thinned on an open mill. The tensile strength of the prepared sheet is 23.3MPa, the elastic modulus is 1.7MPa, the elongation at break is 1350%, and the self-repairing efficiency at 100 ℃ is 75%.
Example 6
A mechanical blending method is adopted, firstly 2.5g of (3-methyl-4-amino) pyridine, 2.5g of 4-carboxypyridine and 100g of brominated butyl rubber are blended, then 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent and 40g of carbon black are added and mixed uniformly, and the mixture is subjected to compression molding at 135 ℃ after being thinned on an open mill. The tensile strength of the prepared sheet is 19.6MPa, the elastic modulus is 3.4MPa, the elongation at break is 750 percent, and the self-repairing efficiency at 100 ℃ is 46 percent.
Example 7
A mechanical blending method is adopted, firstly 2.5g of (3-methyl-4-amino) pyridine, 2.5g of 4-carboxypyridine, 50g of brominated butyl rubber and 50g of chlorinated butyl rubber are blended, then 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent and other auxiliary agents are added and mixed uniformly, and the mixture is molded by die pressing at 135 ℃ after being thinned on an open mill. The prepared sheet has the tensile strength of 22MPa, the elastic modulus of 1.8MPa, the elongation at break of 1310 percent and the self-repairing efficiency of 82 percent at 100 ℃.
Example 8
A mechanical blending method is adopted, firstly, 2.5g of 4-aminopyridine, 2.5g of 4-carboxypyridine and 100g of brominated butyl rubber are blended, then, 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent and other auxiliary agents are added and mixed uniformly, and the mixture is subjected to compression molding at 135 ℃ after being thinned on an open mill. The prepared sheet has the tensile strength of 21MPa, the elastic modulus of 1.9MPa, the elongation at break of 1430 percent and the self-repairing efficiency of 84 percent at 100 ℃.
Example 9
a mechanical blending method is adopted, firstly 2.5g of (3-methyl-4-amino) pyridine, 2.5g of 4-carboxypyridine and 100g of brominated butyl rubber are blended, then 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent and other auxiliary agents are added and mixed uniformly, and the mixture is subjected to compression molding at 165 ℃ after being thinned on an open mill. The tensile strength of the prepared sheet is 17MPa, the elastic modulus is 2.1MPa, the elongation at break is 1030 percent, and the self-repairing efficiency at 100 ℃ is 42 percent.
Example 10
The mechanical blending method is adopted, firstly 5g of 4-tert-butylpyridine and 100g of brominated butyl rubber are blended, then 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent, 40g of carbon black and other auxiliary agents are added and mixed uniformly, and the mixture is subjected to compression molding at 135 ℃ after being thinly passed on an open mill. The prepared sheet has the tensile strength of 16MPa, the elastic modulus of 2.6MPa, the elongation at break of 1256 percent and the self-repairing efficiency of 56 percent at 100 ℃.
Example 11
The mechanical blending method is adopted, firstly 5g of 4-phenylpyridine and 100g of brominated butyl rubber are blended, then 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent, 40g of carbon black and other auxiliary agents are added and mixed uniformly, and the mixture is subjected to compression molding at 135 ℃ after being thinned and passed on an open mill. The prepared sheet has the tensile strength of 21MPa, the elastic modulus of 2.9MPa, the elongation at break of 1156 percent and the self-repairing efficiency of 52 percent at 100 ℃.
Example 12
A mechanical blending method is adopted, firstly, 2.5g of 4-aldehyde pyridine, 2.5g of (4-diethyl) aminopyridine and 100g of butyl bromide rubber are blended, then, 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent, 40g of carbon black and other auxiliary agents are added and mixed uniformly, and the mixture is subjected to compression molding at 135 ℃ after being thinned on an open mill. The prepared sheet has the tensile strength of 17MPa, the elastic modulus of 1.4MPa, the elongation at break of 1456 percent and the self-repairing efficiency of 72 percent at 100 ℃.
Example 13
The mechanical blending method is adopted, firstly, 2.5g of 4-amido pyridine, 2.5g of 4-methylpyridine and 100g of brominated butyl rubber are blended, then 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent, 40g of carbon black and other auxiliary agents are added and mixed uniformly, and the mixture is molded under the compression condition at 135 ℃ after being thinned on an open mill. The tensile strength of the prepared sheet is 19MPa, the elastic modulus is 1.6MPa, the elongation at break is 1320 percent, and the self-repairing efficiency at 100 ℃ is 74 percent.
Comparative example 1
3g of sulfur, 5g of ZnO, 1.5g of stearic acid, 1g of accelerator, 3g of anti-aging agent and 50g of brominated butyl rubber are blended by adopting a mechanical blending method, placed for 24 hours, thinly passed on an open mill, and molded under pressure at 143 ℃. The tensile strength of the prepared sheet is 7.5MPa, the elongation at break is 720%, and the self-repairing efficiency at 100 ℃ is 5%.
Comparative example 2
A mechanical blending method is adopted, firstly 2.5g of (3, 5-diethyl-4-amino) pyridine, 2.5g of 4-carboxypyridine and 100g of brominated butyl rubber are blended, then 2g of magnesium oxide, 3g of zinc oxide, 3g of anti-aging agent and other auxiliary agents are added and mixed uniformly, and the mixture is subjected to compression molding at 135 ℃ after being thinned on an open mill. The tensile strength of the prepared sheet is 18.7MPa, the elastic modulus is 1.6MPa, the elongation at break is 1560%, and the self-repairing efficiency at 100 ℃ is 91%.
Comparative example 3
1g of stearic acid, 5g of zinc oxide, 2g of accelerator, 2g of antioxidant and 50g of brominated butyl rubber are blended by adopting a mechanical blending method, and are subjected to compression molding at 170 ℃ after being thinly passed on an open mill. The tensile strength of the prepared sheet is 13.6MPa, the elongation at break is 870%, and the self-repairing efficiency at 100 ℃ is 2%.
It can be seen from the data of example 1, comparative example 1 and comparative example 3 that, under the same process preparation conditions, pyridine derivatives, sulfur and pure metal oxides are respectively adopted as cross-linking agents to cross-link brominated butyl rubber, an ionic cross-linking network formed by the pyridine derivatives can realize high tensile strength and high self-repairing efficiency of the brominated butyl rubber, and covalent cross-linking rubber materials of sulfur and metal oxides have low mechanical properties and extremely low self-repairing efficiency; from the examples 1,2 and 3, it can be seen that the solution blending method and the mechanical blending method have little influence on the mechanical properties of the material, and are both suitable for molding and processing the material, and the addition of the metal oxide and the anti-aging agent has a small promotion effect on the tensile strength and the elastic modulus of the material, but cannot cause essential difference, because the crosslinking is mainly generated by pyridine derivatives; from examples 3,5 and 7, it can be seen that the halogen counter ions on the brominated chlorinated butyl rubber have an influence on the mechanical properties of the material, because the ionic radii of the halogen counter ions are different, the acting force formed between the halogen counter ions and the positive charge of pyridine is different, but the influence on the mechanical properties is small whether the material is used alone or in a blending manner, because migration and exchange of different halogen negative ions exist under the blending condition, the whole blending system is homogenized; from example 6, it can be seen that the addition of the reinforcing filler remarkably improves the elastic modulus of the material, but the tensile strength is slightly reduced, and the self-repairing efficiency is obviously reduced. From the example 8 and the comparative example 2, it can be seen that the size of the alkyl group on the pyridine ring in the pyridine derivative has a large influence on the self-repair efficiency of the brominated butyl rubber material, and has a small influence on the mechanical properties, which indicates that the alkyl group as a large steric hindrance group improves the movement of the molecular chain to a certain extent, and meanwhile, because the pyridine ring has a certain extent of pi-pi interaction and the alkyl group increases the dispersion force between the ionic groups, the electrostatic interaction with strong spatial distance sensitivity is reduced to a certain extent, and the dispersion force with low spatial distance sensitivity is increased, so that the influence of the increase of the steric hindrance on the strength of the ionic groups is small, and the improvement of the self-repair efficiency is facilitated. From example 9 and comparative example 3, it is known that metal zinc oxide can be directly subjected to covalent crosslinking, the tensile strength is lower than the crosslinking strength of pyridine derivatives, and the self-repair efficiency is very low, but in the added pyridine derivatives, because the vulcanization temperature is lower, ionic crosslinking of pyridine derivatives is an absolute advantage, and metal oxides such as zinc oxide only play a role in promoting and assisting crosslinking, but when the vulcanization temperature is further increased, a large amount of metal oxides participate in the vulcanization crosslinking reaction, so that the covalent component in a crosslinking network is increased, and the mechanical property and the self-repair efficiency of the material are influenced. From examples 10 to 13, it is understood that the pyridine derivatives having different groups can form a high tensile strength either alone or in combination, but have a certain influence on the self-healing efficiency.
Claims (9)
1. A high-mechanical-property self-repairing halogenated butyl rubber material is characterized in that pyridine derivatives are used as dynamic ionic cross-linking agents, the pyridine derivatives are uniformly dispersed in a brominated butyl rubber or/and chlorinated butyl rubber matrix through a solution blending method or a mechanical blending method to form dynamic ionic cross-linked bonds, and the rubber material is endowed with high mechanical properties and self-repairing properties, and the high-mechanical-property self-repairing halogenated butyl rubber material comprises 100 parts by mass of brominated butyl rubber or/and chlorinated butyl rubber and 0.5-10 parts by mass of the pyridine derivatives.
2. The high-mechanical-property self-repairing halogenated butyl rubber material of claim 1, wherein the rubber material comprises no more than 10 parts by mass of metal oxide.
3. The high mechanical property self-healing halogenated butyl rubber material of claim 2, wherein the metal oxide is at least one of magnesium oxide, zinc oxide and lead oxide.
4. the high-mechanical-property self-repairing halogenated butyl rubber material as claimed in claim 1, wherein the rubber material comprises not more than 10 parts by mass of rubber antioxidant.
5. The high mechanical property self-healing halogenated butyl rubber material of claim 1, wherein the rubber material comprises no more than 80 parts by mass of reinforcing filler.
6. The high mechanical property self-repairing halogenated butyl rubber material as claimed in one of claims 1 to 5, wherein the pyridine derivative is a pyridine derivative with at least one of alkyl, amino, phenyl, N- (dialkyl) amino, amide, carboxyl, epoxy and aldehyde group as the substituent on the pyridine ring.
7. The high-mechanical-property self-repairing halogenated butyl rubber material as claimed in claim 6, wherein the pyridine derivative comprises 1.0-10 parts by mass of the components.
8. The preparation method of the high-mechanical-property self-repairing halogenated butyl rubber material as claimed in one of claims 1 to 7, characterized in that the preparation method is one of the following methods:
(1) Solution blending method: according to the formula, brominated butyl rubber or/and chlorinated butyl rubber are dissolved in a solvent, then other components at least comprising pyridine derivatives are added into the solution to form a uniform and stable dispersion system, the solvent is removed, and the halogenated butyl rubber material with high mechanical property is obtained after vulcanization at 100-160 ℃;
(2) Mechanical blending method: according to the formula, the brominated butyl rubber or/and chlorinated butyl rubber and other components at least comprising pyridine derivatives are added into an internal mixer or an open mill for mixing, the mixed rubber obtained after uniform mixing is vulcanized at 100-160 ℃, and the high-mechanical-property self-repairing halogenated butyl rubber material is obtained.
9. The preparation method of the high-mechanical-property self-repairing halogenated butyl rubber material as claimed in claim 8, wherein the solvent is tetrahydrofuran or dichloromethane.
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