CN109503913A - One kind is exempted to inflate fretting map rickshaw tire raw material and exempts to inflate fretting map rickshaw tire and preparation method thereof - Google Patents
One kind is exempted to inflate fretting map rickshaw tire raw material and exempts to inflate fretting map rickshaw tire and preparation method thereof Download PDFInfo
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- CN109503913A CN109503913A CN201710829165.3A CN201710829165A CN109503913A CN 109503913 A CN109503913 A CN 109503913A CN 201710829165 A CN201710829165 A CN 201710829165A CN 109503913 A CN109503913 A CN 109503913A
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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
- C08L17/00—Compositions of reclaimed rubber
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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
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/107—Nitroso compounds
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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
- B60C2001/0091—Compositions of non-inflatable or solid tyres
-
- 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
- B60C2200/00—Tyres specially adapted for particular applications
-
- 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
- B60C2200/00—Tyres specially adapted for particular applications
- B60C2200/12—Tyres specially adapted for particular applications for bicycles
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- C08J2317/00—Characterised by the use of reclaimed rubber
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- 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
- C08J2409/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Exempt to inflate fretting map rickshaw tire raw material the invention discloses one kind and exempts to inflate fretting map rickshaw tire and preparation method thereof, tyre material includes the SSBR of Narrow Molecular Weight Distribution, width distribution contains the powdery PSBR every agent, ground rubber, filled rubber oil and auxiliary agent, auxiliary agent is mainly foaming agent, pigment, promotor, anti-aging agent, activator and crosslinking agent etc., these raw materials pass through extruding pelletization-extrusion injection molding, the fretting map rickshaw tire of exempting to inflate of preparation has good resilience and weatherability, intensity is high, high temperature is indeformable, low temperature is not cracked, wear-resisting tear-proof, rolling resistance is small, the features such as long service life.
Description
Technical field
The present invention relates to a kind of tire materials, and in particular to one kind is with the butylbenzene rubber such as SSBR, PSBR, SBS and ground rubber
Glue is the tyre material of primary raw material, and the side of fretting map, high intensity, high abrasion manpower tire for vehicles is prepared with tyre material
Method；Belong to technical field of polymer composite materials.
Background technique
Existing non-aerating rickshaw (containing trolley, shared bicycle and bicycle etc.) is with the material of tire by thermoplasticity
The composition such as elastomer, polyurethane, polyolefin and thermosetting resin.For example, Japanese patent application (JP-A) N0.2003-104008
The pneumatic tire formed by using thermoplastic macromolecule material is disclosed with N0.03-143701；Chinese patent (publication number
CN1348878A a kind of solid type for manpower vehicle) is disclosed, is suitble to use on rickshaw, bicycle.It specifically discloses existing
Solid inner tube is set in the cover tire of somebody's cycle tyre, to replace inflated inner tyre, which is made of rubber-plastics material,
Its material forms 15~30%wt% containing rubber, and 70~85wt% of polyurethane, manufacturing method is as follows, rubber and polyurethane by than
After example is mixed with fluid state, injection molding in-mold molding becomes solid inner tube after cooling.Its main feature is that having certain
Elasticity and wearability, simple production process is easy to operate, and assembly is simple；Chinese patent (Publication No. CN105295216A)
It discloses a kind of antifatigue, heatproof and exempts from air tyre thermoplastic elastic material and preparation method thereof, hydrogenated by super high molecular weight
100-150 parts of styrenic elastomer, 80-150 parts of white oil, 10-50 parts of polyphenylene oxide, 20-50 parts of polypropylene, 5-15 parts of polyethylene,
Polyolefin blend toughener 5-15,10-30 parts of minerals powder, silicone powder 3-8,0.2-0.5 parts of stabilizer, first by above-mentioned superelevation
Molecular weight hydrogenated styrenic elastomer is sufficiently mixed with white oil, then it is mixed with remaining material, is placed in double screw extruder, warp
Melting extrusion is granulated, and which overcome conventional styrene analog thermoplastic elastomer material over time to use fatigability difference and height
Temperature uses heatproof.For another example Chinese patent (publication number CN105017595A) discloses a kind of preparation of microporous foam tire Tire & Tube
Method, specifically disclosing a kind of microporous foam tire, it includes cover tire and the inner tube of a tyre, and the inner tube of a tyre is by 200 parts of latex reclaimed rubber, promotor
It is 3.45~3.60 parts, 5~6.5 parts of vulcanizing agent, 24~27 parts of foaming agent, 20~30 parts of filler, 5.5~7.5 parts of activator, soft
8~15 parts of agent, while preparation method is specifically disclosed, provided microporous foam tire has following characteristics: one, no
Be afraid of thorn, be not required to inflate；Two, cushion performance is good, makes to travel safer, more stable；Three, weatherproof, will not be because of summer
Weather is overheated and is blown out；Four, cover tire is protected, the service life of cover tire is extended；Without replacement, to increase old cover tire again
Utility value.Chinese patent (publication number CN91106451.6A) discloses a kind of non-inflatable bicycle tyre and moulding process, no
Inflatable bicycle tyre is by the entity structure of polyurethane material machine-shaping, and inside has been equipped with the cord of muscles and bones effect, intermediate
Further equally it is equipped with multiple contract holes.Its structure is simple, is not afraid of bundle, is not required to inflate, and service performance is good.Its moulding process includes mixed
Close stock, casting, stripping forming, the processes such as curing.Feature is to be poured rear mold on centrifugation random with 150~450 revs/min
Speed rotates 20~80 seconds, then stripping forming, can guarantee there is the knot bubble of change of gradient in tire in this way, tire it is elastic, resistance to
Mill property is moderate.
In addition, there are also following documents to report about solid tyre and preparation process:
In (" manufacturing method of Method for Solid Tire of Cellular PU Elastomer ", " rubber industry ", 05 phase in 2010) text
The raw material and composition principle of Method for Solid Tire of Cellular PU Elastomer are disclosed, the raw material of synthetic microporous elastomer include more
First alcohol, diisocyanate, chain extender, catalyst, foaming agent, foam stabilizer and other additives.Polyalcohol has polyester polyol (such as
Polyadipate ethylene glycol propylene glycol ester) etc. and polyether polyol (such as polytetrahydrofuran ether glycol)；Diisocyanate is common
TDI, MDI etc.；Chain extender has 1,4-butanediol etc.；Foaming agent has water and methylene chloride etc.；Catalyst have triethylenediamine and
Dibutyl tin dilaurate；Foam stabilizer L-520 etc.；Other auxiliary agents include fire retardant, antioxidant and colorant etc..It is real by research
It tramples, it is believed that had compared with other processing methods in the moulding process of Method for Solid Tire of Cellular PU Elastomer using centrifugal casting
Following advantages: microporous polyurethane elastomer manufactures solid tyre, is all to be directly injected into material using static method in the past
Mold, using horizontal direction centrifugal casting, so as to obtain even density variation, without apparent lamination between each layer,
Mutual integral homogeneous strata each other.Meanwhile solid tyre is manufactured using the method for horizontal direction centrifugal casting, it fully demonstrates
Polyurethane material itself and its convenient advantage of processing, overcome traditional solid tire and only have vulcanization for a long time just to can guarantee tire
Face and inside tires state of cure (vulcanization) match, but tend to that tyre surface over cure, tire core is caused to owe the drawbacks such as sulphur, substantially increase
Production efficiency.
Zhao Fei write " polyurethane elastomer fills research " " the international rubber in 2004 of solid tire formulation and technique
Proceeding (C) " in by the synthesis technology of polyurethane elastomer filler material by polyether polyol, filling oil be proportionally added
In reaction kettle, in the TD l that metering is added, performed polymer (component A) is obtained.Polyalcohol, chain extender, catalysis separately will proportionally be added
Agent, filling oil are added in reaction kettle, carry out dehydration degassing reaction l h or so, sealing is used as B component.A, B component are passed through into metering
Pump enters a static mixer according to 1:1 ratio and is mixed, injects tyre cavity by valve cock after mixing, reach one
Stop injection after constant-pressure, closes sprue.Tire vulcanizes 2 4h in 5 DEG C of 60 scholar of drying chamber, at room temperature after cure for 24 hours, i.e.,
?.The test of filler material physical mechanical property is that after mixing A B component, it is laggard that standard test piece is molded on vulcanizing press
Capable.
Tannus TIRE bicycle company was once proposed a kind of solid bicycle tyre of on-inflatable, used one kind
It is called the special material of micro- closed pore fretting map polymer resin, can punctures anti-, corrodes and while aging, also there is light matter
The appearance of amount and fashion, the tire of three kinds of hardness, while having black, yellow is red, and white etc. plants color, but resinification scientific name
It is not introduced.In addition some companies have used styrene-butadiene elastomer and its hydride and PP, white oil etc. to cooperate,
It is merely the horizontal garden circumferential direction etc. in tire using solid bicycle (or shared bicycle) tire made of Shooting Technique is squeezed out
Away from the uniform garden hole for having left 6-8mm, for the purpose of having reduced material utilization amount and tire quality, referred to as aperture solid tyre.
In general, the characteristic behavior of existing solid tyre there are several types of.
It is that base material has been molded into hole solid tyre that the first, which is with thermoplastic elastomer (TPE), polyolefin, mineral oil etc.,.This tire
The shortcomings that be high material consumption, carcass is heavy, at high cost, easily bursts, and deformation is big, elasticity and antifatigue difference, and rolling resistance is big, resistance to
Wait property and wear no resistance, aging speed is fast, easily relaxation deformation or fragmentation tread flaking, service life was less than 1 year.
Be for second using polyurethane, plastics or rubber, recycling vulcanized rubber powder as foam solid tyre made of material.It is this
The shortcomings that tire be carcass be it is plastic foamed form, therefore especially continuous fair speed run when fetal rhythm foam segment it is soft rapidly
Change, then fragmentation and be not available, carcass is easy to harden, hardening lost its bounce, and tearing-resistant performance is poor, bearing capacity and weak heat-dissipating, rolling
Dynamic resistance is big, and temperature Gao Shiyi softens, and is easy tread flaking, not wear-resisting.
Summary of the invention
For the automobile-used tire material dosage consumption of inflation manpower is exempted from the prior art greatly, carcass is heavy, at high cost, explosive
It splits, elasticity and weatherability are poor, and rolling resistance is big, and aging speed is fast, easily relaxation deformation or fragmentation tread flaking and the easy plate of carcass
Knot hardens lost its bounce, tearing-resistant performance, bearing capacity and weak heat-dissipating, temperature Gao Shiyi softening tread flaking, not wear-resisting, service life
The defect and disadvantage of short and vulcanization time length etc..
The first purpose of this invention is to be to provide one kind with butylbenzene copolymer and ground rubber rubber as main component
Collagen material can obtain resilience and good weatherability by simple extruding pelletization and extrusion injection molding process, and intensity is high, high temperature
The rickshaw tire for the advantages that indeformable, low temperature is not cracked, wear-resisting tear-proof, rolling resistance is small, long service life.
Second object of the present invention is to be that providing one kind has good resilience and weatherability, and intensity is high, high temperature
The fretting map for the advantages that indeformable, low temperature is not cracked, and wear-resisting, tear-proof and fatigue resistance are good, and rolling resistance is small, long service life
Rickshaw tire.
Third object of the present invention is to be to provide described in a kind of simple process, with short production cycle, inexpensive preparation
The method of fretting map manpower tire for vehicles.
In order to achieve the above technical purposes, exempt to inflate fretting map rickshaw tire raw material, packet the present invention provides one kind
Include following content of component: SSBR10~60 part；10~60 parts of PSBR (PSBR, P are Powder abbreviation)；SBS20~60 part；Again
40~60 parts of raw rubber powder；20~50 parts of softer filler rubber oil；20.5~31 parts of auxiliary agent.
Of the invention has selected butylbenzene copolymer and ground rubber to make for exempting to inflate in fretting map rickshaw tire raw material
For primary raw material, these types of raw material can be carried out by crosslinking agent it is micro- be crosslinked, give tire with good resilience and weather-proof
Property, intensity is high, and high temperature resistant is indeformable, and low temperature is not cracked, and wear-resisting, tear-proof is antifatigue, rolling resistance is small, long service life etc.
Feature.
Preferred scheme, the SSBR are the solution polymerized butadiene styrene rubber of Narrow Molecular Weight Distribution, molecular weight distributing index≤1.15.
More preferably number average molecular weight Mn=120000~150000 of SSBR, Mooney viscosity are ML=55~70.Further preferably
SSBR include polystyrene block mass percentage content be 15~20%, block mass ratio S/B=(25~35)/(65
~75).The easy-to-use batch mixer of SSBR polymer or pulverizer, which smash blocky SSBR, to granulate, convenient for mixing, be granulated, both can low temperature
Be kneaded again can high-temperature injection molding, while absorbing rubber oil (and briquetting viscosity and the big wide molecular weight point of cold flow in low-high Wen Shiyi
The SSBR of cloth such as 2557S or VSL5025 etc. not can be carried out granulation).The present invention can be selected it is existing such as commercially available SSBR1205 or
Dynasol 1205。
Preferred scheme, the PSBR are wide molecular weight distribution containing the powder shape emulsion polymerized styrene butadiene rubber every agent, molecule
Measure profile exponent >=2.5.More preferably number-average molecular weight Mn=200000~300000 of PSBR, Mooney viscosity ML=40~
80.Further preferred PSBR be it is powdered, partial size be 20~80 mesh.There is PSBR polymer low temperature to be easier to mixing, elasticity
Appropriate and VISCOUS FLOW is good, oil absorbency high and low temperature or high temperature process performance are good.It can be selected existing such as commercially available PSBR
1502 or PSBR 1588.
Preferred scheme, block mass ratio S/B=(25~35)/(65~75) of the SBS.More preferably SBS is
Linear or hub-and-spoke configuration, number-average molecular weight Mn=80000~200000.The SBS selected in tire formulation not only contains largely
Vulcanization double bond crosslinking points, another effect be SBS and Narrow Molecular Weight Distribution the mixed granulation material of SSBR it is strong, not cold
It is agglomerating that adhesion is not generated between stream, pellet, is convenient for subsequent tire injection molding.It is wherein most preferably for example commercially available Ba Ling board of SBS
The kinds such as YH-796, YH-791, YH-803, YH-805 or at least one of the SBS of other companies production.
Preferred scheme, the ground rubber fineness are 80~120 mesh.The ground rubber is discarded or waste tire powder
Rubber powder after broken.The present invention, as aggregate, has elasticity using ground rubber, can participate in vulcanization and have certain oil absorbency, can be bright
It is aobvious to improve its wearability, extend the service life of tire, wear-resisting property is increased to maximum.
Preferred scheme, the softer filler rubber oil include white oil, naphthenic oil, Valelinum Liquidum, environment-friendly rubber oil, Gao Fang
At least one of hydrocarbon ils.More preferably softer filler rubber oil is naphthenic oil or environment-friendly aromatic oil.Such as commercially available NAP-10, middle sea
At least one of oily 322# and TDAE oil.
Preferred scheme, the auxiliary agent include foaming agent, pigment, promotor, anti-aging agent, activator and crosslinking agent.It is more excellent
Foaming agent in the auxiliary agent of choosing, pigment, promotor, anti-aging agent, activator and crosslinking agent mass ratio be 1.5~2:8~10:2~
4:2~3:5~9:2~3.
Preferred foaming agent is organic compound that small molecule compound can be discharged at a temperature of 120~200 DEG C.It is further excellent
The foaming agent of choosing includes at least one of azodicarbonamide, blowing agent H, ADC, DNTA, DAB, AIBN.Most preferably send out
Infusion is azodicarbonamide (AC).
Preferred promotor include accelerator TBBS, diphenylguanidine, accelerant CZ, hypervelocity grade dithiocarbamate class,
At least one of xanthate accelerator, thuriam acceserator.Further preferred promotor is aminodithioformic acid
At least one of zinc, PZ, ZDC, BZ, tetraethylthiuram disulfide, tetrabutylthiuram disulfide.Promotor of the invention can
Select the common accelerator TBBS of tire industry, diphenylguanidine, accelerant CZ and hypervelocity grade dithiocarbamate class or xanthan
At least one of Barbiturates promotor and thuriam acceserator；Further preferred active height, for short vulcanization and
The hypervelocity grade promotor of cryogenic vulcanization, such as dithiocarbamates such as zinc dithiocarbamate, PZ, ZDC, BZ and two
At least one of tetraethylthiuram sulfide (TETD), tetrabutylthiuram disulfide (TBTD).
Preferred anti-aging agent is amines antioxidants.Because whether heat ageing, Weather-resistant, ozone are old for amines antioxidants
Better than antiageing effects such as Hinered phenols, aldehydes and heterocyclics in terms of the agings such as change, light and surrender, it is advantageous to prevent for amine
At least one of old agent, such as antioxidant D, A, OD, 405, DFL, DNPA, RD, AW, DD.
Preferred pigment is carbon black.Pigment is not limited to carbon black, can be other pigment, can be carried out according to tire color
Appropriate selection.The present invention selects most conventional carbon black as raw material.
Preferred crosslinking agent is sulphur.
Preferred activator includes inorganic activator and organic activator；Wherein, inorganic activator and organic activator
Mass ratio is 2~8:2~6.Preferred inorganic activator is zinc oxide.Preferred organic activator is stearic acid.
The raw material for exempting to inflate fretting map rickshaw tire of the invention has selected short vulcanization promotor, shortens injection mould
Take turns tyre stock vulcanization time in tool, accelerate the yield in the unit time of tire, select amines antioxidants substitute it is traditional by
It hinders phenolic antioxidant and realizes manpower tire for vehicles anti-aging property, weatherability；Foaming agent is selected to make to take turns tyre stock in injection mold
Resolving into micro-molecular gas when vulcanization under the influence of temperature makes vulcanizate fretting map, to make tire lightweight and to reduce cost.
The raw material for preferably exempting from inflation fretting map rickshaw tire, is made of: SSBR 20~30 following content of component
Part；20~30 parts of PSBR；SBS 30~40；40~60 parts of ground rubber；20~50 parts of softer filler rubber oil；Foaming agent 1.5
~2 parts；Pigment is 8~10 parts；2~4 parts of promotor；2~3 parts of anti-aging agent；3~5 parts of inorganic activator；Organic activator 2~4
Part；2~3 parts of crosslinking agent.
Exempt to inflate fretting map rickshaw tire the present invention also provides one kind, passes through extruding pelletization and extrusion by above-mentioned raw materials
Injection molding is prepared.
300% stress at definite elongation of the automobile-used tire building sizing material of preferred fretting map manpower is 4~5MPa, and the A hardness that continues is 60
~70, it is permanently deformed to 16~24%, elongation rate of tensile failure is 280~320%, and elasticity is 30~40%, density is 0.60~
0.65g/cm3。
The present invention also provides the preparation methods for exempting to inflate fretting map rickshaw tire comprising following steps:
1) SSBR powder, SBS, ground rubber, softer filler rubber oil, pigment, anti-aging agent, activator and crosslinking agent are existed
It is stirred at room temperature uniformly, obtains bulk sizing material；(note: should not carry out PSBR to make material, otherwise can lose pellet adhesion, interleaving agent
Effect)；
2) the bulk sizing material is granulated by Screw Extrusion, obtains being granulated sizing material；
3) the granulation sizing material is stirred evenly with PSBR, promotor, foaming agent and softer filler rubber oil, is mixed
Material；
4) by mixture by injection molding, curing to get.
Preferred scheme, in step 1), softer filler rubber oil dosage is the 3/4~4/5 of softer filler oil total amount.
Preferred scheme, in step 1), the time being stirred is 5~8min.
Preferred scheme, in step 2), prilling temperature is 190~210 DEG C.
Preferred scheme, it is described to be granulated the columnar-shaped particle that sizing material is ∮ (3~6) х (3~6).
Preferred scheme, in step 3), softer filler rubber oil dosage be softer filler oil total amount 1/5~1/4 (note:
A small amount of oil, which is added, to adhere to auxiliary agent and pellet-powder uniformly, and oil has been added PSBR adhesion easily).
Preferred scheme, in step 3), the time being stirred is 3~6min.
Preferred scheme, in step 4), in injection molding process, melting temperature is 190~210 DEG C, and temperature is tieed up in mold
120~180 DEG C are held, soaking time is 8~12min.
Preferred scheme, in step 4), in maturing process, curing temperature is 80~100 DEG C, the curing time is 10~
15min。
The of the invention manufacturing method for exempting to inflate fretting map manpower tire for vehicles comprising the following specific steps
Step 1: by weighed SSBR, SBS, ground rubber, 3/4~4/5 filled rubber oil of total dosage, carbon black, preventing
Old agent, ZnO, stearic acid and sulphur etc. are put into batch mixer carries out high speed 5~8min of agitation at room temperature, i.e. material is considered as mixing
Uniformly, for use；
Step 2: by the hopper storage bin in the bulk sizing material investment screw extruder of the first step after mixing, in 190
Extruding pelletization at~210 DEG C is cut into the columnar-shaped particle of ∮ (3~6) х (3~6), spare；
Step 3: by second step be granulated sizing material, etc. 1/5~1/4 filling with the promotor of ratio, foaming agent and total dosage
Rubber oil (note: oil product can be by powdery promotor and foaming agent uniform adhesion on the surface of granular blank in mixing) investment mixing
High speed 3~6min of agitation is carried out in machine at room temperature, is uniformly mixed depending on material；(note: third step is resulting uniformly mixed
Material is kneaded at 70~80 DEG C with two roller rubber mixing machines is pressed into mixed sheet, is then sulfided under 145 DEG C/8min on tablet press machine
Type can carry out performance measurement)
Step 4: by the hopper storage bin in the mixture investment injection moulding machine in third step, in 190~210 DEG C
Sizing material melt is injected in tire forming mold under injection temperature, maintaining melt temperature in tire forming mold is 120~180
DEG C, time (note: vulcanization and foaming time) 8~12min, certainly, the sulfidization molding time is longer, and crosslink density is bigger, fourth
Benzene rubber only vulcanization crosslinking degree reach relatively completely after intensity just it is guaranteed, otherwise fetus intensity is inadequate, is then turned on mold
The tire of sulfidization molding, such injection molding-sulfur foam-demoulding are taken out in demoulding, and circulation is prepared repeatedly, take out the wheel of sulfidization molding
Tire continues 10~15min of curing at 80~100 DEG C.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
The composition of raw materials for exempting from the to inflate fretting map manpower tire for vehicles of the invention granular or powder good using fluidity of molten
Shape SSBR, PSBR and SBS give processing performance good in the easy injection molding process of mixture as main material；Three block in formula
Contain a large amount of double bond in butylbenzene (S-B-S) molecule, can under sulphur effect the cross-linked network that be formed, and can and ground rubber with
Chemical bond is connected, and intensity, wearability and the resilience after giving injection molding tyre vulcanization reduce the deformation of carcass, extend and use
Service life.The crosslinked that softened rubber filling oil can be such that micro- crosslinked after S-B or vulcanization is formed with ground rubber, which has, preferably to be filled out
Compatibility is filled, the hardness of carcass is adjusted, the rolling resistance for increasing elasticity, reducing tire.The ultrahigh speed vulcanization accelerator that uses and
Sulphur accelerates curingprocess rate, shortens the machine-shaping time, avoids injection molding cured tire base and burns；Foaming is used
Agent reduces the density of micro- crosslinking carcass, saves material；Amines antioxidants is used, increase tire uses the time.
Of the invention exempts from inflation fretting map rickshaw tire excellent combination property, has good resilience and weatherability,
The features such as intensity is high, and high temperature is indeformable, and low temperature is not cracked, wear-resisting tear-proof, rolling resistance is small, long service life.Such as fretting map
300% stress at definite elongation of the automobile-used tire building sizing material of manpower is 4~5MPa, and the A hardness that continues is 60~70, it is permanently deformed to 16~
24%, elongation rate of tensile failure is 280~320%, and elasticity is 30~40%, and density is 0.60~0.65g/cm3。
The Tire & Tube for exempting to inflate fretting map manpower tire for vehicles of the invention is an entirety, is not required to inflate.
It is of the invention to exempt to inflate simple fretting map manpower tire for vehicles preparation method, short preparation period, at low cost, be conducive to
Industrialized production.
Specific embodiment
The present invention is illustrated with following embodiment, does not constitute the limitation to the scope of the invention or implementation method.
The mixing pellet in the 4th step of manufacturing method of the present invention is vulcanized using YXE-50 type pressure forming machine, is vulcanized
145 DEG C of х 8min of condition.
Using the physical property of INSTRON5565 type puller system measurement sulfide film.
Using the abrasion of abrasion machine measurement sulfur foam film in the room VIM company LAT100.
Using the rolling resistance of POLYSAR company DUNLOP power loss instrument measurement vulcanizate.
Examples 1 to 7 and comparison implement 1~2:
Examples 1 to 7 and comparative example 1~2 are by the first to the of the manufacturing method of manpower tire for vehicles of the present invention
Three-step approach operation preparation pellet, then the pellet of production is passed through into the 4th step sulfidization molding；
Step 1: by weighed SSBR1205, SBS, ground rubber, total dosage 3/4~4/5 filled rubber oil, carbon
Black, anti-aging agent, ZnO, stearic acid and sulphur etc. are put into batch mixer carries out high speed 5~8min of agitation at room temperature, i.e. material regards
Be it is uniformly mixed, for use.
Step 2: the sizing material of the first step after mixing is added in the funnel in screw extruder, squeezed out at 200 DEG C
It is granulated, the columnar-shaped particle for being cut into ∮ (3~5) х (3~5) is spare.
Step 3: by second step be granulated sizing material, etc. with the PSBR of ratio, promotor, foaming agent and total dosage 1/5~1/
4 filled rubber oil are put into batch mixer carries out high speed agitation 5min at room temperature, is uniformly mixed depending on material.
Step 4: by the funnel in the mixture investment injection moulding machine in third step, under 200 DEG C of injection temperature
Sizing material melt is injected in tire forming mold, after melt temperature is 160 DEG C of 8~12min of time in maintenance tire forming mold,
It is then turned on mold releasability, takes out the tire of sulfidization molding, such injection molding-sulfur foam-demoulding, circulation is prepared repeatedly, is taken out
The tire of sulfidization molding continues 10~15min of curing in air oven at 80~100 DEG C.
The manufacturing process that Examples 1 to 7 and comparative example 1~2 detect print is: by the above-mentioned first step to third step fabrication
Material, then the material of production is through mixing and hot-forming on vulcanizing press.Each molded samples are finally subjected to physical property
Detection, the physical property of each contrast sample of embodiment are shown in Table 2.
Example 1~7 and comparative example 1~2 formula such as table 1:
Table 1
Embodiment 1
SBS is YH-805, foaming agent H, promotor PZ, anti-aging agent D, other components such as table 1.
Embodiment 2
SBS is YH-791, foaming agent AC, promotor ZDC, anti-aging agent OD, other components such as table 1.
Embodiment 3
SBS is YH-796, foaming agent AC, promotor PZ, anti-aging agent A, other components such as table 1.
Embodiment 4
SBS is YH-801, foaming agent AC, promotor BZ, anti-aging agent 405, other components such as table 1.
Embodiment 5
SBS is YH-791H, foaming agent DNTA, promotor TETD, anti-aging agent D, other components such as table 1.
Embodiment 6
SBS is LG411, foaming agent DAB, promotor TBTD, anti-aging agent RD, other components such as table 1.
Embodiment 7
SBS is LG411, foaming agent AIBN, promotor BZ, anti-aging agent DD, other components such as table 1.
Comparative example 1
Formula and composition are merely that promotor is changed to 2.0 parts of TBBS, 1.5 parts of accelerant CZ with embodiment 6.
Comparative example 2
Formula and composition are merely that promotor is changed to 2.0 parts of diphenylguanidine, 1.8 parts of accelerant CZ with example 5.
YH type series SBS product is the production of synthetic rubber division department, China Petrochemical Corporation Ba Ling petro-chemical corporation, can
Directly to be bought by market approach.
LG411 is the SBS of LG Chem. company production.
Table 2
It indicates:
The present invention is compared and general mild of tire industry using the micro foaming composite material of ultra-rapid vulcanization promotor preparation
Or MC medium curing diphenylguanidine, TBBS are compared with the CZ micro foaming composite material prepared, the vulcanization in Comparative result example 1-2 is answered
The corresponding abrasion of condensation material are higher, and rolling resistance and density are larger, and elasticity, hardness, intensity and elongation rate of tensile failure are lower.
The result shows that the present invention has obtained apparent beneficial effect.(it cannot overrun or over cure, keep away when the vehicle tire sulfuration of higher-end
Exempt from incipient scorch；The man power driven cart tyre of low side wants short vulcanization mainly to improve per unit area yield certainly.)
Sulfidization molding glue sample of the invention in Examples 1 to 3 is made detection print with comparative example 1~2 to be respectively put into
Heat ageing is carried out in thermal aging oven.150 DEG C of х 72h of aging condition, the results are shown in Table 3.
Table 3
Illustrate:
After heat ageing, composite material strength conservation rate of the invention is relatively high, and deformation ratio loss is smaller, elastically keeps
Degree is big, abrasion climbing is smaller.The automobile-used Tire Composites of manpower i.e. of the invention have preferable anti-aging property.
Claims (34)
1. one kind is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: including following content of component:
SSBR10~60 part；
PSBR10~60 part；
SBS20~60 part；
40~60 parts of ground rubber；
20~50 parts of softer filler rubber oil；
20.5~31 parts of auxiliary agent.
2. one kind according to claim 1 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the SSBR is
The solution polymerized butadiene styrene rubber of Narrow Molecular Weight Distribution, molecular weight distributing index≤1.15.
3. one kind according to claim 2 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the SSBR's
Number average molecular weight Mn=120000~150000, Mooney viscosity are ML=55~70.
4. one kind according to claim 1,2 or 3 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: described
The polystyrene block mass percentage content that SSBR includes is 15~20%, block mass ratio S/B=(25~35)/(65~
75)。
5. one kind according to claim 1 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the PSBR is
Wide molecular weight distribution contains the powder shape emulsion polymerized styrene butadiene rubber every agent, molecular weight distributing index >=2.5.
6. one kind according to claim 5 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that:
Number-average molecular weight Mn=200000~300000 of the PSBR, Mooney viscosity ML=40~80.
7. according to claim 1, one kind described in 5 or 6 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: described
The partial size of PSBR is 20~80 mesh.
8. a kind of raw material for exempting to inflate fretting map rickshaw tire according to claim 1, it is characterised in that: the SBS
Block mass ratio S/B=(25~35)/(65~75).
9. one kind according to claim 1 or 8 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the SBS
It is linear or hub-and-spoke configuration, number-average molecular weight Mn=80000~200000.
10. one kind according to claim 1 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the regeneration
Rubber powder fineness is 80~120 mesh.
11. one kind according to claim 1 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the softening
Filled rubber oil includes at least one of white oil, naphthenic oil, Valelinum Liquidum, environment-friendly rubber oil, high aromatic oil.
12. one kind according to claim 11 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the softening
Filled rubber oil is naphthenic oil or environment-friendly aromatic oil.
13. described in any item one kind are exempted to inflate fretting map rickshaw tire raw material according to claim 1~12, feature exists
In: the auxiliary agent includes foaming agent, pigment, promotor, anti-aging agent, activator and crosslinking agent.
14. one kind according to claim 13 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: foaming agent,
Pigment, promotor, anti-aging agent, activator and crosslinking agent mass ratio be 1.5~2:8~10:2~4:2~3:5~9:2~3.
15. one kind according to claim 14 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the foaming
Agent is that organic compound of small molecule compound can be discharged at a temperature of 120~200 DEG C.
16. one kind according to claim 15 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the foaming
Agent includes at least one of azodicarbonamide, blowing agent H, ADC, DNTA, DAB, AIBN.
17. one kind according to claim 14 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the promotion
Agent include accelerator TBBS, diphenylguanidine, accelerant CZ, hypervelocity grade dithiocarbamate class, xanthate accelerator,
At least one of thuriam acceserator.
18. one kind according to claim 17 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the promotion
Agent is zinc dithiocarbamate, at least one in PZ, ZDC, BZ, tetraethylthiuram disulfide, tetrabutylthiuram disulfide
Kind.
19. one kind according to claim 14 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: described anti-old
Agent is amines antioxidants.
20. one kind according to claim 14 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the pigment
For carbon black.
21. one kind according to claim 14 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the crosslinking
Agent is sulphur.
22. one kind according to claim 14 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: the activation
Agent includes inorganic activator and organic activator；Wherein, the mass ratio of inorganic activator and organic activator is 2~8:2~6.
23. one kind according to claim 22 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: described inorganic
Activator is zinc oxide.
24. one kind according to claim 22 is exempted to inflate fretting map rickshaw tire raw material, it is characterised in that: described organic
Activator is stearic acid.
25. described in any item one kind are exempted to inflate fretting map rickshaw tire raw material according to claim 1~24, feature exists
In: it is made of following content of component:
20~30 parts of SSBR；
20~30 parts of PSBR；
SBS 30~40；
40~60 parts of ground rubber；
20~50 parts of softer filler rubber oil；
1.5~2 parts of foaming agent；
Pigment is 8~10 parts；
2~4 parts of promotor；
2~3 parts of anti-aging agent；
3~5 parts of inorganic activator；
2~4 parts of organic activator；
2~3 parts of crosslinking agent.
26. one kind is exempted to inflate fretting map rickshaw tire, it is characterised in that: led to by any one of claim 1~25 raw material
It crosses extruding pelletization and squeezes out injection molding and be prepared.
27. one kind according to claim 26 is exempted to inflate fretting map rickshaw tire, it is characterised in that: fretting map rickshaw
It is 4~5MPa with 300% stress at definite elongation of tire building sizing material, the A hardness that continues is 60~70, is permanently deformed to 16~24%, draws
Disconnected elongation is 280~320%, and elasticity is 30~40%, and density is 0.60~0.65g/cm3。
28. exempting from the preparation method of inflation fretting map rickshaw tire described in claim 26 or 27, it is characterised in that: including following
Step:
1) by SSBR powder, SBS, ground rubber, softer filler rubber oil, pigment, anti-aging agent, activator and crosslinking agent in room temperature
It stirs evenly, obtains bulk sizing material；
2) the bulk sizing material is granulated by Screw Extrusion, obtains being granulated sizing material；
3) the granulation sizing material is stirred evenly with PSBR, promotor, foaming agent and softer filler rubber oil, obtains mixture；
4) by mixture by injection molding, curing to get.
29. exempting from the preparation method of inflation fretting map rickshaw tire according to claim 28, it is characterised in that: step 1)
In, softer filler rubber oil dosage is the 3/4~4/5 of softer filler oil total amount；The time being stirred is 5~8min.
30. exempting from the preparation method of inflation fretting map rickshaw tire according to claim 28, it is characterised in that: step 2)
In, prilling temperature is 190~210 DEG C.
31. exempting from the preparation method of inflation fretting map rickshaw tire according to claim 28, it is characterised in that: the granulation
Sizing material is the columnar-shaped particle of ∮ (3~6) х (3~6).
32. exempting from the preparation method of inflation fretting map rickshaw tire according to claim 28, it is characterised in that: step 3)
In, softer filler rubber oil dosage is the 1/5~1/4 of softer filler oil total amount；The time being stirred is 3~6min.
33. exempting from the preparation method of inflation fretting map rickshaw tire according to claim 28, it is characterised in that: step 4)
In, in injection molding process, melting temperature be 190~210 DEG C, in mold temperature maintain 120~180 DEG C, soaking time be 8~
12min。
34. exempting from the preparation method of inflation fretting map rickshaw tire according to claim 28, it is characterised in that: step 4)
In, in maturing process, curing temperature is 80~100 DEG C, and the curing time is 10~15min.
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| CN110294872A (en) * | 2019-05-24 | 2019-10-01 | 南京海旗新材料科技有限公司 | A kind of inner tube of a tyre foamed material of high-elastic damping |
| CN111777806A (en) * | 2020-07-21 | 2020-10-16 | 四川远星橡胶有限责任公司 | Maintenance-free tire rubber material and preparation method thereof |
| CN111777835A (en) * | 2019-04-04 | 2020-10-16 | 中国石油化工股份有限公司 | Inflation-free tire material and preparation method thereof |
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