CN110016151B - Modified butadiene rubber and preparation method and application thereof - Google Patents

Modified butadiene rubber and preparation method and application thereof Download PDF

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CN110016151B
CN110016151B CN201810014254.7A CN201810014254A CN110016151B CN 110016151 B CN110016151 B CN 110016151B CN 201810014254 A CN201810014254 A CN 201810014254A CN 110016151 B CN110016151 B CN 110016151B
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rubber
butadiene rubber
weight
parts
mixture
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CN110016151A (en
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杨广明
杨亮
韩明哲
闫蓉
韩艳
詹续芹
李博泉
费宇晶
关宇辰
仝璐
张素彬
王薇
张玺
于琦周
张学全
胡雁鸣
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Petrochina Co Ltd
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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
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2457/00—Characterised by the use of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08J2457/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
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  • Tires In General (AREA)

Abstract

The invention provides a modified butadiene rubber and a preparation method and application thereof. The preparation method of the modified butadiene rubber comprises the following steps: dissolving butadiene rubber in an organic solvent to obtain a rubber solution; uniformly mixing a rubber anti-tearing agent, a rubber reinforcing agent and the rubber solution to obtain a mixture; and removing the organic solvent in the mixture to obtain the modified butadiene rubber. The preparation method of the modified butadiene rubber provided by the invention can obviously improve the tear strength, puncture resistance and chipping resistance of vulcanized rubber and rubber products after vulcanization processing and other treatments.

Description

Modified butadiene rubber and preparation method and application thereof
Technical Field
The invention belongs to the technical field of rubber modification, and particularly relates to modified butadiene rubber, a preparation method and application thereof, in particular to modified butadiene rubber with high tear resistance, a modification process thereof, and application of the modified butadiene rubber in rubber products such as automobile tires.
Background
Butadiene Rubber (BR) is a short for cis-1, 4-polybutadiene rubber, is a synthetic rubber with a regular structure formed by polymerizing butadiene monomers, and has a cis structure content of more than 95%. Because the molecular structure of the butadiene rubber is regular and the molecular chain is very flexible, compared with synthetic rubber such as natural rubber or styrene butadiene rubber, the butadiene rubber usually has more outstanding flexibility, elasticity, wear resistance, flex resistance, low temperature resistance and the like, so the butadiene rubber has very wide application in the fields of automobile tires, shoe making, buildings and the like. In particular, the automobile tire prepared by using the butadiene rubber as the raw material and carrying out vulcanization treatment and other processing has the characteristics of high wet skid resistance, low rolling resistance and the like; meanwhile, the preparation process of the butadiene rubber is developed more mature, and the raw material cost and the processing cost are lower, so that the butadiene rubber is always the preferred material for the rubber for the automobile tires.
However, the butadiene rubber is limited in its molecular structure, so that the rubber products such as vulcanized rubber and automobile tires obtained by subsequent processing have low tear strength, and are not ideal in puncture resistance and chipping resistance. Therefore, when the butadiene rubber is used for preparing rubber products such as automobile tires, the butadiene rubber must be used together with other rubber species such as styrene butadiene rubber, and the amount of the butadiene rubber is usually not more than 30% so as to ensure that the tear strength, puncture resistance and chipping resistance of the automobile tires meet the relevant requirements while maintaining high wet skid resistance and low rolling resistance.
Therefore, how to modify the butadiene rubber to ensure that the obtained modified butadiene rubber has good tearing strength, puncture resistance and chipping resistance when being used for vulcanized rubber or further used for rubber products such as automobile tires and the like is a technical problem to be solved at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a modified butadiene rubber and a preparation method thereof, which are used for improving the tearing strength, the puncture resistance and the chipping and chipping resistance of the butadiene rubber when the butadiene rubber is used for vulcanized rubber and rubber products; the invention also provides application of the modified butadiene rubber in rubber products and vulcanized rubber processed by the modified butadiene rubber.
In order to improve the tearing strength of the butadiene rubber, the invention firstly provides a preparation method of modified butadiene rubber, which comprises the following steps:
dissolving butadiene rubber in an organic solvent to obtain a rubber solution;
uniformly mixing a rubber anti-tearing agent, a rubber reinforcing agent and the rubber solution to obtain a mixture;
and removing the organic solvent in the mixture to obtain the modified butadiene rubber.
The preparation method is actually a process of modifying the butadiene rubber by using the rubber anti-tearing agent and the rubber reinforcing agent. In the modification process, the key is to realize the full mixing of the rubber anti-tearing agent, the rubber reinforcing agent and the butadiene rubber.
Firstly, dissolving butadiene rubber in an organic solvent to ensure that the butadiene rubber is used as a solute and is uniformly dispersed in the organic solvent, so as to obtain a uniform rubber solution; and then mixing the rubber solution with the rubber anti-tearing agent and the rubber reinforcing agent to enable the rubber anti-tearing agent and the rubber reinforcing agent to be dispersed in the molecular structure of the butadiene rubber. Compared with the traditional method in which the rubber tearing resistant agent and the rubber reinforcing agent are directly and physically mixed in a solid state or are mixed by heating, melting and stirring, the mixing method provided by the invention is easier to realize the uniform dispersion of the rubber tearing resistant agent and the rubber reinforcing agent in the butadiene rubber.
In addition, researches show that compared with vulcanized rubber prepared by adopting unmodified butadiene rubber, the modified butadiene rubber obtained by adopting the mixing mode and vulcanized rubber obtained by adopting the vulcanization treatment have obviously improved tearing strength, puncture resistance and chipping resistance. The inventor analyzes that the original molecular chain structure of the butadiene rubber is changed probably due to the addition of the rubber anti-tearing agent and the rubber reinforcing agent. Therefore, in the subsequent processes of vulcanizing the modified butadiene rubber and the like to prepare vulcanized rubber and rubber products, the molecular network structure of the butadiene rubber is also changed, which is beneficial to improving the interaction force between the modified butadiene rubber and the filler, and further can improve the tearing strength, puncture resistance and chipping resistance of the vulcanized rubber, even rubber products such as automobile tires and the like.
The mixing process may be carried out by adding the rubber anti-tearing agent and the rubber reinforcing agent into the butadiene rubber solvent, and then fully stirring to uniformly disperse the rubber anti-tearing agent and the rubber reinforcing agent in the butadiene rubber. The organic solvent in the mixture can then be removed.
The removal of the organic solvent from the mixture can be carried out by any means known in the art. In a preferred embodiment of the present invention, the organic solvent in the mixture may be removed by using a terminator. Specifically, a terminator is added into the mixture, so that the rubber anti-tearing agent, the rubber reinforcing agent and the butadiene rubber in the mixture are separated out from the organic solvent, and then solid-liquid separation is carried out to obtain the blocky elastic solid, namely the modified butadiene rubber.
It will be appreciated that the above-described terminating agents, when used, enable the butadiene rubber, rubber tear resistance agent and rubber reinforcing agent in the mixture to be extracted from the organic solvent, and also do not interfere with the uniform mixing of the butadiene rubber, rubber tear resistance agent and rubber reinforcing agent during the process.
Specifically, the terminator may be selected according to the organic solvent, the rubber anti-tearing agent, the physical and chemical properties of the rubber reinforcing agent, and the like, for example, the terminator may contain at least one of methanol, ethanol, ethylene glycol, and glycerol. In the practice of the present invention, the terminating agent typically used is methanol, ethanol, ethylene glycol or glycerol to sufficiently separate the organic solvent from the butadiene rubber, rubber tearing inhibitor and rubber reinforcing agent.
In the specific implementation process of the invention, the terminator is added into the mixture, so that the solid mixture containing the butadiene rubber, the rubber anti-tearing agent and the rubber reinforcing agent is layered with the liquid mixture containing the organic solvent and the terminator, and then the modified butadiene rubber, specifically the blocky elastic solid, is finally obtained through solid-liquid separation.
It is understood that a small amount of organic solvent may remain in the bulk elastic solid, and thus, the bulk elastic solid may be further subjected to a drying treatment to completely remove the organic solvent therefrom.
It can be understood that in the process of modifying the butadiene rubber, the proportion of the butadiene rubber, the rubber anti-tearing agent and the reinforcing agent is reasonably controlled, so that the finally obtained vulcanized rubber and rubber products can keep the original performance advantages of the butadiene rubber, and meanwhile, the tearing strength, the puncture resistance, the chipping and chipping resistance are improved.
In the specific implementation process of the invention, the weight ratio of the butadiene rubber: rubber anti-tearing agent: the weight ratio of the rubber reinforcing agent is 100: (1-50): (1-10). That is, the rubber anti-tearing agent is 1-50 parts by weight and the rubber reinforcing agent is 1-10 parts by weight based on 100 parts by weight of the butadiene rubber.
The modified butadiene rubber used in the invention can be butadiene rubber commonly used in the field, such as butadiene rubber raw material commonly used for preparing automobile tires at present. It can be understood that the reasonable control of the molecular weight and the molecular weight distribution of the butadiene rubber is beneficial to the modified rubber to keep the advantages of low rolling resistance and high wet skid resistance of the butadiene rubber, and the number average molecular weight of the butadiene rubber can be controlled to be 80,000-120,000, and the molecular weight distribution index (the ratio of the weight average molecular weight to the number average molecular weight) is 1.5-5.0.
Accordingly, the organic solvent for dissolving the butadiene rubber may be one or more of organic solvents commonly used in the art for preparing rubber cement, including but not limited to, hexane, cyclohexane, toluene and tetrahydrofuran.
The rubber tear resistance agents used in the present invention are also referred to as tear resistance modifiers. Researches show that if the molecular structure of the rubber anti-tearing agent contains a double-bond functional group and/or an amino group, the rubber anti-tearing agent is very beneficial to improving the tearing strength, the puncture resistance and the anti-chipping and anti-blocking capability of the butadiene rubber after vulcanization. In the practice of the invention, the rubber tear resistant agent used is selected from at least one of the group consisting of phenolic resin, terpene resin, carbon pentapetroleum resin (carbon 5 resin), carbon nonapetroleum resin (carbon 9 resin), acrylamide and polyacrylamide.
Further, the mass ratio of the tear resistance modifier to the butadiene rubber can be (20-50): 100, typically (20-30): 100.
the rubber reinforcing agent used in the invention can be a reinforcing agent commonly used in the existing rubber processing process. In the specific implementation process of the invention, the rubber reinforcing agent can be at least one of carbon black, white carbon black, calcium carbonate and magnesium oxide, and can also be other reinforcing agents.
Specifically, the mass ratio of the rubber reinforcing agent to the butadiene rubber can be (1-8): 100, generally controlling the mass ratio of the rubber reinforcing agent to the butadiene rubber to be (5-8): 100.
the invention also provides the modified butadiene rubber prepared by the preparation method.
It can be understood that due to the preparation method, the obtained modified butadiene rubber can obviously improve the tearing strength, puncture resistance and chipping resistance of vulcanized rubber and rubber products when being used for preparing the vulcanized rubber and the rubber products.
The invention further provides vulcanized rubber which is obtained by vulcanizing the modified butadiene rubber.
Specifically, the existing vulcanization processing technology of the butadiene rubber can be applied to the modified butadiene rubber provided by the invention, and for example, the modified butadiene rubber can be subjected to mixing vulcanization according to the standard test formula (table 1, non-oil-filled rubber) and the method C2 recorded in GB/T8660-2008 solution polymerization type Butadiene Rubber (BR) evaluation method. The concrete mixing formula is as follows: 100 parts by weight of the above-described modified butadiene rubber, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of an accelerator TBBS, 60 parts by weight of a universal industrial reference carbon black, 15 parts by weight of ASTM103# process oil and 1.5 parts by weight of sulfur. Through tests, compared with vulcanized rubber prepared from unmodified butadiene rubber, the vulcanized rubber provided by the invention has the advantages that the tearing strength, the puncture resistance and the chipping and chipping resistance are obviously improved.
The invention finally provides the application of the modified butadiene rubber in rubber products.
The rubber product can be, for example, an automobile tire, a rubber shoe and the like. As described above, the modified butadiene rubber provided by the present invention can impart a relatively high tear strength to a rubber product such as an automobile tire when used for the rubber product.
Taking manufacturing of automobile tires as an example, the modified butadiene rubber provided by the invention is used as a raw material to replace the original butadiene rubber, so that the tear strength of the automobile tires can be improved, and the performance advantage brought by the butadiene rubber can be still maintained.
In addition, the usage amount of the butadiene rubber in the automobile tire is increased, so that the tearing strength of the automobile tire can be improved, and other performances such as high wet skid resistance, low rolling resistance and the like can be well maintained, thereby obviously reducing the raw material cost of the automobile tire.
The invention provides a modified butadiene rubber, which is used for vulcanized rubber, and has the advantages that the tear strength, the puncture resistance and the chipping and dropping resistance are obviously improved, wherein the tear strength of the vulcanized rubber is improved by 30-60% compared with that before modification, the puncture resistance is improved by 45-65%, and the chipping and dropping resistance is also obviously improved.
The invention provides a preparation method of the modified butadiene rubber, which is simple and feasible in steps and convenient for large-scale popularization and application.
The invention also provides vulcanized rubber which is obtained by vulcanizing the modified butadiene rubber. Compared with vulcanized rubber obtained from unmodified butadiene rubber, the vulcanized rubber provided by the invention has obvious improvement on tear strength, puncture resistance and chipping resistance.
The invention also provides the application of the modified butadiene rubber in rubber products such as automobile tires and the like. When the modified butadiene rubber is used as a raw material to manufacture rubber products such as automobile tires and the like, the tear resistance of the rubber products can be improved under the condition of high usage amount of the butadiene rubber, and the performance advantages of the original wet skid resistance, low rolling resistance and the like are still well maintained, so that the raw material cost of the rubber products can be remarkably reduced; on the premise of the same usage amount, the tearing strength, the puncture resistance and the chipping and chipping resistance of the rubber product can be improved, and the excellent performance of the rubber product endowed by the butadiene rubber can be well maintained.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present disclosure and together with the description, serve to explain the principles of the disclosure.
FIG. 1 is a flow chart of a process for preparing modified butadiene rubber provided in an embodiment of the present invention.
Specific embodiments of the present disclosure have been shown by way of example in the drawings and will be described in more detail below. These drawings and written description are not intended to limit the scope of the disclosed concepts in any way, but rather to illustrate the concepts of the disclosure to those skilled in the art by reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, the test for the tear strength complies with the national Standard GB/T529-.
The puncture resistance was measured by a dynamic rubber cutting tester with a puncture frequency of 100 times/min, and the mass was measured before and after puncture, and the puncture resistance was evaluated by the mass reduction of vulcanized rubber.
The anti-chipping and anti-chipping capability is determined by observing the appearance of a sample after the experiment of the rubber dynamic cutting tester is finished, the rubber block which is not more than 0.5cm is excellent, the rubber block which is 0.5 cm-1.0 cm is good, and the rubber block which is more than 1.0cm is poor.
The cis-butadiene rubber used in the following examples and comparative examples was obtained from the oil-in-place petrochemical company.
Example 1
The embodiment provides a preparation method of modified butadiene rubber, and the specific process flow is shown in table 1, and the preparation method comprises the following steps:
dissolving 100 parts by weight of butadiene rubber in hexane to obtain a rubber solution, wherein the number average molecular weight of the butadiene rubber is about 8.2 ten thousand, and the molecular weight distribution index is 1.8;
adding 20 parts by weight of phenolic resin and 5 parts by weight of carbon black into the rubber solution, and uniformly stirring to obtain a mixture;
and adding ethanol into the mixture to separate out and layer a solid mixture consisting of the butadiene rubber, the phenolic resin and the carbon black, carrying out solid-liquid separation, heating and drying the obtained solid mixture, and further removing the organic solvent to obtain the modified butadiene rubber.
According to a standard test formulation (non-oil-extended rubber) described in Table 1 of GB/T8660 + 2008 solution polymerization type Butadiene Rubber (BR) evaluation method and a method C2 described therein, 100 parts by weight of a modified cis-butadiene rubber, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of an accelerator TBBS, 60 parts by weight of a general industrial reference carbon black, 15 parts by weight of ASTM103# process oil and 1.5 parts by weight of sulfur were kneaded and vulcanized in an open kneader to obtain a vulcanized rubber.
The vulcanized rubber was tested for tear resistance, puncture resistance, and chipping resistance, and the specific test results are shown in table 1.
Comparative example 1
The unvulcanized rubber was prepared by following the formulation and method of example 1 using the cis-butadiene rubber before modification of example 1 as a raw rubber.
That is, 100 parts by weight of butadiene rubber, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of an accelerator TBBS, 60 parts by weight of general industrial reference carbon black, 15 parts by weight of ASTM103# process oil and 1.5 parts by weight of sulfur were kneaded and vulcanized in an open mill to obtain a vulcanized rubber.
The vulcanized rubber was tested for tear resistance, puncture resistance, and chipping resistance, and the specific test results are shown in table 1.
The test results of the comparative example 1 and the comparative example 1 show that the vulcanized rubber prepared by using the modified butadiene rubber in the example 1 as the raw material has the advantages of improved tear resistance by 38.2%, improved puncture resistance by 63.5% and obviously improved chipping and chipping resistance.
Example 2
The embodiment provides a preparation method of modified butadiene rubber, and the specific process flow is shown in table 1, and the preparation method comprises the following steps:
100 parts by weight of cis-butadiene rubber having a number average molecular weight of about 10.5 ten thousand and a molecular weight distribution index of 2.0 was dissolved in toluene to obtain a rubber solution.
Adding 25 parts by weight of terpene resin and 6 parts by weight of white carbon black into the rubber solution, and uniformly stirring to obtain a mixture;
and adding methanol into the mixture to separate out and layer a solid mixture consisting of the butadiene rubber, the terpene resin and the white carbon black, carrying out solid-liquid separation, heating and drying the obtained solid mixture, and further removing the organic solvent to obtain the modified butadiene rubber.
The modified butadiene rubber in this example was kneaded and vulcanized in an open mill according to the formulation and method in example 1 to obtain a vulcanized rubber.
The vulcanized rubber was tested for tear resistance, puncture resistance and resistance to chipping and chipping, and the specific test results are shown in table 1.
Comparative example 2
The butadiene rubber before modification in example 2 was used as a raw rubber, and a vulcanized rubber was prepared according to the formulation and method in example 1.
That is, 100 parts by weight of butadiene rubber, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of an accelerator TBBS, 60 parts by weight of universal industrial reference carbon black, 15 parts by weight of ASTM103# process oil and 1.5 parts by weight of sulfur were kneaded and vulcanized in an open mill to obtain a vulcanized rubber.
The vulcanized rubber was tested for tear resistance, puncture resistance and resistance to chipping and chipping, and the specific test results are shown in table 1.
The test results of the comparative example 2 and the comparative example 2 show that the vulcanized rubber prepared by using the modified butadiene rubber in the example 2 as the raw material has the advantages of 56.5% improvement of tear resistance, 56.0% improvement of puncture resistance and obvious improvement of anti-chipping and anti-chipping capabilities.
Example 3
The embodiment provides a preparation method of modified butadiene rubber, and the specific process flow is shown in table 1, and the preparation method comprises the following steps:
100 parts by weight of cis-butadiene rubber, the number average molecular weight of which was about 11.2 ten thousand and the molecular weight distribution index of which was 3.5, was dissolved in tetrahydrofuran to obtain a rubber solution.
Adding 30 parts by weight of carbon penta petroleum resin and 8 parts by weight of calcium carbonate into the rubber solution, and uniformly stirring to obtain a mixture;
and adding ethylene glycol into the mixture to separate out and layer a solid mixture consisting of the butadiene rubber, the carbon penta petroleum resin and the calcium carbonate, carrying out solid-liquid separation, heating and drying the obtained solid mixture, and further removing the organic solvent to obtain the modified butadiene rubber.
The modified butadiene rubber in this example was kneaded and vulcanized in an open mill according to the formulation and method in example 1 to obtain a vulcanized rubber.
The vulcanized rubber was tested for tear resistance, puncture resistance and resistance to chipping and chipping, and the specific test results are shown in table 1.
Comparative example 3
The unvulcanized rubber was prepared by following the formulation and method of example 1 using the cis-butadiene rubber before modification in example 3 as a raw rubber.
That is, 100 parts by weight of butadiene rubber, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of an accelerator TBBS, 60 parts by weight of general industrial reference carbon black, 15 parts by weight of ASTM103# process oil and 1.5 parts by weight of sulfur were kneaded and vulcanized in an open mill to obtain a vulcanized rubber.
The vulcanized rubber was tested for tear resistance, puncture resistance and resistance to chipping and chipping, and the specific test results are shown in table 1.
The test results of the comparative example 3 and the comparative example 3 show that the vulcanized rubber prepared by using the modified butadiene rubber in the example 3 as the raw material has the advantages of improved tear resistance by 44.4%, improved puncture resistance by 52.1% and improved chipping resistance.
Example 4
The embodiment provides a preparation method of modified butadiene rubber, and the specific process flow is shown in table 1, and the preparation method comprises the following steps:
100 parts by weight of cis-butadiene rubber having a number average molecular weight of about 12.3 ten thousand and a molecular weight distribution index of 4.6 was dissolved in cyclohexane to obtain a rubber solution.
Adding 25 parts by weight of acrylamide and 7 parts by weight of magnesium oxide into the rubber solution, and uniformly stirring to obtain a mixture;
and adding glycerol into the mixture to separate out and layer a solid mixture consisting of the butadiene rubber, the acrylamide and the magnesium oxide, carrying out solid-liquid separation, heating and drying the obtained solid mixture, and further removing the organic solvent to obtain the modified butadiene rubber.
The modified butadiene rubber in this example was kneaded and vulcanized in an open mill according to the formulation and method in example 1 to obtain a vulcanized rubber.
The vulcanized rubber was tested for tear resistance, puncture resistance, and chipping resistance, and the specific test results are shown in table 1.
Comparative example 4
The unvulcanized rubber was prepared by following the formulation and method of example 1 using the cis-butadiene rubber before modification in example 4 as a raw rubber.
That is, 100 parts by weight of butadiene rubber, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of an accelerator TBBS, 60 parts by weight of general industrial reference carbon black, 15 parts by weight of ASTM103# process oil and 1.5 parts by weight of sulfur were kneaded and vulcanized in an open mill to obtain a vulcanized rubber.
The vulcanized rubber was tested for tear resistance, puncture resistance, and chipping resistance, and the specific test results are shown in table 1.
The test results of the comparative example 4 and the comparative example 4 show that the vulcanized rubber prepared by using the modified butadiene rubber in the example 4 as the raw material has the advantages of 48.6% improvement of tear resistance, 46.9% improvement of puncture resistance and obvious improvement of anti-chipping and anti-chipping capabilities.
Example 5
The embodiment provides a preparation method of modified butadiene rubber, and the specific process flow is shown in table 1, and the preparation method comprises the following steps:
100 parts by weight of butadiene rubber having a number average molecular weight of about 10.5 ten thousand and a molecular weight distribution index of 2.0 was dissolved in tetrahydrofuran.
Adding 30 parts by weight of polyacrylamide and 5 parts by weight of carbon black into the rubber solution, and uniformly stirring to obtain a mixture;
and adding ethylene glycol into the mixture to separate out and layer a solid mixture consisting of the butadiene rubber, the polyacrylamide and the carbon black, carrying out solid-liquid separation, heating and drying the obtained solid mixture, and further removing the organic solvent to obtain the modified butadiene rubber.
The modified butadiene rubber in this example was kneaded and vulcanized in an open mill according to the formulation and method in example 1 to obtain a vulcanized rubber.
The vulcanized rubber was tested for tear resistance, puncture resistance, and chipping resistance, and the specific test results are shown in table 1.
Example 6
The embodiment provides a preparation method of modified butadiene rubber, and the specific process flow is shown in table 1, and the preparation method comprises the following steps:
100 parts by weight of cis-butadiene rubber, the number average molecular weight of which was about 11.2 ten thousand and the molecular weight distribution index of which was 3.5, was dissolved in tetrahydrofuran to obtain a rubber solution.
Adding 20 parts by weight of carbon-nine petroleum resin and 8 parts by weight of white carbon black into the rubber solution, and uniformly stirring to obtain a mixture;
and adding ethylene glycol into the mixture to separate out and layer a solid mixture consisting of the butadiene rubber, the carbon-nine petroleum resin and the white carbon black, carrying out solid-liquid separation, heating and drying the obtained solid mixture, and further removing the organic solvent to obtain the modified butadiene rubber.
The modified butadiene rubber in this example was kneaded and vulcanized in an open mill according to the formulation and method in example 1 to obtain a vulcanized rubber.
The vulcanized rubber was tested for tear resistance, puncture resistance, and chipping resistance, and the specific test results are shown in table 1.
TABLE 1 Table of Properties of vulcanizates in examples and comparative examples
Performance of Tear Strength/KN m-1 Puncture resistance/g Resistance to chipping and chipping
Example 1 52.8 0.19 Superior food
Comparative example 1 38.2 0.52 Difference (D)
Example 2 61.2 0.22 Superior food
Comparative example 2 39.1 0.50 Difference (D)
Example 3 55.6 0.23 Good wine
Comparative example 3 38.5 0.48 Difference (D)
Example 4 58.1 0.26 Superior food
Comparative example 4 39.1 0.49 Difference (D)
Example 5 53.1 0.21 Superior food
Example 6 54.2 0.25 Superior food
Example 7
The modified butadiene rubber in example 1 was used as a raw material to prepare an automobile tire, and the raw materials and the mass thereof were as follows:
20 parts by weight of modified butadiene rubber, 82.5 parts by weight of oil-extended styrene-butadiene rubber (zilupetrochemical, reference number 1712), 20 parts by weight of commercial SMR20 natural rubber, 62.5 parts by weight of carbon black N234, 15 parts by weight of white carbon black, 4 parts by weight of coupling agent, 3.5 parts by weight of aromatic oil, an anti-aging system (1 part by weight of anti-aging agent 4020, 2 parts by weight of anti-aging agent RD and 2 parts by weight of protective wax), 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 1.2 parts by weight of accelerator TBBS and 2 parts by weight of sulfur.
A rubber and plastic test internal mixer (the capacity is 1L) is adopted, the initial temperature of the internal mixer is 80 +/-5 ℃, and the rotating speed of a rotor is 70 r/min; XK-200 model 8-inch steam heating open mill for thin passing and back refining, front roll temperature: 50. + -.5 ℃ rear roll temperature: the concrete mixing process is shown in Table 2 at 50 + -5 deg.C.
TABLE 2 mixing Process for automobile tires
Figure BDA0001541390590000131
And (3) placing the plate for vulcanization for more than 12 hours after the plate is removed, wherein an XLB-400 x 40 flat plate vulcanizing machine is used for vulcanization, and the vulcanization condition is 150 ℃ x 30 min.
The tear and mechanical properties of the tread rubber of the tire are tested, and the specific results are shown in table 3.
Comparative example 5
The modified butadiene rubber in example 7 was replaced with butadiene rubber (number average molecular weight about 8.2 ten thousand, molecular weight distribution index 1.8), and the other raw materials and amounts were kept unchanged; and mixing and vulcanizing according to the process method provided in the embodiment 7 to obtain the automobile tire tread rubber. The obtained automobile tire tread rubber is tested for tear performance and mechanical properties, and the specific test results are shown in table 3.
The results of the comparative example 7 and the comparative example 5 show that, under the condition of the same addition amount, the modified butadiene rubber is used to replace the common butadiene rubber, the tear strength of the obtained automobile tire is improved, and the performance parameters such as the wet-skid friction coefficient, the rebound value, the hardness, the tensile strength, the compression fatigue temperature rise and the like are basically maintained, which indicates that the modified butadiene rubber provided by the example 7 can improve the tear resistance of the automobile tire, and the performance advantages such as high wet-skid resistance and low rolling resistance are still well maintained.
Example 8
Using the modified butadiene rubber of example 1 as a raw material, an automobile tire was prepared, in which: the used raw materials and the quality thereof are as follows:
82.5 parts by weight of modified butadiene rubber, 20 parts by weight of oil extended styrene butadiene rubber (zileute, designation 1712), 20 parts by weight of commercially available SMR20 natural rubber for industrial use, the other raw materials and formulation being the same as in example 7.
The automobile tire is obtained by adopting the process conditions completely consistent with those of the example 7, the tear and the mechanical property of the tread rubber of the tire are tested, and the specific test results are shown in the table 3.
As can be seen from Table 3, with the increase of the amount of the modified butadiene rubber, the tear strength and the elongation at break of the automobile tire are increased, and meanwhile, the parameters of the automobile tire, such as hardness, compression fatigue temperature rise, wet-skid friction coefficient, rebound value and the like, are basically kept unchanged, which indicates that the prepared automobile tire keeps the advantages brought by the original butadiene rubber.
Table 3 results of performance test of automobile tires in examples and comparative examples
Example 7 Comparative example 5 Example 8
Shore A hardness, DEG C 65 66 65
Tensile strength, MPa 22.71 21.65 23.15
Elongation at break,% 467 459 489
Permanent deformation by stretching% 12 13 11
Tear Strength, kN/m 72 65 81
Elevated temperature of compression fatigue 24.1 28.2 23.0
Power consumption, J/r 2.05 1.99 1.98
Coefficient of wet friction 38 37 37
Rebound value% 35 33 34
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (5)

1. A vulcanized rubber characterized by being obtained by subjecting a compounded raw material to a compounding vulcanization treatment, said compounded raw material consisting of 100 parts by weight of a modified butadiene rubber, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of an accelerator TBBS, 60 parts by weight of a universal industrial reference carbon black, 15 parts by weight of ASTM103# process oil and 1.5 parts by weight of sulfur;
The preparation method of the modified butadiene rubber comprises the following steps:
dissolving butadiene rubber in an organic solvent to obtain a rubber solution;
uniformly mixing a rubber anti-tearing agent, a rubber reinforcing agent and the rubber solution to obtain a mixture;
removing the organic solvent in the mixture to obtain the modified butadiene rubber;
by weight, cis-butadiene rubber: rubber anti-tearing agent: the reinforcing agent is 100: (20-30): (5-8);
the number average molecular weight of the butadiene rubber is 80,000-120,000, and the molecular weight distribution is 1.5-5.0;
the organic solvent in the mixture is removed, and the method specifically comprises the following steps:
adding a terminator into the mixture to separate out the rubber anti-tearing agent, the rubber reinforcing agent and the cis-butadiene rubber in the mixture from the organic solvent, then carrying out solid-liquid separation to obtain the modified cis-butadiene rubber,
wherein the terminator at least comprises one of methanol, ethanol, glycol and glycerol.
2. The vulcanizate of claim 1, wherein the organic solvent comprises at least one of hexane, toluene, cyclohexane, and tetrahydrofuran.
3. The vulcanizate of claim 1 or 2, wherein the rubber tear resistance agent is selected from at least one of phenolic resin, terpene resin, carbon pentapetroleum resin, carbon nonapetroleum resin, acrylamide, and polyacrylamide.
4. The vulcanized rubber according to claim 1 or 2, wherein the rubber reinforcing agent is at least one selected from the group consisting of carbon black, white carbon, calcium carbonate and magnesium oxide.
5. Use of the vulcanizate of any of claims 1 to 4 in rubber articles.
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