CN108623800A - It is a kind of to reduce the tread mix of tire drag, tread rubber and preparation method thereof - Google Patents
It is a kind of to reduce the tread mix of tire drag, tread rubber and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/24—Epihalohydrins
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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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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- 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 Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of tread mixes reducing tire drag, including unsaturated epoxy epichlorohydrin rubber, SSBR, BR, zinc oxide, stearic acid, white carbon, carbon black, softening agent, silane coupling agent, anti-aging agent, wax, environment-friendly rubber oil, accelerating agent and sulphur；The monomer that the unsaturated epoxy epichlorohydrin rubber is made of allyl glycidyl ether, propylene oxide, ethylene oxide, epoxychloropropane and ethylene glycol diglycidylether carries out ring opening copolymer under the effect of trialkylaluminium series catalysts and forms.The present invention also provides a kind of preparation methods using tread rubber and the tread rubber made from the tire tread compound.The present invention is easily kneaded using the component.Vulcanized rubber has modified rubber material using quantity few as meridian passenger car tire tread material, and vulcanizate intensity is high, earth-grasping force is big, and compression heat generation is low compared with original SSBR compound materials not being modified, rolling resistance improvement rate reaches 26 31%.
Description
Technical field
The present invention relates to a kind of low crystallization, epoxy-epichlorohydrin rubber of unsaturated double-bond and solution polymerized butadiene styrene rubbers to prepare
The method of high-performance tire tire tread material；Belong to the preparation of functionalization very-high performance radial and application field.
Background technology
It is alternately total through open loop under Ziegler-Natta catalyst effect by epoxides such as ethylene oxide, propylene oxide
A kind of polymer obtained from poly- is referred to as epoxy rubber；By epoxychloropropane, ethylene oxide through polymerizeing made of ring opening copolymer
Object claims epichlorohydrin rubber.Above-mentioned epoxy rubber and epichlorohydrin rubber has heat-resisting, oil resistant, weather-proof, resistance to gas permeability, cold resistance good
Rubber.It is widely used in the accessory of automobile, aircraft and various machineries, such as washer, sealing ring, diaphragm, it is also possible to make resistance to factice
Pipe, printing rubber roll, offset plate, lining etc., but cannot act as the material of very-high performance radial.If with ethylene oxide, ring
Such as allyl glycidol of the epoxide containing unsaturated double-bond on a small quantity is added in Ethylene Oxide, epoxychloropropane comonomer
Ether, which carries out copolymerization, can obtain unsaturated epoxy-epichlorohydrin rubber, because containing unsaturated double-bond in this kind of polymer molecule, can use sulphur
Vulcanization is used as tire material.
Red Qi Xing of Xie Ke Chen Yu etc. exist《The preparation and representation of ternary unsaturation chlorohydrin rubber》Non- toluene is used in one text
Class low pole non-toxic organic object is solvent, carries out precipitation polymerization reaction and is prepared for ternary unsaturation chlorohydrin rubber.This method is to use
N-hexane is solvent, by epoxychloropropane, ethylene oxide, allyl glycidyl ether and alkyl aluminum-based catalyst complex compound into
Row copolymerization, but author does not study the molecular configuration configuration of polymer and crystallinity etc., while not to the ternary of preparation
Saturation chlorohydrin rubber does not further apply tire industry.
It is compiled in N.B. jar (unit of capacitance) Monot husbands《Synthetic rubber》The second edition, in Chemical Industry Press to epoxy propane rubber and
Epichlorohydrin rubber has described below：Propylene oxide, ethylene oxide, allyl glycidyl ether and epoxychloropropane are copolymerized constants
Larger, such as r (ethylene oxide)=2.5, r (epoxychloropropane)=0.045, i.e. it is total to carry out binary for ethylene oxide and epoxychloropropane
Poly- that the comonomer chain link generated is caused to be unevenly distributed in polymer chain, ethylene oxide chain link forms block and epoxy chlorine
Propane chain link is related with " head-tail " connection, and copolymer is caused to generate crystallization, and the crystalline content of polymer reaches 13%.This birdss of the same feather flock together
Object is closed because crystallinity is higher, even if the tire made with synthetic rubber such as solution polymerized butadiene styrene rubber, high cis-BR (polybutadiene rubber)
Face glue also has higher " Payen effects ", i.e., it is larger to roll heat for tire.
Document《Γ opu н Ю .A., Γ α Л к u н a г и, pe ü x в н .u Б ρ .- κ ay ц y К и pe3n н
A, 1968, № 8, c.2.》The epoxy propane rubber that Liao Quansu synthetic rubber research institute synthesizes of reporting for work has the following performance：It is mixed
The Mooney viscosity of rubber of kneading is 50-60, and Tg=-74 DEG C, armful roller of rubber compound is good, no incipient scorch phenomenon.If propylene oxide
Non-filling rubber tensile intensity value is relatively low, shows that epoxy propane rubber degree of randomness is high or crystalline texture content is relatively low, it will embody
Go out preferable cold resistance, wearability, the stability for having height to alkali, water and ozonization, it is heat-resisting up to 130-150 DEG C, to oil product
Stablize with solvent action, epoxy third is illustrated close to the level of natural rubber, valuable comprehensive performance in many performance indicators
Alkane rubber is widely applied foreground in terms of rubber product, gummed cloth, the coating of resistance to ozone and other products, high intensity, high-elastic
Property and repeatedly deformation when dynamic loss it is small, preceding Soviet Union scientist once foretold that " characteristic behavior of epoxy propane rubber was in tire product side
Face will become promising glue kind.Technical staff in industry knows, the epoxy propane rubber molecule of single propylene oxide homopolymerization
It, can not be blend sulfurized with solution polymerized butadiene styrene rubber without double bond in structure.On the other hand, before the eighties in last century, high ethylene
A large amount of input industrialized productions, demand of the people to " super- high-performance tire " are not also the solution polymerized butadiene styrene rubber of content not yet
It is very urgent, now, " high-end " super- high-performance tire " recognized extensively by people, that is, anti-slippery, ultralow rolling resistance, low life
The indispensable material of hot, low temperature resistant meridian tyres for passenger cars can be by polynary unsaturated epoxy rubber and SSBR (solution polymerized butadiene styrene rubber)
It is feasible to be combined.
It is well known that the SSBR of high-vinyl-content is to prepare anti-slippery, low-rolling-resistance meridian tyres for passenger cars to have
Effect material still increases with the contents of ethylene in SSBR, and the Tg of material can also rise, and resistance to low temperature declines, compound material
Leather state is showed at -15~-20 DEG C and is followed the string, and the wearability of tread rubber is deteriorated；In addition, even if modified now
SSBR such as HPR yarn row products also are difficult to the rolling resistance of car tire reaching A grades of standards that (rolling resistance reaches A grades, illustrates tire
Rolling resistance is minimum, saves fuel efficiency highest), it is such as copolymerized with butyl lithium initiation butadiene, styrene, using polarity
It closes object and carries out end capping reaction, because of reasons such as moistures, ending ratio can not possibly reach 50%, lead to the cured tire of SSBR and BR mixtures
Face glue has relatively strong " Payne " effect, and the dynamic heat build up and rolling resistance of tire still will produce.In addition, because SSBR polarity is relatively low
It is ineffective that " powder is eaten when being kneaded with white carbon ", and dispersibility of the white carbon in rubber compound is also uneven, also will produce " Payne "
Effect.And highly polar epoxy rubber have with white carbon good mixing property, low temperature resistant, cyclic deformation dynamic loss is small, anti-
The features such as high temperature, resistance to ozone, oil resistant is not available for SSBR, in addition, undersaturated epoxy rubber can use Sulfur with SSBR
Cross moulding can substantially reduce " Payne " effect that SSBR long-chain molecules inert terminal generates under periodic strain effect, make
SSBR long-chain molecules inert terminal " passivation " reduces dynamic heat build up.However, to currently, epoxy rubber is modified SSBR this respects
Research do not appear in the newspapers also to.
Document《Gruber.F.E., MeyerD.A., SwartG.H.et.al-Ind.Eng.chem.,
Proc.Res.Dev., 1964, v.3.No3, p.194-199.》Epoxy propane rubber of having reported for work is contracted by propylene oxide and allyl
Water glycerin ether is copolymerized, and trade name Dynagen and Parel-58, the two belong to binary copolymerization glue, wherein contain in monomer
There are the allyl glycidyl ether of the left and right 2% (mol), the legislate crystallinity of polymer to reach 16-20.Jiang Wanlan is compiled《The world
Rubber industry》, 2003,21 (5)：To by epoxy in 10-14. " processability and its application field of epoxy propane rubber " text
The technique for the epoxy propane rubber that propane is synthesized with allyl glycidyl ether, the composition of catalyst and preparation, polymerization regulation etc.
It is studied.The copolyreaction of the propylene oxide and allyl glycidyl ether is in ingredients concentration 9~1O% (matter
Amount) toluene solution in carry out.The ratio of propylene oxide, allyl glycidyl ether in dispensing is 50：1(mol).Mesh
Before, ratio 2% and 20% of the allyl glycidyl ether in polymerizeing total monomer in the epoxy rubber of the prior art, polymer
Or double key number in is relatively low or higher, that is, when the double key number content of epoxy rubber is relatively low, will there is the epoxy rubber of part
Glue does not carry out vulcanization crosslinking with diene-based synthetic rubber (such as SSBR), and crosslink density can be low；Second, when pair of epoxy rubber
When bond number content is higher, epoxy rubber will have itself vulcanization crosslinking of part, compound adhesive to detach forming portion split-phase state, and vulcanizate is hard
The defects of there is difference in degree, filling oil is unevenly distributed in vulcanizate.In addition, existing epoxy propane rubber molecular structure is
Linear structure, polymer molecular weight distribution is not wide enough, and tack is low, and banding characteristics can be bad；Third, polymer is binary or ternary
Monomer composition, is also easy to produce the crystalline element block of stereotyped structure, and the high polymer of block concentration can increase the rolling life of tread rubber
Heat.
The epoxy rubber H1100 principal monomers of auspicious urn (ZEON) the company production of Japan are by epoxychloropropane (ECH) and allyl
Two kinds of monomer compositions of base glycidol ether (AGE), epoxy rubber T3100 by tri- kinds of monomer compositions of ECH/EO/AGE, H1100 and
T3100 contains unsaturated double-bond, and available sulfur cross-linking, but the crystallinity of this kind of polymer, block concentration and in height
Application in performance tire, which yet there are no, reports for work.
Currently, main as high-performance tire tread rubber with glue is SSBR, then coordinate the auxiliary agents such as high cis-BR, white carbon
Mixing vulcanizes.Such as in CN201210440907.0 " application of a kind of solution polymerized butadiene styrene rubber and its synthetic method and acid anhydrides " and
It is situated between respectively in CN201210121049.3 " preparation and application of a kind of styrene-conjugated diene copolymer containing activity in conjunction with sulphur "
It has continued and has used the polymer of the invention as main glue, coordinated high cis-BR, tread mix is used as made of the vulcanization of the auxiliary agents such as white carbon
The earth-grasping force of high-performance meridian tire, tire is B grades, and rolling resistance is C grades, i.e. the industrial grade of tire is not achieved at all
Double A class criterias.Li Hantang compiles improved compound rubber [J] modern rubber skills of white carbons and carbon black-filled tread rubber
Art, 2012,38 (5)：It is reacted with sodium hydride using 18 carbon mercaptan -1,18 of straight chain in mono- texts of 12-17. and generates 18 carbon dithiols
Then sodium adds edittrialkyl chlorosilane and reacts the modifying agent for generating 18 carbon sulphur-trialkyl silica -1,18 with dithiol sodium, will
This modifying agent is used as the backbone modification agent of SSBR, is used as the basis glue of high-performance tire, then coordinates white carbon for car
Tyre surface materials, are used to prepare high-performance tire, and this polymer chain by less polar functionalities constitutes new backbone modification
Technology can further decrease the hysteresis loss of vulcanizate and reduce the rolling resistance of tire.In addition, the document has also related to
When butadiene one is styrene copolymerized, the polar group containing monomer of growing polymer chain is introduced, unfortunately, additional monomer is normal
It often influences whether kinetics of polymerization, therefore the performance of original non-modified polymer can be changed.In addition, original polymeric object is usually difficult
To remove unconverted backbone modification agent from the liquid stream of conventional polymeric factory (such as from solvent stream), therefore Third monomer can be with
Conversion between accumulation and prevention polymer rank.The polar compound of the base containing both-end in the above-mentioned molecules of SSBR in the prior art
SSBR modifying agent polar groups are introduced into long flow path in strand, difficulty in process, and the polar group deal contained is few, for drop
Heat and hysteresis loss of the low vulcanized rubber in cyclomorphosis are limited, that is, it is weaker to reduce Payne effects.
In addition, introducing the condensate of highly polar high molecular weight in high-performance tire formula, there is presently no documents to report for work.
Invention content
It is lacked present on molecular configuration construction and microstructure for epoxy rubber in the prior art or chlorohydrin rubber
It falls into and is less than with the backbone modification agent complex manufacturing technology of existing SSBR and existing SSBR molecular ends functionalization enclosed
50%, when applied to high-performance tire tread rubber, made tread rubber is to reducing tire heat unobvious, payne effects
Still higher deficiency.The present invention provides a kind of tread mixes reducing tire drag, it is intended to pass through the sizing material
It is prepared the tire tread glue with very-high performance, such as improve tire tread glue grab ground tractive force and rolling resistance.
The present invention also provides the tire treads that the tread mix using the reduction tire drag is prepared
Material and the preparation method.
A kind of tread mix reducing tire drag, including unsaturated epoxy-epichlorohydrin rubber, SSBR and BR；
Unsaturated epoxy-the epichlorohydrin rubber is by allyl glycidyl ether, propylene oxide, ethylene oxide, epoxy chlorine
Mix monomer including propane and ethylene glycol diglycidylether carry out ring opening copolymer under the effect of trialkylaluminium series catalysts and
At.
The epoxy containing unsaturated double-bond-epichlorohydrin rubber (unsaturation ring that the present invention passes through the polynary monomer composition
Oxygen-epichlorohydrin rubber) modified material as SSBR, the epoxy containing unsaturated double-bond-chlorine ether rubber of this polynary monomer composition
Glue has the characteristics that crystallinity is low, undefined structure content is high, crystalline blocks unit content is low.The present invention is by the unsaturation
Epoxy-epichlorohydrin rubber, which is applied to be kneaded, is made meridian passenger car tire tread sizing material, can obviously maintain original high-vinyl SSBR
Tire tread compound grab ground tractive force it is unaffected under, the rolling resistance improvement rate of tire is reached into 26-31%；Tire rolls
Resistance reaches B grades or higher A pole marks is accurate, can largely reduce vehicle fuel consumption.
Preferred scheme, the mole percent level of each monomer is in the mix monomer：Allyl glycidyl ether 5~
10%；Ethylene glycol diglycidylether 0.05%~0.1%；Propylene oxide 70~80%；Epoxychloropropane 5~12.5%；Ring
Oxidative ethane 5~12.5%.Technical scheme of the present invention, can be by ring by introducing a small amount of ethylene glycol diglycidylether monomer
Oxygen-epichlorohydrin rubber carries out cladodification, to increase the elasticity and cohesive force of polymer, while also helping polymer and voluntarily glues and being unified into
Grain, improves the banding characteristics and processing performance of polymer.Due to epoxychloropropane, ethylene oxide, allyl glycidyl ether, epoxy
The unexpectedly poly- rate of propane and ethylene glycol diglycidylether difference is larger, selects polynary component to carry out copolymerization and is conducive to each monomer progress
Alternating copolymerization is reduced to the greatest extent amorphous polymer generation, propylene oxide chain link is avoided to be joined with " head-tail " or " head-head " (" tail-tail ")
The generation of knot mode reduces the crystallinity of polymer.
Preferred scheme, trialkylaluminium series catalysts system include by trialkylaluminium, ether, water and acetylacetone,2,4-pentanedione catalyst
The catalyst and organic solvent of composition.Trialkylaluminium can be made to hydrolyze using ether in the trialkylaluminium series catalysts system of the present invention
Become milder, promote the generation of trialkylaluminium oxirane, improve yield, composition is uniform.Triethyl aluminum and triisobutyl aluminium phase
Than the former places or heat without prolonged, allyl glycidyl ether in copolymer can be made unsaturated using triethyl aluminum
The content of chain link is unrelated with the conversion level of monomer, and the allyl glycidyl ether chain link in epoxy propane copolymer can be made to present
It is random to be uniformly distributed, help to establish uniform vulcanization net, propylene oxide and allyl glycidyl are sweet when because using triethyl aluminum
Data are consistent similar in oily ether copolymerization constant.The acetylacetone,2,4-pentanedione of use is that the structure during Polymerization of Propylene Oxide is adjusted
Agent, can also three-dimensional adjustment effect in a slight decrease and reduction polymer crystallinity.
More preferably scheme, catalyst is by trialkylaluminium, ether, water and acetylacetone,2,4-pentanedione in molar ratio 1: 1.5: (0.5~
1.0): (0.5~1.5) composition.
Preferred scheme, catalyst amount are the 2~4% of mix monomer integral molar quantity, wherein catalyst is with trialkyl
Aluminium measures.
Further preferred scheme, trialkylaluminium include triisobutyl aluminium and/or triethyl aluminum.
More preferably scheme, organic solvent are at least one of toluene, thiacyclohexane and methyl cyclohexanol.Most preferably hexamethylene
Alkane.
In the trialkylaluminium series catalysts system of the present invention, it is preferred to use the triethyl group that mass percentage content is 20%
Aluminium/cyclohexane solution.The ether mass percentage content used is 99.5%.The water used is deionized water.The acetyl of use
Acetone quality degree is 99.8%.
More preferably scheme, the mass percent concentration of mix monomer in organic solvent are 10~12%.
The process conditions of preferred scheme, ring opening copolymer are：Temperature is 75~85 DEG C, and the time is 8~10h, pressure 0.3
~0.4MPa.
The preparation method of the trialkylaluminium series catalysts of the present invention, at -5~5 DEG C, by trialkylaluminium: ether: water: second
Acyl acetone is by molar part than 1: 1.5: (0.5~1.0): (0.5~1.5) puts into successively to clean dried transposed through nitrogen
In container, after agitated 30min to get.If be not required to for a long time using triethyl aluminum series catalysts prepared by triethyl aluminum
Placement or heating can come into operation.A concentration of 0.8~1.3mol/L of aluminium in trialkylaluminium series catalysts.Trialkylaluminium system urges
Agent preparation process medium temperature is spent low, and water can freeze；Temperature is excessively high, and complex compound activity reduces.
Unsaturated epoxy-the epichlorohydrin rubber has 1 structure of formula：
Wherein, m, n, p, q, s are respectively epoxychloropropane, ethylene oxide, allyl glycidyl ether, propylene oxide and second
The constitutional repeating unit number of Hexanediol diglycidyl ether, in formula 1, the ratio of the respective content of m, n, p, q, s and the addition of corresponding monomer
Example is related, this belongs to the scope that the art is appreciated that；R is epoxychloropropane, ethylene oxide, allyl glycidol
The branched structure that ether, propylene oxide, ethylene glycol diglycidylether monomer etc. are formed by ring-opening polymerisation.
Preferably, the monomer composition ratio of the unsaturated epoxy-epichlorohydrin rubber is allyl glycidyl ether mol numbers
The 5~10% of total monomer amount are accounted for, ethylene glycol diglycidylether mol numbers account for the 0.05%~0.1% of total monomer amount, propylene oxide
Mol numbers account for the 70~80% of total monomer amount, and epoxychloropropane mol numbers account for the 5~12.5% of total monomer amount, ethylene oxide mol numbers
Account for the 5~12.5% of total monomer amount；Wherein the catalyst composition of monomer polymerization and ratio are triethyl aluminum: ether: water: acetyl
The molar ratio of acetone is 1: 1.5: 0.5~1.0: 0.5~1.5.
Unsaturated epoxy-epichlorohydrin rubber preparation method of the present invention is as follows：Solvent ring has been added in the polymeric kettle of steel
Then alkane is added quantitative epoxychloropropane, ethylene oxide, allyl glycidyl ether, propylene oxide and ethylene glycol two and shrinks
Temperature of charge in polymeric kettle is risen to 75~85 DEG C with hot bath later, sucks quantitative three with syringe at this time by glycerin ether
Alkyl aluminum-based catalyst simultaneously injects in polymeric kettle visor, then catalyst is pressed into polymeric kettle with nitrogen, and keeps pressure in kettle
For 0.3~0.4MPa, after 8~10h under strong stirring the suspension polymerisation of epoxy-epichlorohydrin rubber can complete, be then added quantitative
Water terminate polymerisation 15min, antioxidant 1076 is added later, finally by suspension polymer with water vapor accumulation remove it is molten
Agent, granular polymer carry out drying.
In the present invention, the unsaturated preferred Mooney viscosity of epoxy-epichlorohydrin rubber is 60-70.
Preferably, the vulcanized rubber 300% of the unsaturated epoxy-epichlorohydrin rubber non-filling skeleton filler is stretched and is answered surely
Power is not higher than 0.5MPa, and stretch breaking strength is not higher than 1.2MPa, and specific elongation rate is higher than 500%.It is strongly low to show polymer without fixed
Type structural content is high, and crystallinity is low.
Preferably, in the tread mix, the SSBR weight by dry rubber, the unsaturated epoxy-chlorine ether rubber
The weight ratio of glue, SSBR and BR is 15~30: 80~82: 36~40.
In the present invention, the tread mix, except comprising unsaturated epoxy-epichlorohydrin rubber of the present invention, SSBR and
Also include the material for allowing addition that those skilled in the art can recognize outside BR；For example, vulcanization aid, coloured material, enhancing
Material etc..
Preferably, the tread mix also includes activator, white carbon, carbon black, softening agent, anti-aging agent, silane idol
Join agent, wax, environment-friendly rubber oil and accelerating agent and sulphur.
Preferably, in SSBR molecules 1, the 2- additions unit content of polybutadiene unit in 55-70moL%, in conjunction with
Styrene units content is in 20-30wt%.
SSBR used uses glue, SSBR that commercially available VSL-5025HM-2, SSBR2563, SSBR can be selected as main
The productions such as the functionalized SSBR of the organosilicon such as HPR of JSR companies production also can be selected in the universal SSBR such as 2557S, SSBR 3830
Product.
Preferably, in the tread mix of the reduction tire drag, the unsaturated epoxy-chlorine ether rubber
The mass ratio of glue/SSBR dry glues is (1~2)/5.45.The unsaturated excessively high dosage of epoxy-epichlorohydrin rubber is excessively high, can lead to unsaturation
Epoxy-epichlorohydrin rubber and SSBR compatibilities and Composite rubber material deterioration in physical properties；Unsaturated epoxy-epichlorohydrin rubber dosage is too low,
Compound tread mix rolling resistance improvement rate is relatively low, and improved effect is not achieved.
In the present invention, 1, the 2- addition units of the BR are more than 95moL%.
In the present invention, the polybutadiene rubber is preferably BR-9000, further preferably neodymium series catalytic polymerization
BR。
The BR for example can be used the Sinopec Beijing Yanshan Mountain branch company production Nd-40 or Lanxess Corporation production
CB-24。
Further preferably, the mass ratio of BR and SSBR (dry glue) is 1/2.17.
The white carbon is preferably MP1165.
Further preferably, the mass ratio of SSBR (non-oil-filled glue)/white carbon is 1/1.10~1.38.
The carbon black can be well known to existing tread mix field material, the further preferred trade mark is the carbon black of N234.
Preferably, the softening agent is dibutyl phthalate or dioctyl phthalate.The preferred strong pole of institute
Insatiable hunger epoxy-epichlorohydrin rubber can be effectively plasticized compatible by the softening agent of property.
Preferably, the mass ratio of the softening agent/insatiable hunger epoxy-epichlorohydrin rubber is 1/2~4.
Conventionally known sulphur (sulphur) can be selected in the vulcanizing agent.
Preferably, the environment-friendly rubber oil is TDAE oil.
The softened rubber oil (environment-friendly rubber oil) of preferred SSBR and BR be commercially available environment-friendly type TDAE oil, dosage
Than for SSBR (dry glue)/TDAE=1/0.24~0.73.
Preferably, silicon -69, silicon -75 or KH-550 that the silane coupling agent is well known to those skilled in the art；
Further preferably silicon -69 or silicon -75.
The material that the accelerating agent can be well known to those skilled in the art, further preferably accelerant CZ and/or
Diphenylguanidine；Most preferably accelerant CZ and diphenylguanidine.
The material that the anti-aging agent can be well known to those skilled in the art, further preferably anti-aging agent RD and/or
Antioxidant 4020；Most preferably anti-aging agent RD and antioxidant 4020.
The activator is zinc oxide and/or stearic acid；Preferably zinc oxide and stearic acid.
Preferably, in the tread mix of the reduction tire drag, the parts by weight of each component are：
15~30 parts of the unsaturated epoxy-epichlorohydrin rubber；
Weight by dry rubber, 80~82 parts of SSBR；36~40 parts of BR；
4~5 parts of zinc oxide；2~2.5 parts of stearic acid；
90~112.5 parts of white carbon；9.5~10.5 parts of carbon black；
7~8 parts of softening agent；20-60.0 parts of TDAE oil；
10~11 parts of silane coupling agent；4~6 parts of anti-aging agent；
1.8~2.5 parts of sulphur；
1~2 part of wax；4.5~5.3 parts of accelerating agent.
Further preferably, the tread mix of the reduction tire drag includes the unsaturated epoxy-chlorine ether
Rubber, SSBR, BR, zinc oxide, stearic acid, white carbon, N234, softening agent, TDAE, siloxanes, anti-aging agent, wax, sulphur and rush
Into agent.
Still more preferably, the tread mix of the reduction tire drag, the parts by weight of each component are：
The unsaturated epoxy -15-30 parts of epichlorohydrin rubber；
Weight by dry rubber, SSBR81.5 parts；BR37.5 parts；
4.5 parts of zinc oxide；2.25 parts of stearic acid；
90~112.5 parts of white carbon MP1165；10 parts of N234；
7.5 parts of softening agent；20-60.0 parts of TDAE；
10.5 parts of silane coupling agent；
3.0 parts of antioxidant 4020；1.5 parts of anti-aging agent RD；
1.5 parts of wax；2.1 parts of sulphur；
2.55 parts of accelerant CZ；2.25 parts of diphenylguanidine.
The invention also discloses a kind of preparation methods of tire tread glue, and the component of each parts by weight is mixed
Refining, obtains rubber compound；And vulcanize the rubber compound, obtain tire tread glue.
Preferably, in the preparation method, include the following steps：
Step (1)：One section of mixing：
One section of mixing carries out on mixer or open mill, and one section of mixing process is：First by insatiable hunger epoxy-epichlorohydrin rubber,
It is kneaded 2~4min in SSBR and softening agent input mixer or open mill, then adds silane coupling agent, TDAE oil and white carbon
Enter in rubber mixing machine and be kneaded at less than 120 DEG C, then will be less than 140 in temperature in carbon black, anti-aging agent, wax input rubber mixing machine afterwards
Mixing 2-3min is carried out at DEG C；First refining glue is completed to obtain in just refining；
Step (2)：Two-stage mixing：
By on first refining glue input open mill made from step (1), after sizing material packet roller, sulphur, accelerating agent are put into refining glue
1.5~3.5min of mixing is carried out in machine at 50-60 DEG C, refining glue is completed, obtains rubber compound；
Step (3)：The rubber compound that step (2) obtains is vulcanized on vulcanizing press, 160 DEG C of curing temperature, when vulcanization
Between 16-18min.
Further preferably, in step (1), insatiable hunger epoxy-epichlorohydrin rubber, SSBR and polar emollients are first put into mixer
Or in open mill and be kneaded 3min, then by silane coupling agent, TDAE oil and white carbon be added in two times in rubber mixing machine less than
It is kneaded at 120 DEG C, then will be less than afterwards in temperature in N234, antioxidant 4020 2.0, anti-aging agent RD, wax input rubber mixing machine
Mixing 2-3min is carried out at 140 DEG C；First refining glue (masterbatch) is completed to obtain in just refining.
Further preferably, in step (2), after packet roller on first refining glue (masterbatch) the input cooled open mill,
Mixing process can be completed after carrying out mixing 2.5min at 50-60 DEG C in sulphur, accelerating agent input rubber mixing machine.
The present invention also provides tire tread glues (vulcanized rubber) made from a kind of preparation method.
Preferably, 300% stress at definite elongation of the vulcanized rubber >=9MPa, specific elongation rate >=350%；Shore A types
Hardness is 65-68.
A kind of SSBR very-high performance tire treads being more preferably modified comprising the insatiable hunger epoxy-epichlorohydrin rubber of the present invention
The preparation method of glue, it is specific as follows：
Insatiable hunger epoxy-epichlorohydrin rubber, SSBR and polar emollients are first put into mixer or open mill and are kneaded 3min,
Then siloxanes, TDAE oil and white carbon are added in rubber mixing machine at less than 120 DEG C and are kneaded in two times, then afterwards will
In N234, antioxidant 4020, anti-aging agent RD, wax, accelerating agent input rubber mixing machine mixing 2-3min is carried out in the case where temperature is less than 140 DEG C
Afterwards, i.e., after masterbatch is completed, masterbatch will be placed on water cooled rolls after masterbatch cooled to room temperature, is being opened
Roller, roll spacing 1.5mm, roller temperature be 50-60 DEG C at after masterbatch packet after slow rollers, sulphur and accelerating agent is added, waits for its dispersion
Cutter again after the completion makees 3/4 cutter three times per side, per knife interval 15s, roll spacing is then adjusted to 0.8mm, by rubber compound clot,
Alternately from every one end be added it is longitudinal it is thin it is six times logical after, then sizing material is pressed into the film of thickness about 2.2mm.Finally by sample flat
Sulfidization molding on plate vulcanizer, vulcanizate after molding carry out physical property and dynamic mechanical analysis.
In the present invention, the unsaturated epoxy-epichlorohydrin rubber is by allyl glycidyl ether, propylene oxide, epoxy second
The random copolymer of alkane, epoxychloropropane and ethylene glycol diglycidylether；Highly polar unsaturated epoxy-chlorine ether of selecting type 1
Modifying agent of the rubber as SSBR, main purpose are the compatibilities strengthened with the white carbon in tread glue formula, improve hard charcoal
Black dispersibility reduces the Payne effects of composite material vulcanization tread rubber；Another aspect sulphur can simultaneously with unsaturated epoxy-
Double bond in epichlorohydrin rubber in double bond and SSBR molecules is crosslinked jointly, and the macromolecular in formula 1 is led to the double bond in SSBR molecules
Over cure bond one network-like macromolecule of synthesis, the polymer of highly polar ether-containing key can be effectively by the long-chain molecule end of SSBR
Inertia styrene units or butadiene unit obtain " being passivated ", so as to avoid tire roll when cyclic stress become deformation
In heat and hysteresis loss, i.e. the rolling resistance of tire effectively reduced.
Compared with the prior art, the advantageous effect that technical scheme of the present invention is brought：
(1) the unsaturated epoxy-of the highly polar polynary monomer composition selected by very-high performance tire tread glue of the invention
There is epichlorohydrin rubber the unformed molecular structure of random alternating copolymerization, 5- component units can reduce amorphous polymer generation, avoid
Propylene oxide chain link generates block with " head-tail " or " head-head " (" tail-tail ") bind mode, reduces the crystallinity of co-polymer.
The comprehensive physical performance for imparting that copolymer is low without filling and vulcanization glue intensity, filling vulcanizate intensity is high, elasticity is good etc..
(2) random distribution having in unsaturated epoxy-epichlorohydrin rubber molecule of polynary monomer composition of the invention is double
Key unit and the highly polar ehter bond formed containing no less than 17% oxygen atom, while also there is a certain amount of branched structure, it assigns
Given rubber have preferable processing performance, particularly banding characteristics can it is good and with after solution polymerized butadiene styrene rubber and the compound mixing of white carbon
Vulcanizate made of passenger car tire tread glue have extremely low rolling resistance, be the car for preparing of main glue kind with traditional SSBR
Tread rubber is compared, and the rolling resistance of tire is effectively reduced, and rolling resistance improvement rate has reached 26-31%, from real
It is said in meaning and has achieved the purpose that the tire of the present invention can be saved compared with multiple fuel.
(3) the car tyre surface that prepared by the epoxy of the polynary monomer composition of selection of the invention-Modified By Polyepichlorohydrin Rubber SSBR is multiple
Sizing material is closed, raw material sources are wide, easy to make, can meet tire industry production requirement using existing technique.
Specific implementation mode
Following embodiment is intended to illustrate the content of present invention, and the protection domain of the claims in the present invention is not implemented
The limitation of example.
In the following example：
(1) TD-6020 type Mooney viscosity instrument is used to measure the Mooney viscosity of rubber compound.
(2) CMT4104 type tensilons is used to measure the tensile property of vulcanizate.
(3) wet-sliding resistant performance and rolling resistance of dynamic viscoelasticity spectrum analysis-e/or determining vulcanizate are used.
(4) RSS-II type rubber rolling resistance test machines is used to measure the heat of vulcanizate.
Implement 1
It is prepared by catalyst complex：
It is embedded in the ice-water bath at -5~5 DEG C with the transposed bis- mouthfuls of ox horn bottles of 200mL of dry nitrogen, then with note
Emitter respectively by 20% triethyl aluminum 110mL, ether 23mL, water 1.6mL, acetylacetone,2,4-pentanedione 10.2mL injection ox horn bottle (more than
It is mass content), after magnetic agitation 30min, catalyst complex can the reaction was complete, and wherein aluminium contains in complex solution
Amount is 1.21mol/L.
Thiacyclohexane 2900mL, epoxychloropropane 37.0g, ethylene oxide 8.8g, allyl are added in the polymeric kettle of 5L steels
Base glycidol ether 20.8g, propylene oxide 185.6g and ethylene glycol diglycidylether 0.70g will be polymerize with hot bath later
Temperature of charge in kettle rises to 75~85 DEG C, is sucked at this time by triethyl aluminum with syringe: ether: water: acetylacetone,2,4-pentanedione=1: 1.5
: (wherein aluminium content is the catalyst complex 26mL of 0.5: 0.5 (mol ratios) composition in catalyst complex cyclohexane solution
1.21mol/L), and to keep in kettle nitrogen pressure be 0.3~0.4Mpa, and after strong stirring polymerize 8h, 10ml water is then added
Polymerisation 15min is terminated, antioxidant 1076 7.5g is added later and stirs 15min, finally by polymer with water devaporation
Solvent is removed, it is 61 that granular polymer dries 60min up to the Mooney viscosity of polymer at 80 DEG C.
Implement 2
It is in embodiment 1 that other process conditions are constant, be merely that catalyst is changed to by triethyl aluminum: ether: water:
Acetylacetone,2,4-pentanedione=1: (wherein aluminium content is 1.5: 1.0: 1.5 catalyst complex in catalyst complex cyclohexane solution
1.05mol/L), it is added in polymeric kettle and is reacted with syringe sucking 30mL.Finally obtained random alternately unsaturated epoxy-
The Mooney viscosity of epichlorohydrin rubber, polymer is 68.
Implement 3
160 × 320 2 roller open mills are preheated to 80-120 DEG C, the unsaturated epoxy-chlorine ether prepared in 1 will be implemented at this time
Rubber 15g, VSL5025-2HM 112.5g (wherein, oil content 27.3wt%, contents of ethylene 63moL%, S/B=25/75),
BR-9000 37.5g, dibutyl phthalate 7.5g are put on two roller open mills, and regulating roller is away from breaking glue to sizing material and wrap completely
In on roller, hereafter 20g TDAE oil and Si-69 10.5g are mixed in 90g white carbons, and are added on open mill in two times
On blend glue stuff, next by carbon black 10g, zinc oxide 4.5g, stearic acid 2.25g antioxidant 4020s 3.0g, anti-old on roller
Agent RD 1.5g, wax 1.5g are added on the sizing material of roller, after above-mentioned powder completely by sizing material " suffering all " after, cutter two is to after three times
Masterbatch is cooled to room temperature by bottom sheet.Next masterbatch input is had turned on cooled open mill, and is passed through chilled water, controlled
50-60 DEG C of roller temperature processed, it is after the complete packet roller of masterbatch, sulphur 2.1g, accelerant CZ 2.55g, diphenylguanidine 2.35g inputs is cold
But it is kneaded on formula open mill, after auxiliary agent is scattered in sizing material, 3/4 cutter is made three times per side, per knife interval 15s, then by roll spacing
Be adjusted to 0.8mm, by rubber compound clot, alternately from every one end be added it is longitudinal it is thin it is six times logical after, sizing material is pressed into thickness about 2.2mm
Film.Finally sample is vulcanized on vulcanizing press, 160 DEG C of curing temperature, vulcanization time 16-18min, sulphur after molding
Change film and carries out physical property and dynamic mechanical analysis.
Implement 4
By implementing, the condition in 3 is constant, is merely to adjust the formula of unsaturated epoxy-epichlorohydrin rubber modification SSBR
It is whole：Implement the insatiable hunger epoxy-epichlorohydrin rubber 22g prepared in 1, SSBR2563 112.5g (wherein, oil content 27.3wt%, ethylene
Base content 63moL%, S/B=25/75), CB-24 37.5g, white carbon 95g, Si-75 10.5g, dioctyl phthalate
7.5g, TDAE 35g, zinc oxide 4.5g, stearic acid 2.25g, N234 10.0g, antioxidant 4020 3g, anti-aging agent RD 1.5g,
Wax 1.5g, sulphur 2.1g, accelerant CZ 2.55g, diphenylguanidine 2.25.Sulfide film after molding carries out physical property and dynamic
Mechanics property analysis.
Implement 5
By implementing, the condition in 3 is constant, is merely that the formula progress of unsaturated epoxy-epichlorohydrin rubber modification SSBR is as follows
Adjustment：Implement 2 in prepare insatiable hunger epoxy-epichlorohydrin rubber 30g, SSBR 2557S 112.5g (wherein, oil content 27.3wt%,
Contents of ethylene 57moL%, S/B=25/75), Nd-40 37.5g, white carbon 100g, Si-69 10.5g, phthalic acid two
Monooctyl ester 7.5g, TDAE 45.0g, zinc oxide 4.5g, stearic acid 2.25g, N234 10.0g, antioxidant 4020 3g, anti-aging agent RD
1.5g, wax 1.5g, sulphur 2.1g, accelerant CZ 2.55g, diphenylguanidine 2.25.Sulfide film after molding carries out physical property
It is analyzed with dynamic mechanical.
Implement 6
Implement the unsaturated epoxy-epichlorohydrin rubber 30g, VSL5025-2HM 112.5g, CB-2437.5g, the neighbour that are prepared in 2
In dibatyl phithalate 7.5g input 1.0L mixers, after control rotating speed 50rpm is kneaded 180 seconds, mixer mixing temperature is controlled
Degree be less than 140 DEG C, hereafter by 50g TDAE oil, Si-75 10.5g, white carbon 105g, carbon black 10g, antioxidant 4020 3.0g,
After anti-aging agent RD 1.5g, wax 1.5g, zinc oxide 4.5g, stearic acid 2.25g are added at one time in mixer and are kneaded 240 seconds, row
Go out masterbatching sizing material and blend glue stuff is down to room temperature.Next masterbatch is added on two roller cooled open mills, waits for sizing material packet
Sulphur 2.1g, accelerant CZ 2.55g, diphenylguanidine 2.25 are added after roller and is kneaded, and calendering process is identical to implementation 3.
Sulfide film after molding carries out physical property and dynamic mechanical analysis.
Implement 7
Associated process conditions in embodiment 6 are constant, it is merely to be adjusted to formula：Implement the unsaturation prepared in 2
Epoxy-epichlorohydrin rubber 20g, SSBR2563 112.5g, Nd-40 37.5g, dibutyl phthalate 7.5g put into 1.0L mixings
In machine, after control rotating speed 50rpm is kneaded 180 seconds, control mixer mixing temperature is less than 140 DEG C, hereafter that 60g TDAE is oily,
Si-75 10.5g, white carbon 112.5g, carbon black 10g, antioxidant 4020 3.0g, anti-aging agent RD 1.5g, wax 1.5g, zinc oxide
After 4.5g, stearic acid 2.25g are added at one time in mixer and are kneaded 240 seconds, masterbatching sizing material is discharged and is down to blend glue stuff
Room temperature.Next masterbatch is added on two roller cooled open mills, sulphur 2.1g, accelerant CZ is added after sizing material packet roller
2.55g, diphenylguanidine 2.25 are simultaneously kneaded, and calendering process is identical to implementation 3.Sulfide film after molding carries out physical property
It is analyzed with dynamic mechanical., sizing material after mixing carries out sulfidization molding, and sulfide film after molding carries out physical property and dynamic
State mechanics property analysis.
Implement 8
Associated process conditions in embodiment 6 are constant, it is merely to be adjusted to formula：Implement the unsaturation prepared in 2
(wherein, this glue is non-oil-filled glue, contents of ethylene 59moL%, S/B=27/ by epoxy-epichlorohydrin rubber 25g, HPR850 81.8g
73), Nd-40 37.5g, dioctyl phthalate 7.5g, TDAE 60g, white carbon 105g, other same embodiments of material amounts
6, the sizing material after mixing carries out sulfidization molding, and sulfide film after molding carries out physical property and dynamic mechanical analysis.
Implement 9
By implementing, the condition in 3 is constant, is merely that the formula progress of unsaturated epoxy-epichlorohydrin rubber modification SSBR is as follows
Adjustment：Implement the insatiable hunger epoxy-epichlorohydrin rubber 28g, SSBR 2557S 110.5g, Nd-40 40g, the white carbon that are prepared in 2
102g, Si-69 10g, dioctyl phthalate 7.0g, TDAE 48.0g, zinc oxide 4.5g, stearic acid 2.25g, N234
10.0g, antioxidant 4020 3.0g, anti-aging agent RD 1.5g, wax 1.0g, sulphur 2.5g, accelerant CZ 3.05g, accelerating agent
D2.25.Sulfide film after molding carries out physical property and dynamic mechanical analysis.
Implement 10
By implementing, the condition in 3 is constant, is merely that the formula progress of unsaturated epoxy-epichlorohydrin rubber modification SSBR is as follows
Adjustment：Implement the insatiable hunger epoxy-epichlorohydrin rubber 15g, VSL5025-2HM 112.5g, BR-9000 36g, the white carbon that are prepared in 2
108g, Si-75 11g, dibutyl phthalate 8.0g, TDAE 54.0g, zinc oxide 5.0g, stearic acid 2.0g, N234
9.5g, prevent old 4020 3.0g, anti-aging agent RD 3.0g, wax 2.0g, sulphur 2.0g, accelerant CZ 3.0g, diphenylguanidine 2.3.At
Sulfide film after type carries out physical property and dynamic mechanical analysis.
Comparative example 1
Associated process conditions in embodiment 6 are constant, it is merely to substitute the unsaturated epoxy in formula-epichlorohydrin rubber
For epoxy rubber H1100 25g, other materials composition and dosage are constant, and the sizing material after mixing is carried out sulfidization molding, molding
Sulfide film afterwards carries out physical property and dynamic mechanical analysis.
Comparative example 2
Associated process conditions in embodiment 10 are constant, be merely by unsaturated epoxy-epichlorohydrin rubber in formula more
For for epoxy rubber H1100 20g, other materials composition and dosage are constant, and the sizing material after mixing is carried out sulfidization molding, at
Sulfide film after type carries out physical property and dynamic mechanical analysis.
Comparative example 3
By implementing, the process conditions in 3 are constant, are merely to be added without unsaturated epoxy-epichlorohydrin rubber in formula, tool
Body formula is as follows：SSBR2563 112.5g, CB-24 37.5g, white carbon 112.5g, Si-75 10.5g, phthalic acid two
Monooctyl ester 7.5g, TDAE 50g, zinc oxide 4.5g, stearic acid 2.25g, N234 10.0g, antioxidant 4020 3g, anti-aging agent RD
1.5g, wax 1.5g, sulphur 2.1g, accelerant CZ 2.55g, diphenylguanidine 2.25.
Sizing material after mixing carries out sulfidization molding, and the physical property of sample is modified with unsaturated epoxy-epichlorohydrin rubber
SSBR samples are compared.
Comparative example 4
By implementing, the process conditions in 8 are constant, are merely to be added without unsaturated epoxy-epichlorohydrin rubber in formula, tool
Body formula is as follows：HPR850 82g, Nd-40 36g, dioctyl phthalate 7.5g, white carbon 105g, Si-75 10.5g,
TDAE 50g, zinc oxide 4.5g, stearic acid 2.25g, N234 10.0g, antioxidant 4020 3g, anti-aging agent RD 1.5g, wax
1.5g, sulphur 2.1g, accelerant CZ 2.55g, diphenylguanidine 2.25.
Sizing material after mixing carries out sulfidization molding, and the physical property of sample is modified with unsaturated epoxy-epichlorohydrin rubber
SSBR samples are compared.
Embodiment 3-10 and the comparison of vulcanizating glue physical performance in comparative example 1~4 and dynamic mechanical are shown in Table 1：
Table 1
It explains：1. the SSBR tyre surface vulcanized rubbers that the unsaturated epoxy rubber H1100 of dibasic monomer composition is modified embody
Hardness and glass transition temperature is relatively high, rolling resistance improvement rate unobvious.
2. in composite modified SSBR tread mixes, increases with polynary not unsaturated epoxy rubber consumption, roll resistance
Power improvement rate has the trend of faint increase, but vulcanized rubber glass transition temperature height is consequently increased, so polynary unsaturation epoxy
Dosage of the rubber in tread rubber is unsuitable excessively high.
Claims (16)
1. a kind of tread mix reducing tire drag, which is characterized in that include unsaturated epoxy-epichlorohydrin rubber, SSBR
And BR；
Unsaturated epoxy-the epichlorohydrin rubber is by allyl glycidyl ether, propylene oxide, ethylene oxide, epoxychloropropane
Ring opening copolymer is carried out with the mix monomer including ethylene glycol diglycidylether under the effect of trialkylaluminium series catalysts to form.
2. reducing the tread mix of tire drag as described in claim 1, which is characterized in that the unsaturation ring
Than accounting for the 5~10% of total monomer amount for allyl glycidyl ether mol numbers, ethylene glycol two contracts the monomer composition of oxygen-epichlorohydrin rubber
Water glycerin ether mol numbers account for the 0.05%~0.1% of total monomer amount, and propylene oxide mol numbers account for the 70~80% of total monomer amount, epoxy
Chloropropane mol numbers account for the 5~12.5% of total monomer amount, and ethylene oxide mol numbers account for the 5~12.5% of total monomer amount.
3. reducing the tread mix of tire drag as claimed in claim 2, which is characterized in that wherein monomer polymerization
Catalyst forms and ratio is triethyl aluminum: ether: water: acetylacetone,2,4-pentanedione molar ratio is 1: 1.5: 0.5~1.0: 0.5~1.5；It urges
Agent dosage is the 2~4% of mix monomer integral molar quantity, wherein catalyst is measured with trialkylaluminium.
4. reducing the tread mix of tire drag as claimed in claim 3, which is characterized in that the technique item of ring opening copolymer
Part is：Temperature is 75~85 DEG C, and the time is 8~10h, and pressure is 0.3~0.4MPa.
5. reducing the tread mix of tire drag as claimed in claim 4, which is characterized in that the unsaturation ring
The Mooney viscosity of oxygen-epichlorohydrin rubber is 60-70.
6. reducing the tread mix of tire drag as described in claim 1, which is characterized in that polybutadiene in SSBR molecules
1, the 2- additions unit content of alkene unit in 55-70moL%, in conjunction with styrene units content in 20-30wt%.
7. reducing the tread mix of tire drag as described in claim 1, which is characterized in that 1, the 2- of the BR adds
It is more than 95moL% at unit.
8. as claim 1~7 any one of them reduces the tread mix of tire drag, which is characterized in that described
SSBR weight by dry rubber, the weight ratio of the unsaturated epoxy-epichlorohydrin rubber, SSBR and BR is 15~30: 80~82: 36~
40。
9. reducing the tread mix of tire drag as claimed in claim 8, which is characterized in that also include activator, white
Carbon black, carbon black, softening agent, anti-aging agent, silane coupling agent, wax, environment-friendly rubber oil, accelerating agent and sulphur.
10. reducing the tread mix of tire drag as claimed in claim 9, which is characterized in that the softening agent is
Dibutyl phthalate or dioctyl phthalate；
The silane coupling agent is silicon -69, silicon -75 or KH-550；
The accelerating agent is accelerant CZ and/or diphenylguanidine；
The anti-aging agent is anti-aging agent RD and/or antioxidant 4020；
The environment-friendly rubber oil is TDAE oil；
The activator is zinc oxide and/or stearic acid.
11. reducing the tread mix of tire drag as claimed in claim 10, which is characterized in that the parts by weight of each component
Number is：
15~30 parts of the unsaturated epoxy-epichlorohydrin rubber；
Weight by dry rubber, SSBR80~82 part；36~40 parts of BR；
4~5 parts of zinc oxide；2~2.5 parts of stearic acid；
90~112.5 parts of white carbon；9.5~10.5 parts of carbon black；
7~8 parts of softening agent；20-60.0 parts of TDAE oil；
10~11 parts of silane coupling agent；4~6 parts of anti-aging agent；
2.0~2.5 parts of sulphur；
1~2 part of wax；4.5~5.3 parts of accelerating agent.
12. reducing the tread mix of tire drag as claimed in claim 10, which is characterized in that the parts by weight of each component
Number is：
15~30 parts of the unsaturated epoxy-epichlorohydrin rubber；
Weight by dry rubber, 81.8 parts of SSBR；37.5 parts of BR；
4.5 parts of zinc oxide；2.25 parts of stearic acid；
90~112.5 parts of white carbon；10 parts of carbon black；
7.5 parts of softening agent；20-60.0 parts of TDAE oil；
10.5 parts of silane coupling agent；
3.0 parts of antioxidant 4020；1.5 parts of anti-aging agent RD；
1.5 parts of wax；2.1 parts of sulphur；
2.55 parts of accelerant CZ；2.25 parts of diphenylguanidine.
13. a kind of preparation method of tire tread glue, which is characterized in that by any one of claim 1~12 parts by weight
Component is kneaded, and rubber compound is obtained；And vulcanize the rubber compound, obtain tire tread glue.
14. the preparation method of tire tread glue as claimed in claim 13, which is characterized in that include the following steps：
Step (1)：One section of mixing：
One section of mixing carries out on mixer or open mill, and one section of mixing process is：First by insatiable hunger epoxy-epichlorohydrin rubber, SSBR
It is put into softening agent and is kneaded 2~4min in mixer or open mill, refining then is added in silane coupling agent, TDAE oil and white carbon
It is kneaded at less than 120 DEG C in glue machine, then is afterwards put into carbon black, anti-aging agent, wax in rubber mixing machine in the case where temperature is less than 140 DEG C
Carry out mixing 2-3min；First refining glue is completed to obtain in just refining；
Step (2)：Two-stage mixing：
By made from step (1) just refining glue input open mill on, after sizing material packet roller, will sulphur, accelerating agent input rubber mixing machine in
1.5~3.5min of mixing is carried out at 50-60 DEG C, is completed refining glue, is obtained rubber compound；
Step (3)：The rubber compound that step (2) obtains is vulcanized on vulcanizing press, 160 DEG C of curing temperature, vulcanization time 16-
18min。
15. tire tread glue made from the preparation method described in a kind of claim 13 or 14.
16. tire tread glue as claimed in claim 15, which is characterized in that 300% stress at definite elongation of tire tread glue
>=9MPa, specific elongation rate >=350%, shore A type hardness testers are 65-68.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710181579.XA CN108623800B (en) | 2017-03-23 | 2017-03-23 | Tread rubber material capable of reducing rolling resistance of tire, tread rubber and preparation method of tread rubber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710181579.XA CN108623800B (en) | 2017-03-23 | 2017-03-23 | Tread rubber material capable of reducing rolling resistance of tire, tread rubber and preparation method of tread rubber |
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| Publication Number | Publication Date |
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| CN108623800A true CN108623800A (en) | 2018-10-09 |
| CN108623800B CN108623800B (en) | 2021-10-12 |
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| CN201710181579.XA Active CN108623800B (en) | 2017-03-23 | 2017-03-23 | Tread rubber material capable of reducing rolling resistance of tire, tread rubber and preparation method of tread rubber |
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| CN109467770A (en) * | 2017-09-08 | 2019-03-15 | 北京化工大学 | A kind of rubber composite material and preparation method thereof using cardanol glycidyl ether modified white carbon black |
| CN109796647A (en) * | 2019-01-09 | 2019-05-24 | 建大橡胶（中国）有限公司 | A kind of high grip performance low rolling resistance tyre tread mix and its synthetic method |
| CN111073200A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Environment-friendly rubber composition and preparation method thereof |
| CN111801380A (en) * | 2018-07-27 | 2020-10-20 | 住友橡胶工业株式会社 | Rubber composition and tire |
| CN111801378A (en) * | 2018-07-27 | 2020-10-20 | 住友橡胶工业株式会社 | Rubber composition and tire |
| CN116855002A (en) * | 2023-09-04 | 2023-10-10 | 山东昊华轮胎有限公司 | Wear-resistant anti-skid tread material and preparation method thereof |
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| CN116855002A (en) * | 2023-09-04 | 2023-10-10 | 山东昊华轮胎有限公司 | Wear-resistant anti-skid tread material and preparation method thereof |
| CN116855002B (en) * | 2023-09-04 | 2023-11-17 | 山东昊华轮胎有限公司 | Wear-resistant anti-skid tread material and preparation method thereof |
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