CN108017728B - Rubber composition, modified rubber with self-healing function and preparation method and application thereof - Google Patents
Rubber composition, modified rubber with self-healing function and preparation method and application thereof Download PDFInfo
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- CN108017728B CN108017728B CN201610943368.0A CN201610943368A CN108017728B CN 108017728 B CN108017728 B CN 108017728B CN 201610943368 A CN201610943368 A CN 201610943368A CN 108017728 B CN108017728 B CN 108017728B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
Abstract
The invention relates to the field of rubber, in particular to a rubber composition, modified rubber with a self-healing function, and a preparation method and application of the modified rubber with the self-healing function. The modified rubber with the self-healing function contains diene groups and dienophile groups, and the diene group content is 0.01-5 mol parts and the dienophile group content is 0.01-5 mol parts based on 100 mol parts of rubber structural units in the modified rubber. The modified rubber has good self-healing performance, the optimum self-healing temperature of the modified rubber approximately coincides with the service temperature of a tire, so that the self-healing performance can be effectively exerted, and the modified rubber still has good comprehensive performance such as aging resistance.
Description
Technical Field
The invention relates to the field of rubber, in particular to a rubber composition, modified rubber with a self-healing function, and a preparation method and application of the modified rubber with the self-healing function.
Background
With the gradual implementation of the European Union tire labeling method and the United states 'double-reverse' method, the requirements of the automobile industry at home and abroad on the safety, energy conservation and durability of tires are more and more urgent.
In 2015, the total production of tires in China is 5.65 hundred million, wherein the production of radial tires is 5.15 hundred million (1.1 hundred million of all-steel tires and 4.05 hundred million of semi-steel tires), and the production of bias tires is 0.5 hundred million. If the quality of the domestic tire can be improved, the domestic tire has a self-repairing function, the durability and the safety are improved, a large amount of precious rubber and other raw material resources can be saved every year, the environmental pollution is reduced, and the market competitiveness of the domestic tire is improved.
9 months in 2015, the Korea tire announces that an automatic repair tire with the model of 215/55R17Ventus Prime2 SEALGARD is provided to be matched with public Touran. The tire is the first automatic repair tire developed by Hantai, and has superior safety performance compared with the common tire. The tire is made by the Korean Tai 'automatic repair technology', a layer of self-repairing tire viscous material is coated inside the tire, and when pricked, the tire body can automatically seal the pricked holes with the diameter not more than 5 mm, so that the tire surface is repaired. Therefore, the automobile provided with the automatic tire repairing device does not need to carry a spare tire, and the trouble of replacing the tire by the automobile owner on the roadside is also saved while the space in the automobile is released.
US8962730B2 discloses a self-healing tire shoulder rubber material formulation. Firstly, styrene-butadiene rubber and mercapto group-containing compoundReacting with a terpyridine group compound to obtain terpyridine group grafted styrene butadiene rubber; the rubber formulation further comprises a metal salt, such as one or more of ferrous sulfate heptahydrate, ferrous chloride, nickel dichloride, ruthenium chloride, cobalt stearate, zinc stearate, etc., to provide Cu2+、Fe2+、Co2+、Ni2+、Zn2+、Ru2+Plasma; in the using process of the rubber material, Zn is contained in the material2+、Co2+The plasma and terpyridine groups of the styrene butadiene rubber generate coordination reaction and reverse reaction, so that the self-healing of the rubber material is realized.
Patent WO 2013/164843A 1 discloses a self-healing heat-reversible butadiene rubber blend, butadiene rubber and polypropylene grafted by maleic anhydride are blended, then 3-amino-1, 2, 4-benzotriazole is added, and the heat-reversible self-healing of the blend is realized by utilizing the heat-reversible hydrogen bond interaction between polar groups in the blend.
In some patented technologies for preparing self-healing tire rubber compositions, metal ions are one of participants of material self-healing reaction, but the metal ions affect the aging resistance of the rubber material, and the prepared rubber composition has the self-healing capability but the anti-aging performance is affected. In other patent technologies, the self-healing function of the material is realized by utilizing thermally reversible hydrogen bonds or ionic bonds, the technology has an imperfect surface, the hydrogen bonds belong to intermolecular acting force, and the optimal temperature range of the self-healing is not consistent with the temperature range of the tire, so the self-healing material is not suitable for being used as the self-healing material of the tire. Therefore, there is a need to propose a novel method for producing a self-healing rubber composition that can solve the above problems.
Disclosure of Invention
The invention aims to overcome the defects that the self-healing temperature range of the existing modified rubber with the self-healing function is not consistent with the temperature range of the tire and/or the self-healing modification influences the original performance of the rubber, and provides a rubber composition, the modified rubber with the self-healing function, and a preparation method and application of the modified rubber with the self-healing function. The modified rubber has good self-healing performance, the optimum self-healing temperature of the modified rubber approximately coincides with the service temperature of a tire, so that the self-healing performance can be effectively exerted, and the modified rubber still has good comprehensive performance such as aging resistance.
The inventor of the present invention finds that the rubber of the tire shoulder is subjected to reciprocating action force, is easy to generate heat, has cracks and even has structural damage, and greatly improves the safety and the service life of the tire if the material can be self-healed, however, the method used in the prior art enables the tire material to realize reversible chemical reaction of self-healing capacity, the optimal reaction temperature of the reversible chemical reaction is not coincident with the service temperature range of the tire, so that the self-healing effect of the tire material in the use process is influenced, and when some methods in the prior art try to improve the self-healing performance of the material, other performances (such as anti-aging performance) of the material are reduced.
The inventor of the invention unexpectedly discovers in the process of in-depth research that the diene group and the dienophile group form weak connection by modifying rubber through the diene group and the dienophile group, random chain scission occurs when a tire material is fractured, the diene and the dienophile generated by chain scission can react again, and cracks are repaired at the molecular level, so that the self-healing function of the material is realized. In addition, the diene group and the dienophile group are organic compound groups, do not contain metal elements, and cannot influence the aging resistance of the tire material. When the preferred diene group and dienophile group are used, the temperature range of self-healing reaction and reverse reaction is in the range of room temperature to 120 ℃, which is the temperature range of the inner part of a tire body in the using process of the tire, and the self-healing requirement in the using process of the tire can be better met. The self-healing reaction of the invention has the characteristics of high selectivity, high efficiency, mild reaction conditions and the like.
The invention provides a modified rubber with a self-healing function, wherein the modified rubber with the self-healing function contains diene groups and dienophile groups, and the diene group content is 0.01-5 mol parts and the dienophile group content is 0.01-5 mol parts based on 100 mol parts of rubber structural units in the modified rubber.
In a second aspect, the invention provides a rubber composition comprising a first agent and a second agent each independently maintained, the first agent comprising a base rubber, a coupling agent and a compound of formula XaR1Y, said second agent comprising a compound of formula R2ZnThe content of the coupling agent is 0.01-5 molar parts based on 100 molar parts of the molar number of the rubber structural unit in the base rubber, and the molecular formula is XaR1The content of Y compound is 0.01-5 mol portions calculated by X group, and the molecular formula is R2ZnThe content of the compound (b) is 0.01-5 molar parts based on the Z group;
wherein any one of the X group and the Z group is a dienophile group, and the other is a dienophile group; r1Is a C1-C16 aliphatic group with or without a polysulfide bond; y is selected from hydroxyl, sulfhydryl and amine; r2Selected from aliphatic groups of C1-C16 and aromatic hydrocarbon groups of C6-C30; n is an integer not less than 2; a is an integer of 1 to 3.
The third aspect of the invention provides a preparation method of modified rubber with a self-healing function, wherein the method comprises the following steps:
(1) mixing base rubber, coupling agent and molecular formula XaR1Carrying out first contact on the compound of Y to obtain the rubber modified by the X group;
(2) modifying the X group modified rubber obtained in the step (1) with a molecular formula of R2ZnThe compound of (a) is subjected to a second contact;
the coupling agent is used in 0.01-5 molar parts based on 100 molar parts of rubber structural units in the base rubber, and the molecular formula is XaR1The compound of Y is used in 0.01-5 molar parts based on X group and has the formula of R2ZnThe amount of the compound (b) is 0.01 to 5 parts by mole based on the Z group;
any one of the X group and the Z groupOne is a dienophile group and the other is a dienophile group; r1Is a C1-C16 aliphatic group with or without a polysulfide bond; y is selected from hydroxyl, sulfhydryl and amine; r2Selected from aliphatic groups of C1-C16 and aromatic hydrocarbon groups of C6-C30; n is an integer not less than 2; a is an integer of 1 to 3.
The fourth aspect of the invention provides the modified rubber with the self-healing function prepared by the method of the third aspect of the invention.
The fifth aspect of the invention provides the application of the modified rubber with the self-healing function of the invention on a tire.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a graph showing the torque with time of the rubber products H1, H2, DH3 and DH4 obtained in the examples and comparative examples.
FIG. 2 is a graph showing the temperature changes with time of rubber products H1, H2, DH3 and DH4 obtained in examples and comparative examples.
FIG. 3 is a graph of the storage shear modulus G' as a function of temperature for three temperature scans of rubber products H2 and DH4 from examples and comparative examples.
FIG. 4 is a graph of the storage shear modulus differential dG'/dT as a function of temperature for three temperature sweeps of the rubber products H2 and DH4 from examples and comparative examples.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a modified rubber with a self-healing function, wherein the modified rubber with the self-healing function contains diene groups and dienophile groups, and the diene group content is 0.01-5 mol parts and the dienophile group content is 0.01-5 mol parts based on 100 mol parts of rubber structural units in the modified rubber.
In the invention, the contents of the diene group, the dienophile group and the coupling agent structural unit in the modified rubber can meet the requirements, namely, a good self-healing function can be realized. Preferably, the diene group content is 0.05 to 2 parts by mole and the dienophile group content is 0.05 to 2 parts by mole based on 100 parts by mole of the rubber structural unit in the modified rubber; more preferably, the diene group content is 0.1 to 1.5 parts by mole and the dienophile group content is 0.1 to 1.5 parts by mole based on 100 parts by mole of the rubber structural unit in the modified rubber; further preferably, the diene group content is 0.2 to 1 part by mole and the dienophile group content is 0.2 to 1 part by mole based on 100 parts by mole of the rubber structural unit in the modified rubber.
In the present invention, preferably, the content of the dienophile group and the dienophile group satisfies the following condition in the case of satisfying the above requirement: the ratio of the mole parts of the diene group and the dienophile group is 0.8-1.2: 1, more preferably 0.9 to 1.1: 1.
in the present invention, the terms "dienophile group" and "dienophile group" are used along the ordinary meaning of the art.
The term "dienic group" generally refers to a group containing a carbon-carbon conjugated double bond, the group attached to the conjugated double bond may be an electron withdrawing group or an electron donating group, and the conjugated double bond may be located on a ring or a straight chain of the compound molecule. In the present invention, the diene group is preferably furyl and/or isobenzofuryl, and most preferably furyl.
The term "dienophile group" generally refers to a group containing an unsaturated carbon-carbon bond such as a carbon-carbon double bond, and the group attached to the carbon-carbon double bond may be an electron withdrawing group or an electron donating group. In the present invention, the dienophile group is most preferably a maleimide group.
In the present invention, the "dienophile group" and the "dienophile group" are preferably arranged in a manner of furyl and maleimide groups and isobenzofuryl and maleimide groups.
When the diene group and the dienophile group are selected in the above preferred embodiment of the present invention, the temperature range at which the diene group and the dienophile group reversibly react is from room temperature to 120 ℃, which is approximately the same as the internal temperature range of the carcass when the tire is used. The modified rubber containing the above-mentioned preferred diene group and dienophile group is more suitable for application to tires.
In the present invention, the rubber structural unit in the modified rubber is the structural unit in the base rubber of the modified rubber, for example, the base rubber may be selected from one or more of butadiene rubber, isoprene rubber, styrene-butadiene rubber, ternary integrated rubber and ethylene-propylene rubber, and the molecular structural formula of the modified rubber is [ -CH ] as exemplified by butadiene rubber2-CH＝CH-CH2-]nOr [ -CH2-CH(-CH＝CH2)-]mThen one [ CH2-CH＝CH-CH2]Or [ -CH2-CH(-CH＝CH2)]The structure is a rubber structural unit in the modified rubber.
In the present invention, the modified rubber having a self-healing function further contains a coupling agent residue structural unit, which is a coupling agent residue introduced into the modified rubber through a reaction of a coupling agent used in the preparation process of the modified rubber having a self-healing function. The kind and content of the structural unit of the residue of the coupling agent are determined in accordance with the kind and content of the coupling agent used in the production process of the modified rubber having a self-healing function (for example, the coupling agent used in the second aspect or the third aspect of the present invention).
Depending on the amount of the coupling agent used, the content of the structural unit of the coupling agent residue is preferably 0.01 to 5 parts by mole, more preferably 0.01 to 2 parts by mole, still more preferably 0.02 to 1.5 parts by mole, and further preferably 0.2 to 1 part by mole, based on 100 parts by mole of the rubber structural unit in the modified rubber. Preferably, the content of the coupling agent residue structural unit also satisfies the following condition in the case that the above requirements are satisfied: the ratio of the coupling agent residue structural unit to the dienophile group or the diene group in parts by mole is 1: 0.8 to 6, preferably 1: 0.9 to 4, more preferably 1: 0.9-1.1.
In a second aspect, the invention provides a rubber composition comprising a first agent and a second agent each independently maintained, the first agent comprising a base rubber, a coupling agent and a compound of formula XaR1Y, said second agent comprising a compound of formula R2ZnThe content of the coupling agent is 0.01-5 molar parts based on 100 molar parts of the molar number of the rubber structural unit in the base rubber, and the molecular formula is XaR1The content of Y compound is 0.01-5 mol portions calculated by X group, and the molecular formula is R2ZnThe content of the compound (b) is 0.01-5 molar parts based on the Z group;
wherein any one of the X group and the Z group is a dienophile group, and the other is a dienophile group; r1Is a C1-C16 aliphatic group with or without a polysulfide bond; y is selected from hydroxyl, sulfhydryl and amine; r2Selected from aliphatic groups of C1-C16 and aromatic hydrocarbon groups of C6-C30; n is an integer not less than 2; a is an integer of 1 to 3.
In the present invention, it is preferable that the molecular formula is X based on 100 parts by mole of the rubber structural unit in the base rubberaR1The content of Y compound is 0.05-2 mole parts calculated by X group, and the molecular formula is R2ZnThe content of the compound (b) is 0.05-2 molar parts in terms of Z group; more preferably, in terms of moles of rubber structural units in the base rubberThe molecular formula is X in 100 molar partsaR1The content of Y compound is 0.1-1.5 mole parts calculated by X group, and the molecular formula is R2ZnThe content of the compound (b) is 0.1-1.5 molar parts based on the Z group; further preferably, the molecular formula is X based on 100 parts by mole of the rubber structural unit in the base rubberaR1The content of the compound of Y is 0.2-1 molar part calculated by X group, and the molecular formula is R2ZnThe content of the compound (b) is 0.2 to 1 molar part based on the Z group.
In the present invention, preferably, the formula is XaR1Y and the formula R2ZnThe content of the compounds of (a) also satisfies the following ratio in the case of satisfying the above requirements: the molecular formula is XaR1The content of the compound of Y in terms of X group and the molecular formula are R2ZnIn a content of compounds (c) in terms of Z groups in a molar ratio of 0.8 to 1.2: 1, more preferably 0.9 to 1.1: 1.
in the present invention, any one of the dienophile group and the dienophile group may be either an X group or a Z group, that is, any one of the dienophile group and the dienophile group may be bonded to the base rubber in step (1) first, or may be bonded to the base rubber in step (2) as a small molecule compound (i.e., R)2Zn) Is connected with the rubber obtained in the step (1). R2ZnWherein the number of Z groups is at least two.
In the present invention, the definition, selection and collocation of the dienophile group and the dienophile group are the same as those described above, and are not described herein again.
In the present invention, R1Is an aliphatic group, the number of carbon atoms of the aliphatic group is preferably C1-C12, more preferably C1-C8; r1May or may not contain polysulfide linkages when R1When a polysulfide linkage is contained, for example, 1 polysulfide linkage may be contained, and the number of S in the polysulfide linkage may be 1 to 8, preferably 1 to 4.
In the present invention, preferably, Y is selected from hydroxyl and mercapto.
In the present invention, preferably, when R is2When the aliphatic group is used, the number of carbon atoms of the aliphatic group is preferably from C1 to C12, more preferably from C1 to C8; when R is2In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having not more than 3 benzene rings, more preferably an aromatic hydrocarbon group having 1 to 2 benzene rings and having carbon atoms of from C6 to C16.
In the present invention, n is preferably an integer of 2 to 4.
In the present invention, preferably, a is 1 or 2.
According to a preferred embodiment of the invention, the formula XaR is1And the compound of Y is 4-maleimide phenol when the X group is dienophile, and is selected from one or more of 2-furancarbinol, 2-furanmethanethiol, difurfuryl disulfide, 2-furanmethylamine, homopolymer of 2-furancarbinol and furan resin when the X group is dienophile.
According to a preferred embodiment of the invention, the formula R2ZnWhen the Z group is a dienophile, one or more compounds selected from the group consisting of N, N '- (4,4' -methylenediphenyl) bismaleimide, N '- (1, 4-phenylene) bismaleimide and N, N' -m-phenylene bismaleimide, and when the Z group is a dienophile, one or more compounds selected from the group consisting of homopolymers of 2-furancarbinols and furan resins.
In the present invention, the content of the coupling agent is preferably 0.01 to 2 parts by mole, more preferably 0.02 to 1.5 parts by mole, and still more preferably 0.2 to 1 part by mole, based on 100 parts by mole of the rubber structural unit in the base rubber.
In the present invention, it is preferable that the content of the coupling agent satisfies the following condition in addition to the above requirement: the content of the coupling agent and the molecular formula are XaR1The content of the compounds of Y in terms of Y groups is in a molar ratio of 1: 0.8 to 6, preferably 1: 0.9 to 4, more preferably 1: 0.9-1.1. The coupling agent is preferably a silane coupling agent.
In the present invention, the kind of the coupling agent is not particularly limited, and may be a conventional one in the artThe coupling agent used. According to a preferred embodiment of the invention, the coupling agent from which the structural units of the coupling agent originate is of formula R3(SiX1X2X3)mThe silane coupling agent of (1); wherein R is3Aliphatic groups of C1-C16 or aromatic hydrocarbon groups of C6-C30 to which one or more groups of vinyl, epoxy, amino, methacryloxy, mercapto, 3-propionylthio-1-propyl and polysulfide bonds are attached; wherein when R is3When the aliphatic group is an aliphatic group, the number of carbon atoms of the aliphatic group is preferably C1-C12, more preferably C1-C8, and the group attached thereto is preferably one or more of an amino group, an epoxy group, a mercapto group and a polysulfide bond; wherein when R is3When the aromatic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having a benzene ring number of not more than 3, more preferably an aromatic hydrocarbon group having a benzene ring number of 1 to 2 and a carbon number of C6 to C16, and the group attached thereto is preferably one or more of an amino group, an epoxy group, a mercapto group, and a polysulfide bond; x1、X2And X3Identical or different, are each a functional group capable of hydrolysis, preferably X1、X2And X3Each independently selected from methoxy, ethoxy or chloro; and m is 1 or 2. Wherein the polysulfide bond is of the structure-SxThe number of S in the polysulfide linkage may be from 1 to 8, preferably from 1 to 4.
According to a preferred embodiment of the invention, the coupling agent is selected from one or more of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, bis (triethoxypropylsilane) disulfide and 3-propionylthio-1-propyl-trimethoxysilane.
In the present invention, the base rubber is not particularly limited, and may be, for example, one or more selected from the group consisting of cis-butadiene rubber, isoprene rubber, styrene-butadiene rubber, tertiarydiene rubber, and ethylene-propylene rubber.
The third aspect of the invention provides a preparation method of modified rubber with a self-healing function, wherein the method comprises the following steps:
(1) mixing base rubber, coupling agent and molecular formula XaR1Carrying out first contact on the compound of Y to obtain the rubber modified by the X group;
(2) modifying the X group modified rubber obtained in the step (1) with a molecular formula of R2ZnThe compound of (a) is subjected to a second contact;
the coupling agent is used in 0.01-5 molar parts based on 100 molar parts of rubber structural units in the base rubber, and the molecular formula is XaR1The compound of Y is used in 0.01-5 molar parts based on X group and has the formula of R2ZnThe amount of the compound (b) is 0.01 to 5 parts by mole based on the Z group;
any one of the X group and the Z group is a diene group, and the other is a dienophile group; r1Is a C1-C16 aliphatic group with or without a polysulfide bond; y is selected from hydroxyl, sulfhydryl and amine; r2Selected from aliphatic groups of C1-C16 and aromatic hydrocarbon groups of C6-C30; n is an integer not less than 2; a is an integer of 1 to 3.
In the present invention, it is preferable that the molecular formula is X based on 100 parts by mole of the rubber structural unit in the base rubberaR1The compound of Y is used in 0.05-2 mole parts based on X group, and the molecular formula is R2ZnThe amount of the compound (b) is 0.05-2 molar parts based on the Z group; more preferably, the molecular formula X is 100 parts by mole of the rubber structural unit in the base rubberaR1The compound of Y is used in 0.1-1.5 mole parts based on X group, and the formula is R2ZnThe amount of the compound (b) is 0.1 to 1.5 molar parts based on the Z group; further preferably, the molecular formula is X based on 100 parts by mole of the rubber structural unit in the base rubberaR1The compound of Y is used in 0.2-1 mole part based on X group, and the molecular formula is R2ZnThe amount of the compound (b) is 0.2 to 1 molar part based on the Z group.
In the present invention, preferably, the formula is XaR1Y and the formula R2ZnOf (a) a compoundThe amount of (c) also satisfies the following ratio in the case of satisfying the above requirements: the molecular formula is XaR1The amount of the compound of Y in terms of X group and the molecular formula R2ZnIn a molar ratio of 0.8 to 1.2, calculated as the Z group: 1, more preferably 0.9 to 1.1: 1.
in the present invention, either of the dienophile group and the dienophile group may be an X group or a Z group, that is, either of the dienophile group and the dienophile group may be bonded to the base rubber in step (1) first, or may be bonded to the base rubber in step (2) as a small molecule compound (i.e., R)2Zn) Is connected with the rubber obtained in the step (1). R2ZnWherein the number of Z groups is at least two.
In the present invention, the definition, selection and collocation of the dienophile group and the dienophile group are the same as those described above, and are not described herein again.
In the present invention, R1Is an aliphatic group, the number of carbon atoms of the aliphatic group is preferably C1-C12, more preferably C1-C8; r1May or may not contain polysulfide linkages when R1When a polysulfide linkage is contained, for example, 1 polysulfide linkage may be contained, and the number of S in the polysulfide linkage may be 1 to 8, preferably 1 to 4.
In the present invention, preferably, Y is selected from hydroxyl and mercapto.
In the present invention, preferably, when R is2When the aliphatic group is used, the number of carbon atoms of the aliphatic group is preferably from C1 to C12, more preferably from C1 to C8; when R is2In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having not more than 3 benzene rings, more preferably an aromatic hydrocarbon group having 1 to 2 benzene rings and having carbon atoms of from C6 to C16.
In the present invention, n is preferably an integer of 2 to 4.
In the present invention, preferably, a is 1 or 2.
According to a preferred embodiment of the invention, said formula is XaR1The compound of Y is 4-maleimidobenzene when the group X is a dienophileAnd phenol, when the X group is a diene, is selected from one or more of 2-furancarbinol, 2-furanmethanethiol, difurfuryl disulfide, 2-furanmethylamine, a homopolymer of 2-furancarbinol, and a furan resin.
According to a preferred embodiment of the invention, the formula R2ZnWhen the Z group is a dienophile, one or more compounds selected from the group consisting of N, N '- (4,4' -methylenediphenyl) bismaleimide, N '- (1, 4-phenylene) bismaleimide and N, N' -m-phenylene bismaleimide, and when the Z group is a dienophile, one or more compounds selected from the group consisting of homopolymers of 2-furancarbinols and furan resins.
In the present invention, the coupling agent is preferably used in an amount of 0.01 to 2 parts by mole, more preferably 0.02 to 1.5 parts by mole, and still more preferably 0.2 to 1 part by mole, based on 100 parts by mole of the rubber structural unit in the base rubber.
In the present invention, it is preferable that the amount of the coupling agent satisfies the following condition in addition to the above requirement: the dosage of the coupling agent and the molecular formula are XaR1The ratio of the molar parts of the compound of Y used based on the Y group is 1: 0.8 to 6, preferably 1: 0.9 to 4, more preferably 1: 0.9-1.1. The coupling agent is preferably a silane coupling agent.
In the present invention, the first contacting means is not particularly limited, and may be carried out, for example, under conditions of melt shearing or solution stirring; the temperature of the first contact can be 140-160 ℃, preferably 145-150 ℃ and the time can be 0.1-3h, preferably 0.1-0.5 h. The rotation speed of the rotor for shearing the melt is 10-30 r/min, and the rotation speed of the stirring paddle for stirring the solution is 10-50 r/min.
In the present invention, the second contacting means is not particularly limited, and may be carried out, for example, under conditions of melt shearing or solution stirring; the second contacting may be at a temperature of 20-70 deg.C, preferably 20-40 deg.C, and for a time of 0.1-0.7h, preferably 0.3-0.5 h. The rotation speed of the rotor for shearing the melt is 10-30 r/min, and the rotation speed of the stirring paddle for stirring the solution is 10-50 r/min.
In the present invention, the base rubber is not particularly limited, and may be, for example, one or more selected from the group consisting of cis-butadiene rubber, isoprene rubber, styrene-butadiene rubber, tertiarydiene rubber, and ethylene-propylene rubber.
In the present invention, the coupling agent is not particularly limited, and may be a coupling agent conventionally used in the art. According to a preferred embodiment of the invention, the coupling agent is of formula R3(SiX1X2X3)mSilane coupling agent of the formula R3(SiX1X2X3)mThe silane coupling agent of (a) is the same as that described previously in the present invention and will not be described herein. According to a preferred embodiment of the invention, the coupling agent is chosen from bis- [ gamma- (triethoxysilyl) propyl ] s]One or more of tetrasulfide, bis (triethoxypropylsilane) disulfide, and 3-propionylthio-1-propyl-trimethoxysilane.
In the reaction process of the step (1), the coupling agent has the function of being capable of reacting with the molecular formula XaR1X such as alkoxy group to which Y group in Y compound is reacted1X2X3A group and a functional group R capable of reacting with an unsaturated carbon-carbon double bond in a rubber molecule, thereby enabling a small molecule containing the functional group to be covalently bonded to a rubber macromolecule, thereby obtaining a modified rubber having the functional group. The reaction is schematically shown below (the reaction formula is only schematic and can not be used as a limitation to the invention):
(in Rubber) C ═ C + R3(SiX1X2X3)m+XaR1Y → Rubber- (coupling agent structural unit and YR)1The structure obtained by the reaction) -X,
thus, the X group is attached to the rubber by the reaction of step (1).
In the reaction process of the step (2), the rubber obtained in the step (1) and the molecular formula R2ZnThe reaction scheme of the compound (A) is as follows (the reaction scheme is only schematic and can not be used as a limitation of the present invention):
n rubber-X+R2Zn→R2—(Z---X—rubber)n
x groups and R in the rubber2ZnZ groups in the compound form Z- - -X reversible crosslinking points which are used as weak connection, random chain scission occurs when a tire material is fractured, diene and dienophile generated by chain scission can react again, and cracks are repaired at a molecular level, so that the self-healing function of the material is realized.
The fourth aspect of the invention provides the modified rubber with the self-healing function, which is prepared by the method.
The modified rubbers of the first and fourth aspects of the present invention have excellent self-healing functions, and the principle thereof may be that: in the modified rubber, a diene group and a dienophile group form weak connection, random chain scission occurs when the material is fractured, the diene and the dienophile generated by chain scission can react again, and cracks are repaired at the molecular level, so that the self-healing function of the material is realized. In addition, the diene group and the dienophile group are organic compound groups, do not contain metal elements, and do not influence the aging resistance of the material.
The fifth aspect of the invention provides the application of the modified rubber with the self-healing function of the invention on a tire. The modified rubber of the present invention is particularly suitable for use in tires because of its excellent self-healing function and aging resistance. The temperature of the tire can rise to about 100 ℃ in the using process, the tire is easy to fatigue under high temperature for a long time so as to generate cracks, and when the cracks are generated, the diene and the dienophile can react again so as to repair the cracks. On the microscopic level, the tire has the processes of cracking and repairing the cracks, and on the macroscopic level, the tire of the invention still has no visible cracks after long-term continuous use, is extremely durable and has long service life.
The present invention will be described in further detail below by way of specific examples.
The materials used in the examples and comparative examples are as follows:
polybutadiene rubber brand: BR9000, produced by Yanshan division of China petrochemical Co., Ltd., Mooney viscosity ML (1+4min, 100 ℃) of 45 +/-4; the weight average molecular weight is 38.2 ten thousand, and the molecular weight distribution is 3.91; wherein the cis-1, 4-butadiene structure content was 96.5 wt%, the trans-1, 4-butadiene structure content was 2.0 wt%, and the 1, 2-butadiene structure content was 1.5 wt%.
Silane coupling agent Si 69: purchased from Nanjing eosin-photonics general chemical industry, the active ingredient is bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, the total sulfur content: 22.0 +/-1.0%.
2-Furanomethanol: purchased from chemical reagents of yinaoka, beijing, chemically pure.
N, N '- (4,4' -methylenediphenyl) bismaleimide: purchased from sahn chemical technology (shanghai) ltd, purity 98%.
Examples 1 to 5 are intended to illustrate the modified rubber having a self-healing function of the present invention and the process for producing the same.
Example 1
(1) 200gBR9000, 2g Si69 and 0.674g 2-furancarbinol were mixed on a two-roll mill for 10min at a temperature of 20 ℃ to give a gum stock. 50.15g of the rubber was taken out of the kneaded rubber mass and sheared at 145 ℃ for 10 minutes in a Hakk rheometer (HAKKE, a product of Thermo Electron Corporation, hereinafter the same), to obtain a furan group-grafted polybutadiene rubber BR-F-1. The molar content n (furyl) in BR-F-1 is calculated as follows: n (butadiene unit) ═ 0.002: the molar ratio of 1, Si69 to the amount of 2-furancarbinol in terms of hydroxyl groups is 1: 1.
(2) 47.56g of BR-F-1 rubber stock was mixed with 0.30g of N, N '- (4,4' -methylenediphenyl) bismaleimide (bismaleimide for short, BMI) on a two-roll mill for 10min at a temperature of 20 ℃ to give 47.83g of modified rubber H1 having a self-healing function. It can be found by calculation that n (furyl)/n (bmi) ═ 2, i.e., n (furyl)/n (maleimide) ═ 1 in H1.
Example 2
(1) 200gBR, 10g Si69 and 3.370g of 2-furancarbinol were mixed on a two-roll mill for 20min at a temperature of 20 ℃ to give a gum stock. 53.09g of rubber is taken out of the mixed rubber material, and the rubber is sheared for 10min at 145 ℃ on a haake rheometer to obtain the furan group grafted polybutadiene rubber BR-F-2. The molar content n (furyl) in BR-F-2 is calculated as follows: n (butadiene unit) ═ 0.01: the molar ratio of 1, Si69 to the amount of 2-furancarbinol in terms of hydroxyl groups is 1: 1.
(2) 51.96g of BR-F-2 rubber stock and 1.52g of N, N '- (4,4' -methylenediphenyl) bismaleimide (bismaleimide for short) are mixed on a two-roll open mill for 30min at the temperature of 30 ℃ to obtain the modified rubber H2 with the self-healing function. It can be found by calculation that n (furyl)/n (bmi) ═ 2, i.e., n (furyl)/n (maleimide) ═ 1 in H2.
Example 3
(1) 200gBR, 6.6g Si69 and 2.178g 2-furancarbinol were mixed on a two-roll mill for 20min at a temperature of 20 ℃ to give a gum stock. 51.32g of rubber is taken out from the mixed rubber material, and the rubber is sheared for 30min at 150 ℃ on a haake rheometer to obtain the furan group grafted polybutadiene rubber BR-F-3. The molar content n (furyl) in BR-F-3 is calculated as follows: n (butadiene unit) ═ 0.006: the molar ratio of 1, Si69 to the amount of 2-furancarbinol, calculated as hydroxyl groups, is 1.1: 1.
(2) 52.19 BR-F-3 rubber stock and 3.58g of N, N '- (4,4' -methylene diphenyl) bismaleimide (bimaleimide for short, BMI) are mixed on a two-roll open mill for 40min at the temperature of 40 ℃ to obtain the modified rubber H3 with the self-healing function. It can be found by calculation that n (furyl)/n (bmi) in H3 is 1.8, that is, n (furyl)/n (maleimide) is 0.9.
Example 4
The procedure was followed as in example 1, except that the amount of N, N '- (4,4' -methylenediphenyl) bismaleimide was changed so that N (furyl)/N (maleimido) became 1.2. Finally obtaining the modified rubber H4 with the self-healing function.
Example 5
The procedure is as in example 1, except that the amount of 2-furancarbinol is varied so that the molar content n (furanyl): n (butadiene unit) ═ 0.02: 1. finally obtaining the modified rubber H5 with the self-healing function.
Comparative examples 1 to 6 are for explaining modified rubbers not obtained according to the process of the present invention and the process for producing the same.
Comparative example 1
200gBR, 2g of Si69 and 0.674g of 2-furancarbinol are mixed on a double-roll mill for 10min at the temperature of 20 ℃, and the final rubber material product DH1 is obtained.
Comparative example 2
200gBR, 10g of Si69 and 3.370g of 2-furancarbinol are mixed on a double-roll mill for 20min at the temperature of 20 ℃, and the final rubber material product DH2 is obtained.
Comparative example 3
200gBR, 2g Si69, 0.674g 2-furancarbinol were mixed on a two-roll mill for 10min at a temperature of 20 ℃ to give a gum stock. 50.15g of the rubber is taken out of the rubber obtained in the last step, and the rubber is sheared for 10min at 145 ℃ on a Haake rheometer, so that a final rubber product DH3 is obtained.
Comparative example 4
200gBR, 10g Si69, 3.370g 2-furancarbinol were mixed on a two-roll mill for 20min at 20 ℃ to give a gum stock. 53.09g of the rubber is taken from the rubber obtained in the last step, and the rubber is sheared for 10min at 145 ℃ on a Haake rheometer to obtain the final rubber product DH 4.
Comparative example 5
The procedure is as in example 1, except that 0.30g of BMI is not added in step (2). The final sizing product DH5 was obtained.
Comparative example 6
The procedure is as in example 1, except that 0.674g of 2-furanmethanol is not added in step (1). The final sizing product DH6 was obtained.
Test example
(1) Haake rheometer test
The following tests were carried out, as represented by the rubber products H1, H2, DH3 and DH4 obtained in example 1, example 2, comparative example 3 and comparative example 4: the torque and temperature changes under the action of heat and shear fields were measured during the processing of the rubber compositions with a haake rheometer, in which the torque was measured by a torque sensor in the rheometer and the temperature was measured by a thermometer, and the resulting torque versus time curve is shown in FIG. 1 and the temperature versus time curve is shown in FIG. 2.
As can be seen from FIGS. 1 and 2, the torque-time and temperature-time curves are nearly horizontal after the compound is sheared in the Haake rheometer for approximately 18 minutes, indicating that the coupling reaction is substantially complete and that the furan groups have been covalently grafted onto the butadiene rubber molecules. Thus, it was demonstrated that the calculated molar ratio can substantially reflect the actual molar ratio.
(2) Rheological Property test
The rubber products H2 and DH4 obtained in example 2 and comparative example 4 were tested using a rubber processing analyzer model RPA2000 manufactured by Alpha, USA, in which the frequency of the scanning of three temperature sweeps of RPA was 1Hz and the strain was 7%, the resulting curve of the storage shear modulus G 'as a function of temperature is shown in FIG. 3, the curve of the storage shear modulus differential dG'/dT as a function of temperature is shown in FIG. 4, and (H2 or DH4) -1, (H2 or DH4) -2 and (H2 or DH4) -3 in FIGS. 3 and 4 respectively refer to the results of three temperature sweeps of RPA.
As can be seen from the results of rheological properties of the compositions in FIGS. 3 and 4, the dG'/dT-T curve of the H2 system peaked at 60-70 ℃ and at 110-120 ℃ indicating that DA of furan with maleimide and its reverse reaction occur to a greater extent in the two temperature ranges mentioned above; the dG'/dT-T curve of the DH4 system is weaker and is caused by DA reaction and reverse reaction between furan group (as diene) and double bond (as dienophile) in butadiene rubber, and the dienophile property of the double bond in butadiene rubber is not as strong as that of the double bond in maleimide, so the self-healing effect is not as good as that of the embodiment H2. It can be understood that the self-healing properties of the modified rubbers obtained in the examples of the present invention are all better than those of the rubbers containing only furan groups in the comparative examples.
(3) Crosslink density
By IIC Dr.Kuhn GmbH&The modified rubber products H1 to H6 and DH1-DH4 obtained in examples 1 to 6 and comparative examples 1 to 4 were measured for the crosslink density (10 ℃ C.) (80 ℃ C., (100 ℃ C., (110 ℃ C., (120 ℃ C.)) according to the IIC XLDS-15HT type nuclear magnetic crosslink Density Meter test manufactured by Co KG Co., Ltd.) with a gradual increase in temperature-5mol/cm3) And the temperature is raised to 120 ℃ and the test is completed (this process is the first temperature raising process)) Subsequently, the modified rubber products H1 to H6 obtained in examples 1 to 6 were cooled to 80 ℃ again, and the above-described temperature raising and testing process (i.e., the second temperature raising process) was repeated, with the results shown in Table 1.
TABLE 1
| |
80 |
100℃ | 110 |
120℃ |
| H1-first temperature rise | 2.83 | 3.96 | 4.48 | 4.31 |
| H1-second temperature rise | 2.82 | 3.83 | 4.39 | 4.28 |
| H2-first temperature rise | 2.81 | 4.07 | 4.57 | 4.32 |
| H2-second temperature rise | 2.83 | 3.94 | 4.47 | 4.28 |
| H3-first temperature rise | 2.82 | 4.08 | 4.59 | 4.35 |
| H3-second temperature rise | 2.83 | 3.92 | 4.50 | 4.29 |
| H4-first temperature rise | 2.72 | 3.75 | 4.38 | 4.21 |
| H4-second temperature rise | 2.73 | 3.55 | 4.18 | 4.14 |
| H5-first temperature rise | 2.61 | 3.15 | 3.87 | 3.64 |
| H5-second temperature rise | 2.58 | 3.01 | 3.59 | 3.37 |
| DH 1-first warming | 2.52 | 2.55 | 2.56 | 2.53 |
| DH 2-first warming | 2.44 | 2.48 | 2.53 | 2.50 |
| DH 3-first warming | 2.86 | 2.91 | 2.94 | 2.93 |
| DH 4-first warming | 2.82 | 2.90 | 2.95 | 2.90 |
| DH 5-first warming | 2.40 | 2.43 | 2.45 | 2.42 |
| DH 6-first warming | 2.38 | 2.42 | 2.45 | 2.40 |
In raw gel solid nuclear magnetic data, the total crosslink density XLD includes the sum of the physical entanglement points and the chemical crosslink point density. The total crosslinking density XLD reflects the number of physical entanglement points and chemical crosslinking points in the butadiene rubber molecules, and the XLD at different temperatures can reflect the change of the crosslinking points along with the temperature, thereby representing the self-healing capability of the material. It is generally considered that, as the temperature increases, the faster the value of the crosslinking density increases (without exceeding a certain range), the stronger the self-healing ability of the rubber is represented; in addition, the strong self-healing ability of the rubber is also shown in that the data of the crosslinking density at the second temperature rise is closer to the data of the crosslinking density at the first temperature rise.
As can be seen from Table 1, the XLD of the modified rubber H1-H5 of the invention at 80 ℃ was comparable to that of the modified rubber DH1-DH6 of the comparative example, while the XLD of the modified rubber H1-H5 of the invention increased significantly after the temperature increased to 120 ℃ while the XLD of the modified rubber DH1-DH6 of the comparative example was unchanged; this indicates that the thermally reversible DA reactions occurring in the modified rubbers H1-H5 of the present invention can change the crosslinking density of the system with a change in temperature, thus demonstrating that the modified rubbers of the present invention have better self-healing ability, while the modified rubbers of the comparative examples have poorer self-healing ability. When the temperature is raised for the second time, the XLD of the modified rubber H2 is increased along with the temperature rise, and the XLD is equivalent to the XLD at the corresponding temperature of the first temperature rise, which shows that the crosslinking density of the modified rubber H1-H5 can realize reversible change under the condition of multiple temperature changes, thereby proving that the modified rubber has better self-healing capability.
Therefore, the modified rubber of the invention can have good self-healing capability in the range of 80-120 ℃, namely the service temperature range of the tire. In addition, the modified rubber does not contain metal ions, so that the modified rubber still can keep good ageing resistance.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (19)
1. The modified rubber with the self-healing function is characterized by comprising diene groups and dienophile groups, wherein the diene group content is 0.1-1.5 mol parts and the dienophile group content is 0.1-1.5 mol parts based on 100 mol parts of rubber structural units in the modified rubber;
the diene group is furyl and/or isobenzofuryl;
the dienophile group is a maleimide group;
the ratio of the mole parts of the diene group and the dienophile group is 0.8-1.2: 1;
the rubber structural unit in the modified rubber is a structural unit in a base rubber of the modified rubber, and the base rubber is selected from one or more of butadiene rubber, isoprene rubber, styrene-butadiene rubber, ternary integrated rubber and ethylene-propylene rubber.
2. A rubber composition comprising a first agent and a second agent each separately maintained, the first agent comprising a base rubber, a coupling agent and a compound of the formula XaR1Y, the second agent comprising a compound of the formula R2Zn, the coupling agent being present in an amount of 0.01 to 5 parts by mole based on 100 parts by mole of rubber building blocks in the base rubber, the compound of the formula XaR1Y being present in an amount of 0.1 to 1.5 parts by mole based on X groups, and the compound of the formula R2Zn being present in an amount of 0.1 to 1.5 parts by mole based on Z groups;
wherein any one of the X group and the Z group is a diene group, the diene group is furyl and/or isobenzofuryl, and the other is a dienophile group; the dienophile group is a maleimide group; the ratio of the mole parts of the diene group and the dienophile group is 0.8-1.2: 1;
r1 is a C1-C16 aliphatic group with or without a polysulfide bond; y is selected from hydroxyl, sulfhydryl and amine; r2 is selected from C1-C16 aliphatic group and C6-C30 aromatic hydrocarbon group; n is an integer not less than 2; a is an integer of 1 to 3.
3. The rubber composition according to claim 2, wherein the coupling agent is contained in an amount of 0.01 to 2 parts by mole based on 100 parts by mole of the rubber structural unit in the base rubber, and a molar ratio of a content of the compound of the formula XaR1Y in terms of X groups to a content of the compound of the formula R2Zn in terms of Z groups is 0.8 to 1.2: 1, the molar ratio of the content of the coupling agent to the content of the compound with the molecular formula XaR1Y calculated by Y groups is 0.8-6: 1.
4. the rubber composition according to claim 2, wherein R1 is an aliphatic group having a carbon number of C1-C12; r2 is selected from aliphatic group with carbon atom number of C1-C12 and aromatic hydrocarbon group with benzene ring number not more than 3; y is selected from hydroxyl and sulfhydryl; n is an integer of 2 to 4; a is 1 or 2.
5. The rubber composition of claim 2 or 3, wherein the base rubber is selected from one or more of cis-butadiene rubber, isoprene rubber, styrene-butadiene rubber, terpolymer rubber, and ethylene-propylene rubber.
6. The rubber composition of claim 5, wherein the coupling agent is a silane coupling agent of the formula R3(SiX1X2X3) m, wherein R3 is a C1-C16 aliphatic group or a C6-C30 aromatic hydrocarbon group having attached thereto one or more groups of vinyl, epoxy, amino, methacryloxy, mercapto, 3-propionylthio-1-propyl, and polysulfide bonds; x1, X2 and X3 are the same or different and are each a functional group capable of hydrolysis.
7. The rubber composition of claim 5, wherein X1, X2, and X3 are each independently selected from methoxy, ethoxy, or chloro; m =1 or 2.
8. The rubber composition of claim 5, wherein the coupling agent is selected from one or more of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, bis (triethoxypropylsilane) disulfide, and 3-propionylthio-1-propyl-trimethoxysilane.
9. A preparation method of modified rubber with a self-healing function is characterized by comprising the following steps:
(1) carrying out first contact on base rubber, a coupling agent and a compound with a molecular formula of XaR1Y to obtain X group modified rubber;
(2) carrying out second contact on the X-group modified rubber obtained in the step (1) and a compound with the molecular formula of R2 Zn;
the coupling agent is used in an amount of 0.01 to 5 parts by mole, the compound of formula XaR1Y is used in an amount of 0.1 to 1.5 parts by mole, the compound of formula R2Zn is used in an amount of 0.1 to 1.5 parts by mole, based on 100 parts by mole of the rubber structural unit in the base rubber;
any one of the X group and the Z group is a diene group, the diene group is furyl and/or isobenzofuryl, and the other is a dienophile group; the dienophile group is a maleimide group; the ratio of the mole parts of the diene group and the dienophile group is 0.8-1.2: 1;
r1 is a C1-C16 aliphatic group with or without a polysulfide bond; y is selected from hydroxyl, sulfhydryl and amine; r2 is selected from C1-C16 aliphatic group and C6-C30 aromatic hydrocarbon group; n is an integer not less than 2; a is an integer of 1 to 3.
10. The production method according to claim 9, wherein the coupling agent is used in an amount of 0.01 to 2 parts by mole based on 100 parts by mole of the rubber structural unit in the base rubber, and a molar ratio of an amount of the compound of the formula XaR1Y in terms of X groups to an amount of the compound of the formula R2Zn in terms of Z groups is 0.8 to 1.2: 1, the molar ratio of the amount of the coupling agent to the amount of the compound with the molecular formula XaR1Y calculated by Y groups is 0.8-6: 1.
11. the preparation method according to claim 9, wherein R1 is an aliphatic group having a carbon number of C1-C12; r2 is selected from aliphatic group with carbon number of C1-C12 and aromatic hydrocarbon group with benzene ring number not more than 3; y is selected from hydroxyl and sulfhydryl; n is an integer of 2 to 4; a is 1 or 2.
12. The preparation method according to claim 9 or 10, wherein the first contacting is performed under conditions of melt shear or solution stirring, and the temperature of the first contacting is 140 ℃ and 160 ℃, and the time is 0.1-3 h.
13. The method of claim 9 or 10, wherein the second contacting is performed under conditions of melt shear or solution stirring, and the temperature of the second contacting is 20-70 ℃ for 0.1-0.7 h.
14. The production method according to claim 9 or 10, wherein the base rubber is selected from one or more of cis-butadiene rubber, isoprene rubber, styrene-butadiene rubber, tertiarydiene rubber, and ethylene-propylene rubber.
15. The method of claim 14, wherein the coupling agent is a silane coupling agent of the formula R3(SiX1X2X3) m, wherein R3 is a C1-C16 aliphatic group or a C6-C30 aromatic hydrocarbon group having attached thereto one or more of a vinyl group, an epoxy group, an amino group, a methacryloxy group, a mercapto group, a 3-propionylthio-1-propyl group, and a polysulfide bond; x1, X2 and X3 are the same or different and are each a functional group capable of hydrolysis.
16. The preparation process according to claim 15, wherein X1, X2 and X3 are each independently selected from methoxy, ethoxy or chloro; m =1 or 2.
17. The method of claim 15, wherein the coupling agent is selected from one or more of bis- [ γ - (triethoxysilyl) propyl ] tetrasulfide, bis (triethoxypropylsilane) disulfide, and 3-propionylthio-1-propyl-trimethoxysilane.
18. The modified rubber having a self-healing function, which is prepared by the method according to any one of claims 9 to 17.
19. Use of the modified rubber having a self-healing function according to any one of claims 1 and 18 in a tire.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654368A (en) * | 1995-03-03 | 1997-08-05 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Recyclable cross-linked polymer, method for producing a molded article, and method for recycling the same |
| US6794472B2 (en) * | 2001-06-22 | 2004-09-21 | Acushnet Company | Self healing polymers in sports equipment |
| CN102268154A (en) * | 2003-12-24 | 2011-12-07 | 陶氏环球技术公司 | Thermally-reversible crosslinking of polymers |
| CN102399380A (en) * | 2010-07-30 | 2012-04-04 | 住友橡胶工业株式会社 | Polymer sheet for inner liner, polymer laminate for inner liner, and pneumatic tire |
| CN104193852A (en) * | 2014-08-28 | 2014-12-10 | 上海交通大学 | Modified unsaturated rubber and preparation and use methods thereof |
| CN104628895A (en) * | 2015-01-27 | 2015-05-20 | 上海交通大学 | Method for thermally reversibly crosslinking styrenic thermoplastic elastomer material |
-
2016
- 2016-11-01 CN CN201610943368.0A patent/CN108017728B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654368A (en) * | 1995-03-03 | 1997-08-05 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Recyclable cross-linked polymer, method for producing a molded article, and method for recycling the same |
| US6794472B2 (en) * | 2001-06-22 | 2004-09-21 | Acushnet Company | Self healing polymers in sports equipment |
| CN102268154A (en) * | 2003-12-24 | 2011-12-07 | 陶氏环球技术公司 | Thermally-reversible crosslinking of polymers |
| CN102399380A (en) * | 2010-07-30 | 2012-04-04 | 住友橡胶工业株式会社 | Polymer sheet for inner liner, polymer laminate for inner liner, and pneumatic tire |
| CN104193852A (en) * | 2014-08-28 | 2014-12-10 | 上海交通大学 | Modified unsaturated rubber and preparation and use methods thereof |
| CN104628895A (en) * | 2015-01-27 | 2015-05-20 | 上海交通大学 | Method for thermally reversibly crosslinking styrenic thermoplastic elastomer material |
Non-Patent Citations (2)
| Title |
|---|
| Diels-Alder Reactions with Novel Polymeric Dienes and Dienophiles:Synthesis of Reversibly Cross-Linked Elastomers;Rana Gheneim,Catalina Perez-Berumen,Alessandro Gandini;《Macromolecules》;20020808;第35卷(第19期);第7246-7253页 * |
| 应用Diels-Alder反应制备聚合物的研究进展;杨哲、魏宏亮、楚晖娟等;《高分子通报》;20100131(第1期);第41-49页 * |
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| CN108017728A (en) | 2018-05-11 |
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