CN105802039B - A kind of high-air-tightness tire material and preparation method thereof - Google Patents
A kind of high-air-tightness tire material and preparation method thereof Download PDFInfo
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- CN105802039B CN105802039B CN201610187787.6A CN201610187787A CN105802039B CN 105802039 B CN105802039 B CN 105802039B CN 201610187787 A CN201610187787 A CN 201610187787A CN 105802039 B CN105802039 B CN 105802039B
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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Abstract
The present invention provides a kind of high-air-tightness tire material and preparation method thereof, which is prepared by the raw material of following mass parts: 60~70 parts of brombutyl, 10~15 parts of bromination SBS, 15~20 parts of natural rubber, 5~7 parts of coumarone indene resin, 5~7 parts of kayexalate, 10~15 parts of sheet-like fiber element, 5~7 parts of sheet zinc oxide, 7~10 parts of modified graphene oxide, 7~10 parts of octaphenyl-POSS, 20~30 parts of lignocellulosic, 1~3 part of sulphur, 3~5 parts of stearic acid, 3~5 parts of coupling agent.
Description
Technical field
The present invention relates to a kind of high-air-tightness tire materials and preparation method thereof.
Background technique
Automobile tire is in addition to needing to have the performances such as wear-resisting, stretch-proof, endurance, with greater need for the air-tightness with height,
The air-tightness of automobile tire height has the advantages that
(1) safety, driving performance and the comfort of traveling are improved；
(2) since mileage travelled improves, tread wear is improved, and extends the service life of tire；
(3) due to reducing rolling resistance, reduce the consumption of fuel；
(4) it is convenient for Motor Maintenance, reduces the number for checking tire pressure and inflation；
Since the automobile tire of high-air-tightness has the advantages that many, automobile tire material of the offer with high-air-tightness
Material has important practical significance.
Summary of the invention
The main purpose of the present invention is to provide a kind of tire materials of high-air-tightness, at the same the tire material also have it is excellent
Good mechanical performance.
It is another object of the present invention to provide a kind of high-air-tightness tire material, tire material of the invention is being reduced
While cost of material, guarantee that the air-tightness of tire material, mechanical performance are unaffected, or even is improving compared with prior art
The air-tightness and mechanical performance of tire.
To achieve the above objectives, the present invention provides a kind of high-air-tightness tire material, includes following in the tire material
Raw material: rubber base-material, sheet-like fiber element and sheet zinc oxide.
The sheet-like fiber element can both play the role of increasing the tire material air-tightness in the present invention, also help
The mechanical property for improving tire material, in addition, the sheet-like fiber element also has the function of anti-ultraviolet ageing.The sheet-like fiber
Element can be prepared by the following method:
(1) by cellulosic material and solid-state polymer grinding-material mixed grinding, microscopic appearance is obtained after grinding in the form of sheets
Cellulosic material；
(2) sheet-like cellulosic materials that step (1) obtains are separated with the solid-state polymer grinding-material, thus
Obtain sheet-like fiber element.
Specifically, in step (1), weight ratio that the solid-state polymer grinding-material is mixed with the cellulosic material
For (100~180): 100, the grinding carries out in ball mill or beveller, and grinding rate is 200~500rpm, when grinding
Between be 2~30h.In step (2), the sheet-like cellulosic materials are separated with the solid-state polymer grinding-material with sieve,
By controlling the aperture of sieve, the sheet-like fiber element that partial size is 30~50 microns is obtained.
The solid-state polymer grinding-material is selected from polyene hydrocarbons and their derivates, copolymer, and the cellulosic material is selected from
Native cellulose or regenerated cellulose.It is further preferred that the solid-state polymer is selected from one of following or a variety of: poly- second
Alkene, polypropylene, polystyrene, polyformaldehyde, epoxy resin, polycarbonate.The cellulosic material is selected from following one or more:
Natural herbs, natural xylophyta, viscose rayon.
On the one hand the sheet zinc oxide can play the role of promoting the vulcanization of rubber, to improve the machinery of tire material
Performance, on the other hand, the structure of sheet also has the function of gas barrier, to improve the air-tightness of tire material.This hair
The preparation method bibliography " Nanometer ZnO by Homogeneous Precipitation Method and sheet zinc oxide powder " of bright sheet zinc oxide
The method mentioned in (the 3rd phase of volume 30 " Yunnan chemical " in June, 2003), the partial size of the sheet zinc oxide are 20~150nm.
It preferably, further include graphene oxide in the tire material, the graphene oxide is conducive to improve tire material
The mechanical performance of material, while also having the function of anti-ultraviolet ageing, in the present invention, graphene oxide also have barrier air,
Improve the effect of tire material air-tightness.Further, in order to improve the compatibility performance of graphene oxide Yu rubber base-material, the present invention
Surface modification is selected to have the modified graphene oxide of 2- imidazoles -1- base ethamine, this is because 2- imidazoles -1- base ethamine can be with rubber
Halogen in base-material crosslinks reaction, to be conducive to improve the compatibility of graphene oxide and rubber base-material.
Preferably, further include eight silsesquioxane of octaphenyl (octaphenyl-POSS) in the tire material, be inorganic increasing
The mechanical performance of tire material can be improved in strong material.The experiment proves that octaphenyl-POSS is in formula of the invention
In, also advantageously improve the air-tightness of tire material.
It preferably, further include lignocellulosic in the tire material, the effect of the lignocellulosic mainly enhances
The mechanical performance of tire material.It is noted that sheet-like fiber element described previously is also possible to the lignocellulosic of sheet, this
The lignocellulosic at place refers exclusively to the lignocellulosic handled without sheet.
It preferably, include brombutyl in the rubber base-material.It is further preferred that the rubber base-material further includes
One of following raw material is a variety of: brominated styrene-butadiene-styrene block copolymer (bromination SBS), natural rubber,
Coumarone indene resin, kayexalate.It is further preferred that the rubber base-material by brombutyl, bromination SBS,
Natural rubber, coumarone indene resin, kayexalate composition.
Brombutyl itself has a preferable air-tightness, but the disadvantage is that price is higher, therefore of the invention described
Rubber substrate selects some common, inexpensive rubber to replace part brombutyl, is guaranteeing that tire material is airtight
While property and mechanical performance do not reduce, it is reduced the cost of tire material.
It preferably, further include sulphur, stearic acid and coupling agent in the raw material of the tire material.The wherein coupling agent choosing
Select following one or more: coupling agent KH570, coupling agent KH550, coupling agent KH560, coupling agent KH151, coupling agent KH171.
Preferably, each raw material of the tire material is according to following proportion by weight: 60~70 parts of brombutyl, bromine
10~15 parts of SBS, 15~20 parts of natural rubber, 5~7 parts of coumarone indene resin, 5~7 parts of kayexalate, sheet are fine
It is 10~15 parts of dimension element, 5~7 parts of sheet zinc oxide, 7~10 parts of modified graphene oxide, 7~10 parts of octaphenyl-POSS, wooden
20~30 parts of cellulose, 1~3 part of sulphur, 3~5 parts of stearic acid, 3~5 parts of coupling agent.
The present invention also provides a kind of methods for preparing the high-air-tightness tire material, comprising the following steps:
(1) each component of the rubber base-material is put into mixer and is kneaded, dumping；
(2) it after film is cooled to room temperature, is put into open mill and is kneaded, be alternately added sheet-like fiber element, modified oxygen
Graphite alkene, octaphenyl-POSS and lignocellulosic after band packet roller, add sheet zinc oxide, sulphur, coupling agent and hard
Ester acid, obtains mixture after mixing；
(3) vulcanize the mixture on vulcanizing press and obtain the tire material, conditions of vulcanization is 120 DEG C~160
DEG C, sulfurizing time is 12~15min, 12~18MPa of pressure.
Preferably, the time being kneaded in step (1) is 20~25min, and the time being kneaded in step (2) is 30~40min.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Embodiment 1
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, sheet-like fiber element the preparation method is as follows: the lignocellulosic for taking 50g dry, mixed with 50g polyethylene
It after conjunction, is added in ball mill and grinds 16h, mill ball is the stainless steel ball of diameter 16mm, grinding rate 300r/min.Grinding is completed
Afterwards, it is sieved with stainless steel and separates sheet-like fiber element powder with polyethylene, obtain sheet-like fiber element.
The modified graphene oxide aoxidizes stone the preparation method is as follows: a certain amount of 2- imidazoles -1- base ethamine is added
In the ethanol solution of black alkene, wherein the mass ratio of graphene oxide and ethyl alcohol is 1: (10~20), 2- imidazoles -1- base ethamine and oxygen
The mass ratio of graphite alkene is (4~5): 1,10~20min of ultrasonic disperse, 60~80h of back flow reaction, is removed at 90~120 DEG C
Remove supernatant liquor, be washed to graphene oxide for neutrality, in a vacuum drying oven at 90~100 DEG C drying 12~for 24 hours, be made
Modified graphene oxide.
The tire material is prepared by following steps:
(1) bromobutyl rubber, bromination SBS, natural rubber, coumarone indene resin and polyvinylbenzenesulfonic acid are put in proportion into
It is kneaded into mixer, is kneaded 20~25 minutes back glues；
(2) after film is cooled to room temperature, be put into open mill and be kneaded, alternating be proportionally added into octaphenyl-POSS,
Modified graphene oxide, sheet-like fiber element and lignin after band packet roller, then are proportionally added into sulphur, sheet zinc oxide, idol
Join agent and stearic acid, mixing 30~obtain tire material mixture after forty minutes；
(3) vulcanize the tire material mixture on vulcanizing press and obtain the automobile tire material, conditions of vulcanization
It is 120~160 DEG C, sulfurizing time is 12~15 minutes, and pressure is 12~18MPa.
Embodiment 2
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Embodiment 3
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Embodiment 4
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Embodiment 5
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Embodiment 6
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Embodiment 7
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Embodiment 8
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Embodiment 9
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Embodiment 10
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Embodiment 11
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Embodiment 12
A kind of high-air-tightness tire material, is made of the raw material of following weight parts:
Wherein, the preparation method of the sheet-like fiber element, the modified graphene oxide and the tire material is the same as implementation
Example 1.
Comparative example
Select commercially available Lanxess company dedicated for preparing the brombutyl of tire, it is commercially available by testing
The correlated performance of tire material, to illustrate advantage of the tire material provided by the invention in mechanical performance and air-tightness.
Dependence test is carried out in accordance with the following methods to the tire material obtained in above embodiments 1-12 and comparative example: elongation
Rate and tensile strength are that sample is cut into sub- tinkling of pieces of jade shape, are measured using cupping machine；Tensile strength is according to the mark of ASTM D 790
What standard measured；Fatigue durability is implemented according to ASTM method, measures under 120% state of elongation；Air Porosity is benefit
With diameter 50mm, 250 μm of thickness of sample, the value measured at a temperature of 30 DEG C of measurement based on ASTM test condition, unit is
cc·cm/m2·hr·atm。
For convenient for comparing each embodiment, table 1 lists the mass parts of each raw material in embodiment 1-12.Table 2 gives each reality
Apply the test result of example.
Table 1
Table 2
It can be found by comparative example 1-11 and comparative example, tire material provided by the invention and existing tire material
It compares, mechanical performance and air-tightness have the promotion of certain amplitude；Further, since higher cost in tire material of the invention
The content of bromobutyl rubber is few compared with the content of the bromobutyl rubber of existing air-tightness tire material, therefore its overall cost
Have and largely declines；By comparative example 1 and embodiment 6,7,8, octaphenyl-POSS and lignocellulosic master are illustrated
Play the role of enhancing mechanical performance, while being also beneficial to improve the air-tightness of tire material；By comparative example 1 and in fact
Example 9,10,11 is applied, illustrates that sheet-like fiber element has the function of significantly improving tire material air-tightness and mechanical performance, sheet
The air-tightness and mechanical performance of tire material also can be improved in zinc oxide to a certain extent, and modified graphene oxide is in certain journey
The air-tightness of tire material can be improved on degree；Sheet-like fiber element, sheet zinc oxide and modified graphite are not added in comparative example 12
The air-tightness of alkene, tire material is worst, illustrates sheet-like fiber element, sheet zinc oxide and modified graphene compounding from the negative
When, there is synergistic effect, be more advantageous to the air-tightness for improving tire material.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (4)
1. a kind of high-air-tightness tire material, which is characterized in that the tire material includes following raw material: 95~119 mass parts
Rubber base-material, 10~15 mass parts sheet-like fiber element, the sheet zinc oxide of 5~7 mass parts, 7~10 mass parts modification
Graphene oxide, eight silsesquioxane of octaphenyl of 7~10 mass parts, 20~30 mass parts lignocellulosic, the modification
Graphene oxide is the modified graphene oxide of 2- imidazoles -1- base ethamine, and the rubber base-material includes the bromine of 60~70 mass parts
Change butyl rubber, brominated styrene-butadiene-styrene block copolymer of 10~15 mass parts, 15~20 mass parts day
Right rubber, the coumarone indene resin of 5~7 mass parts, 5~7 parts of mass parts kayexalate.
2. high-air-tightness tire material according to claim 1, which is characterized in that the raw material of the tire material also wraps
It includes: the coupling agent of the sulphur of 1~3 mass parts, the stearic acid of 3~5 mass parts and 3~5 mass parts.
3. high-air-tightness tire material according to claim 1 or 2, which is characterized in that the partial size of the sheet-like fiber element
It is 30~50 μm, the partial size of the sheet zinc oxide is 20~150nm.
4. a kind of method for preparing high-air-tightness tire material as claimed in claim 2, comprising the following steps:
(1) each component of the rubber base-material is put into mixer and is kneaded, dumping；
(2) it after film is cooled to room temperature, is put into open mill and is kneaded, be alternately added sheet-like fiber element, modified oxidized stone
Black alkene, eight silsesquioxane of octaphenyl and lignocellulosic, band packet roller after, add sheet zinc oxide, sulphur, coupling agent and
Stearic acid obtains mixture after mixing；
(3) vulcanize the mixture on vulcanizing press and obtain the tire material.
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| CN201610187787.6A CN105802039B (en) | 2016-03-23 | 2016-03-23 | A kind of high-air-tightness tire material and preparation method thereof |
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| CN201610187787.6A CN105802039B (en) | 2016-03-23 | 2016-03-23 | A kind of high-air-tightness tire material and preparation method thereof |
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| CN105802039B true CN105802039B (en) | 2019-01-11 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106554528B (en) * | 2016-11-14 | 2019-01-01 | 安徽理工大学 | Butadiene-styrene rubber/white carbon black/lignocellulosic/montmorillonite rubber composite material and preparation method thereof |
| CN106750597A (en) * | 2016-12-16 | 2017-05-31 | 芜湖天鸿汽车零部件有限公司 | A kind of age inhibiting tire material of automobile and preparation method thereof |
| CN107057110A (en) * | 2017-01-01 | 2017-08-18 | 薛明天 | The manufacture method of graphene-containing tire |
| JP6999373B2 (en) * | 2017-11-13 | 2022-01-18 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for tires and pneumatic tires |
| CN108276688B (en) * | 2018-03-23 | 2020-06-30 | 常州大学 | Graphene flame-retardant constraint damping sheet for vehicle and preparation method thereof |
| CN110791029B (en) * | 2019-11-14 | 2020-10-27 | 华南理工大学 | Lignin grafted brominated butyl rubber composite material and preparation method thereof |
| CN110964339B (en) * | 2019-12-24 | 2022-03-29 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of bio-based composite material film with good air tightness |
| CN111410847A (en) * | 2020-04-30 | 2020-07-14 | 杭州升策能源科技有限公司 | Naphthenic base rubber oil composition for improving air tightness of tire rubber material and preparation method and application thereof |
| KR102308320B1 (en) * | 2020-09-25 | 2021-10-06 | 넥센타이어 주식회사 | Bead-Apex rubber composition and manufacturing method thereof |
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| CN102516609A (en) * | 2011-11-15 | 2012-06-27 | 常州市华伟医疗用品有限公司 | Chopped fiber rubber |
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