CN110872368B - Formula of multi-double-bond polar compound modified semi-steel radial tire tread rubber - Google Patents

Formula of multi-double-bond polar compound modified semi-steel radial tire tread rubber Download PDF

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CN110872368B
CN110872368B CN201811021069.7A CN201811021069A CN110872368B CN 110872368 B CN110872368 B CN 110872368B CN 201811021069 A CN201811021069 A CN 201811021069A CN 110872368 B CN110872368 B CN 110872368B
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double
polar compound
bond polar
ssbr
bond
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CN110872368A (en
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张千帆
张建国
徐伟箭
蒋文英
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China Petroleum and Chemical Corp
Sinopec Baling Co
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China Petroleum and Chemical Corp
Sinopec Baling Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • 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 

Abstract

The invention discloses a formula of a multi-double-bond polar compound modified semi-steel radial tire tread rubber, which comprises a multi-double-bond polar compound modified SSBR, a multi-double-bond polar compound modified BR, an initiator and other conventional silicon formula auxiliaries. The polyene or unsaturated carbon-carbon double bond polar compound is filled into solution polymerized styrene-butadiene rubber (SSBR) and cis-Butadiene Rubber (BR), the obtained raw rubber is applied to a semi-steel tire tread rubber 'silicon formula', the vulcanized tread rubber has good ground gripping performance and lower rolling resistance, and the rolling resistance improvement rate can reach 40% at most compared with the general SSBR or BR.

Description

Formula of multi-double-bond polar compound modified semi-steel radial tire tread rubber
Technical Field
The invention relates to a formula of a modified semi-steel radial tire tread rubber, in particular to a formula of a semi-steel radial tire tread rubber modified by a multi-double-bond polar compound.
Background
Among the corresponding A-G7 grades in the European Union labeling law, some tire companies in China can only produce B/C grade tires by using the combination of general SSBR and general BR, and the future development target is to move to higher grades such as double B or A/B or double A grade standards. The method is particularly important for selecting new rubber materials, one of the methods is to introduce polar substances into SSBR and BR molecules or into a macromolecular network of vulcanized rubber, the polar groups strengthen the affinity of the rubber and polar fillers, and reduce the Payne effect of self-aggregation of the fillers such as carbon black in rubber materials, so that the hysteresis loss of the rubber is improved, and the high-performance tire is obtained.
Although the content of vinyl units in a molecular structure of the traditional third-generation solution polymerized styrene-butadiene rubber (SSBR) is 40-65%, the molecules have no polar groups, the semi-steel tire prepared by adopting a silicon formula can only reach the B/C grade standard, and the semi-steel tire with higher grade or standard, such as double A or A/B, has not been reported in documents at present. For example, a patent (publication No. CN 103483645A) of Goodyear tire rubber company discloses a preparation method of a pneumatic tire, and specifically discloses a preparation method of a pneumatic tire, wherein the mass fraction of styrene combined with solution polymerized styrene butadiene rubber in a formula of a tread rubber of the pneumatic tire is 20-50%, the mass fraction of 1, 2-vinyl is 10-40% 100 parts, 5-60 parts of low PCA processing oil, 90-150 parts of silicon dioxide, 10-20 parts of sulfur-containing organosilicon compound, 5-30 parts of polyterpene resin and 10 parts of carbon black. The semi-steel tire manufactured according to the formula can only reach grade B in ground gripping and C in rolling resistance. To achieve higher levels of tire rolling resistance, functional group polarization of SSBR molecules is a viable approach. For example, a rubber composition for a tire tread is disclosed in chinese patent application No. CN103221476A to kohama rubber co-Ltd, and specifically discloses that a modified conjugated diene polymer rubber has a terminal modifying group produced by copolymerizing a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent using an organic active metal compound as an initiator and reacting the resulting active conjugated diene polymer chain with a compound having a functional group capable of reacting with the active terminal of the polymer chain, and the terminal modifying group contains a functional group capable of interacting with silica.
Japanese patent (JP 2009287020A) describes a rubber obtained by polymerizing butadiene and styrene in cyclohexane and end-capping and coupling the resulting polymer with 3-N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane and N-benzylidene-3-triethoxysilyl-1-propylamine, which is coupled, polar nitrogen atoms are also in the middle segment of the polymer, the polymer is single-end functionalized, the end capping rate of chain ends is only 25-50%, the terminal of polymer molecular chain is still an inert terminal composed of styrene or butadiene units, and the tread rubber prepared by using the rubber still has certain Payne effect. The synthesis of SSBR is described in the US patent (US5616704A) by reacting secondary amines with butyl lithium to form secondary aminolithium as initiator for the polymerization of styrene and butadiene and finally terminating the polymerization with trialkyltin chloride or 4,4 "-bis (diethylamino) benzophenone or other N, N" -dialkyl-amino-alkyl ketones or aldehydes or N, N "-dialkyl-amino-alkyl alkenes. However, the secondary amino lithium is affected by temperature and equilibrium reaction in the preparation process, and a small amount of secondary amine always exists in the secondary amino lithium solution, which seriously affects the polymerization reaction kinetics, causes incomplete polymerization reaction, does not remove the molecular weight of the polymer, and the like. In the context of (modified synthetic rubber for white carbon black and carbon black filled tread rubber [ J ]. modern rubber technology, 2012,38(5):12-17.) it is proposed to use less polar group-containing polymer chains to constitute new main chain modification technology which can further reduce the hysteresis loss of the vulcanizate and reduce the rolling resistance of the tire, e.g. in the case of butadiene-styrene copolymerization, monomer-containing polar groups of the growing polymer chain, e.g. 4-N- (trimethyl) silyl-methyl-ethyl-styrene, are introduced as comonomers in an amount of 1-2% of the total monomer usage. Unfortunately, the additional monomer often affects the polymerization kinetics and thus alters the properties of the original unmodified polymer. In the US patent (US5521309) it is described the preparation of organolithium compounds as initiators for butadiene-styrene random copolymerization by reacting organoamine compounds with butyllithium at room temperature, such functionalized initiators as N, N-dioctylamino-methallyllithium, hexamethyleneaminoallyl lithium, pyrrolidinyl-o-xylylammonium and the like, the initiated polymer active gum finally being coupled 50% with tin tetrachloride, the resulting polymer being comparable to non-functionalized SSBR, which shows a comparable decrease in hysteresis loss of the functionalized polymer vulcanizate of up to 43%.
The research of professor Liu Da Hua and Liu Qing (handbook of synthetic rubber industry, academician) and doctor A.R. Payne, etc. shows that: the reactivity of the SSBR chain end coupling structure to the carbon black is decreased in the following sequence, wherein the reactivity is modified by the coupling of tin-butadiene-diene group, tin-styryl group, silicon-butadiene-diene group and the end group. According to the conformation analysis of macromolecular chains, the root of the rubber hysteresis loss is that the chain links with larger degree of freedom between the final crosslinking point and the chain ends of network macromolecules are difficult to participate in the effective elastic recovery process of the macromolecules, so that the energy lost in the periodic deformation is easy to be converted into heat.
Existing commercially available Trinseo novel functionalized SPRINTAN TM SLR4633-Schkopau、SPRINTAN TM SLR4630-Schkopau et al, JSR company, HPR-850 series products, and Asahi Kasei corporation, Y-031, etc. The structural characteristics of such polymers have not been described in detail in the literature to date.
At present, in the silicon formulation using SSBR as a high performance green tire, it is common to use a sulfur-containing organosiloxane having no double bond group in the molecule as a coupling agent to achieve filler-filler (silica-silica) interaction and polymer-filler combination, so as to achieve effective dispersion and combination of the filler in the composite, and it is particularly effective as a polar group contained in the SSBR molecular chain.
In addition, in the existing high-performance tire formula prepared by functionalized SSBR, general BR, silicon-69 or silicon 75, white carbon black and the like, for silicon-69 or silicon 75, the silicon-69 or silicon-75 is physically combined with the white carbon black and rubber in a coupling way and cannot participate in elastic recovery of network macromolecules; although functionalized SSBR contains functional groups, rare earth-catalyzed BR (such as CB-24) or nickel-based catalytic BR-9000 is generally used for BR, namely no functional groups exist in BR molecules or at the ends of the BR molecules, so that a certain amount of chain links with larger degrees of freedom between the final crosslinking point of a vulcanized network macromolecule and the chain ends are difficult to participate in the effective elastic recovery process of the macromolecule, and energy lost in periodic deformation is easy to be converted into heat. Which is also a disadvantage of the prior art.
Chinese patent (CN102911298A a catalyst system for isoprene polymerization and a preparation method thereof) introduces that a neodymium neodecanoate-triisobutylaluminum-diethylaluminum chloride catalyst system is adopted to prepare polyisoprene rubber or rare earth polybutadiene rubber, the content of cis-1, 4 in the prepared BR molecule reaches 98%, and no other groups exist in the molecular structure. The rubber can be used for manufacturing B/C class tires only by being matched with SSBR of a general type. Chinese patents (CN104448059A, CN104211838A and CN105601770A) all relate to high cis-1, 4 polybutadiene liquid rubber containing terminal hydroxyl and a preparation method thereof. The polybutadiene rubber containing terminal hydroxyl is not suitable for being used as a tire material as a liquid rubber, and is only suitable for being used as a polyurethane elastic or foaming material.
In the peak, 2018 (fifth world) international green tire technology peak forum [ C ] argument sets "innovative application of graphene in tires" introduces application of graphene in styrene butadiene rubber and natural rubber, namely breaks through the technical bottleneck that graphene nano materials are added into latex and dispersed in glue solution, the graphene nano materials filled into raw rubber are 10-15%, the graphene content in the tire formula is 1%, and the global first-onset graphene tires are produced by double star tire companies, the wet skid resistance is improved by 5%, and the rolling resistance is reduced by 15%.
In Wuhan university's institute of chemistry and molecular science, the fourteenth Chinese academy of organosilicon academy of sciences ' research on crosslinking agents for preparing room temperature vulcanized silicone rubber by addition of octavinyl polyhedral oligomeric silsesquioxane (Vinyl-POSS) and trimethoxysilane with hydrosilylation ' relates to the application of Vinyl-POSS to room temperature silicone rubber, but at present, the application of such polyvinyl-containing organosilicon or compounds or polymers containing other heterocyclic or polar groups and containing a plurality of unsaturated double bonds as modifiers for high performance tires has not been reported.
In conclusion, the preparation of the double B or A/B or double A-grade semi-steel tire by compounding the conventional general type SSBR and the conventional general type BR is difficult. In silica based compounds for full backbone formulations, the SSBR must be either semi-functionalized or fully functionalized, and the BR must also be functionalized in order to meet or achieve higher levels of performance. However, to date, the prior art literature for modifying BR with functionalized materials has been very rare.
Disclosure of Invention
Aiming at the defects of the existing SSBR and BR molecule 'head-tail' or polar functional group introduced in the middle of molecular chain preparation, the first aim of the invention is to provide a method for uniformly doping a compound containing a multi-carbon double bond active unit structure and a polar functional group into an SSBR glue solution and a BR glue solution to be used as a modifier of SSBR and BR so as to obtain multi-double bond polar compound modified SSBR and modified BR. The double-bond polar compound modified SSBR and the double-bond polar compound modified BR are used as the components of the formula of the tire rubber material, so that the affinity between the rubber and the polar filler can be enhanced, and the Payne effect of the filler such as carbon black gathered in the rubber material by itself is reduced, thereby improving the hysteresis loss of the rubber. Moreover, the multi-carbon double bond active functional substance cannot be crosslinked with double bonds in SSBR under the action of sulfur in a tire formula, and can also be effectively linked with double bonds in Butadiene Rubber (BR), namely polar groups are introduced into terminal molecular bonds in SSBR and BR molecules, and the polar groups are randomly and uniformly distributed, the SSBR and the BR are organically combined together by chemical bonds, the length of an inert chain of a styrene or butadiene unit at the tail end of a chain link with larger freedom degree between a final crosslinking point and the chain end in rubber vulcanization is shortened, and the effective elastic recovery process of macromolecules is increased, so that the energy lost in periodic deformation of the tire is reduced and converted into heat, namely the hysteresis loss of the rubber is improved, and the rolling resistance of the tire is reduced.
In order to achieve the purpose, the invention provides a formula of a multi-double-bond polar compound modified semi-steel radial tire tread rubber, which comprises multi-double-bond polar compound modified SSBR, multi-double-bond polar compound modified BR and an initiator.
Preferably, the double-bond polar compound modified SSBR is obtained by dissolving and mixing SSBR glue solution and a multi-double-bond polar compound and condensing steam. The SSBR of the invention can adopt the existing anion polymerization method to synthesize the SSBR glue solution first. And then adding the multi-double-bond polar compound into the SSBR glue solution, stirring and dissolving uniformly, and then carrying out steam condensation to prepare raw rubber, so that the uniform dispersion of the multi-double-bond polar compound in the SSBR matrix can be realized. The above SSBR dry glue can also be dissolved into a glue solution by a solvent and then mixed with a multi-double bond polar compound.
The polar compound with multiple double bonds is preferably dissolved by an organic solvent and then added into SSBR glue solution to be uniformly mixed. The organic solvent is preferably (an inert solvent which does not affect the anionic polymerization) toluene, xylene, THF or the like.
In a preferable scheme, the double-bond polar compound modified BR is obtained by dissolving and mixing BR glue solution and a multi-double-bond polar compound and condensing steam.
The BR of the invention can be synthesized into BR glue solution by adopting the existing anion polymerization method or other metal catalytic polymerization methods. And then adding the multi-double-bond polar compound into BR glue solution, stirring and dissolving uniformly, and then carrying out steam condensation to prepare raw rubber, so that the uniform dispersion of the multi-double-bond polar compound in a BR matrix can be realized. The BR dry glue can also be dissolved into glue solution by adopting a solvent and then mixed with the multi-double bond polar compound.
The polar compound with multiple double bonds is preferably dissolved by an organic solvent and then added into BR glue solution to be uniformly mixed. The organic solvent is preferably (an inert solvent which does not affect the anionic polymerization) toluene, xylene, THF or the like.
In a preferred embodiment, the multiple double bond polar compound comprises at least two carbon-carbon double bonds and at least one polar group. The polar group is preferably a polar group containing at least one of oxygen, silicon, nitrogen, sulfur, and tin. The polar group preferably includes at least one of a carboxyl group, an ester group, and a silicone group.
In a more preferred embodiment, the multiple double bond polar compound includes at least one of a conjugated diene acid, a conjugated diene acid ester, a multiple vinyl group-containing organosilicon compound, and a multiple vinyl group-containing organosilicon oligomer. Preferred polar compounds with multiple double bonds include at least one of octavinyl-pos, maleic acid diacrylate, cis-4, 7,10,13,16, 19-docosahexaenoic acid, cis-5, 8,11,14, 17-eicosapentaenoic acid ester, vinyl-terminated polymethylvinylsiloxane, vinyl-terminated polydimethylsiloxane, methylvinylsiloxane rubber or resin, 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane, maleic anhydride, and maleic acid ester.
The multiple double bond polar compound of the present invention has the following conditions:
1) the molecular structure must contain at least two double bonds, which may be terminal vinyl (CH) 2 CH-) or carbon-carbon double bonds (-CH ═ CH-) in the molecular structure, multiple double bonds may provide multiple crosslinking points;
2) the molecular structure must contain polar group composed of at least one of oxygen, silicon, nitrogen, sulfur, tin and other atoms;
3) the organic modifier may be a low molecular compound or an oligomer or polymer.
The polar compound with multiple double bonds can be at least one of conjugated diene acid and esters thereof, such as maleic anhydride or esters thereof, acrylic acid and esters thereof, diallyl maleate, cis-4, 7,10,13,16, 19-docosahexaenoic acid and esters thereof, cis-5, 8,11,14, 17-eicosapentaenoic acid and esters thereof, bisphenol A glycerol dimethacrylate, diallyl phthalate and the like.
The multiple double bond polar compound of the present invention may be an organosilicon compound or oligomer containing a polyvinyl group: such as common octavinyl-pos (octavinyl octasilsesquioxane), belongs to a nanometer hybrid molecular compound, has a structure of (formula 1),
Figure BDA0001787326560000061
octavinyl-pass is a white powder with melting point >350 ℃ and flash point >200 ℃ and is currently used mainly as coupling agent and silicone nano-additive.
Alternatively, the organosilicon compound containing multiple vinyl groups has the structure of formula 2.
Figure BDA0001787326560000062
Wherein R is 1 、R 2 、R 3 And R 4 It may be a vinyl group, or it may be another alkyl group or a phenyl group or another polar group, but R 1 、R 2 、R 3 And R 4 At least one of the two is vinyl, the content of the vinyl in the organosilicon compound is 0.22-1.9 mol%, the viscosity is 200-60000, m, a and b are all larger than 1, and the viscosity of the multivinyl organosilicon compound is determined. The organic silicon compound with the structure of the formula 2 comprises addition type liquid silicon rubber, organic silicon gel, vinyl-terminated polydimethylsiloxane (Vi-PDMS) of a modifier/reinforcing material of a rubber compound, vinyl-terminated polymethylvinylsiloxane (Vi-PMVS), phenyl vinyl silicone oil or methyl vinyl silicon rubber (or resin) with the mole fraction of vinyl of 0.1-1.8%, and the like. Or 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane and the like can be selected.
The multiple double bond polar compound of the present invention is more preferably at least one of octavinyl-pos, maleic acid diacrylate, cis-4, 7,10,13,16, 19-docosahexaenoic acid, cis-5, 8,11,14, 17-eicosapentaenoic acid and ester compounds thereof, vinyl-terminated polymethylvinylsiloxane, vinyl-terminated polydimethylsiloxane, methyl vinyl silicone rubber or resin, 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane, and maleic anhydride or ester thereof. The acrylic acid and ester compounds are unstable in raw rubber, are easy to self-polymerize and have large odor. Among them, the most preferable multiple double-bond polar compound is octavinyl-pos.
Preferably, the BR comprises at least one of Nd-45, CB-24 or BR-9000.
Preferably, the mass ratio S/B of the styrene block to the butadiene block in the SSBR is 20-40/80-60, and the content of vinyl units in the polybutadiene block is 40-65%.
In a preferable scheme, the mass of the multi-double bond polar compound in the SSBR modified by the multi-double bond polar compound accounts for 2-15% of the mass of the SSBR; more preferably 5 to 15%.
In a preferable scheme, the mass of the multi-double bond polar compound in the BR modified by the multi-double bond polar compound accounts for 10-40% of the mass of the BR; more preferably 15 to 35%.
The preferable scheme is that the formula of the tread rubber of the multi-double-bond polar compound modified semi-steel radial ply tire comprises multi-double-bond polar compound modified SSBR, multi-double-bond polar compound modified BR, white carbon black, filling oil, sulfur, an initiator, carbon black, Si-69 or silicon-75, stearic acid, zinc oxide, an anti-aging agent and an accelerator.
The more preferable formula of the multi-double-bond polar compound modified semi-steel radial tire tread rubber comprises the following components in percentage by mass: 100-130 parts of double-bond polar compound modified SSBR, 30-45 parts of double-bond polar compound modified BR, 100-120 parts of white carbon black GR, 50-60 parts of filling oil, 2.7-3.0 parts of sulfur, 0.1-1.0 part of initiator, Si-69 or silicon-758-12 parts, 6-8 parts of carbon black N3306, 2-4 parts of stearic acid, 4-6 parts of zinc oxide, 40202-3 parts of anti-aging agent, 2-3 parts of accelerator CZ and 2-3 parts of accelerator D.
More preferably, the initiator comprises benzoyl peroxide and/or azobisisobutyronitrile.
The SSBR used in the present invention may be a commercially available SSBR such as VSL series, SPRINTAN TM SLR series, HPR series, and SSBR-2557S or SSBR-2563.
The formula of the tread rubber of the semi-steel radial tire provided by the invention adopts SSBR modified by a compound (also called organic modifier) containing an active unit structure with multiple carbon-carbon double bonds and a functional group consisting of polar atoms to replace conventional SSBR, and simultaneously adopts BR modified by a compound (also called organic modifier) containing an active unit structure with multiple carbon-carbon double bonds and a functional group consisting of polar atoms to replace conventional BR, and then the high-performance tire is prepared according to the tread rubber silicon formula well known in the industry, compared with the tire prepared by general SSBR/BR and white carbon black, the rolling resistance improvement rate can reach 40 percent at most.
The invention relates to a high-performance semi-steel radial tire tread rubber which is a silicon formula known in the industry, and comprises the following main components: SSBR, BR, white carbon black, filling oil, sulfur, carbon black, Si-69/or Si-75, stearic acid, zinc oxide, an anti-aging agent, an accelerator and the like.
The purpose of the free radical initiator selected in the silicon formula is to graft conjugated diene polar compounds (such as maleic anhydride and the like) in the components into double bonds in SSBR or BR, wherein one of benzoyl peroxide or azobisisobutyronitrile and the like is preferably used, and the preferable using amount is 0.5-1.0 part. The initiator has the function of initiating the grafting of the conjugated diene polar compound to the double bonds in the SSBR or BR during the mixing and vulcanization of the composite material.
The white carbon black coupling agent is Si-69 or Si-75, if the multiple double-bond polar compound added into the raw rubber is not the conjugated organic acid, the dosage of the coupling agent can be reduced according to the dosage, if the multiple double-bond polar compound added into the raw rubber is the conjugated organic acid, the dosage of the coupling agent is properly increased, mainly considering that siloxane in the coupling agent reacts with H atoms in the organic acid, and the excessive organic acid consumes the coupling agent.
The molecule of the silicon formula high-performance semi-steel radial tire tread vulcanized rubber has a structure of a formula 3 (one structure is illustrated for specific description):
Figure BDA0001787326560000081
wherein, the structure in formula 3 belongs to a cross-linked network structure of SSBR and BR modified at the middle end of a polar group; a. b, c, d, e, g, h, i, k, m, n, o and the like are natural numbers and are not 0 at the same time. They determine the molecular weight of the SSBR or BR raw rubber and are randomly distributed; f and F are multi-double bond polar compounds, wherein F is a multi-carbon double bond functionalized modifier; f is a conjugated diene functional modifier. f is easy to graft with double bonds in rubber under the action of peroxide and heat; f and F can exist at the same time or only one; -S-is a sulphur bond, -S-F is a functionalised modifier of sulphur with multiple carbon-carbon double bonds and a single back-to-back connection of the rubber molecule for double bond incompleteness, -S-F-S-is a functionalised modifier of sulphur with multiple carbon-carbon double bonds and a complete double back-crosslinking of the rubber molecule.
The mixing of the composite rubber material is characterized in that firstly, the double-bond polar compound modified SSBR, the double-bond polar compound modified BR, white carbon black, filling oil, carbon black, Si-69/or Si-75, stearic acid, zinc oxide, an anti-aging agent, an accelerant, a free radical initiator and the like are put into an internal mixer, the rubber material is mixed for 4-6 min at the temperature of 130-150 ℃ due to friction heat of a rotor, the rubber material and the filler are basically mixed uniformly, the conjugated diene functionalized modifier can be subjected to micro grafting with double bonds in rubber under the action of the initiator, and at the moment, the composite rubber mixture can be discharged to form master batch. And then putting the master batch on an open mill at 50-60 ℃, adding sulfur for mixing, respectively cutting 3/4 positions on the left and right sides for three times at an interval of 15s, adjusting the roller spacing to 0.8mm, alternately passing through each end longitudinally for six times, pressing the rubber material into a rubber sheet with the thickness of about 2.2mm, and then discharging the rubber sheet for vulcanization.
The vulcanization of the rubber compound is carried out under the process conditions well known in the industry, the vulcanization is carried out for 15min at 160 ℃, and micro-crosslinking between sulfur and rubber molecules and micro-crosslinking between sulfur and a multi-double-bond polar compound and double bonds in the rubber molecules exist in the vulcanization process. Meanwhile, the multi-double-bond polar compound contained in the formula and double bonds in rubber molecules can be further subjected to micro-grafting, namely, functional groups are grafted into vulcanized rubber network molecules to achieve tread rubber of the middle-end modified tire. And (3) analyzing the physical property and dynamic mechanical property (DMA) of the molded vulcanized rubber.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention aims at the defects that the existing general functional group-free SSBR and BR and the existing functionalized SSBR have the polar group blocking rate or coupling rate of not higher than 50 percent in the preparation process or have other defects of technical or raw material sources. According to the invention, a multi-double bond polar compound is added into the rubber solution synthesized by SSBR and BR to be used as a modifier to prepare the tread rubber of the high-performance tire, the preparation process is simple, the preparation can be completed by utilizing the existing mature process, and the control and industrialization are easy.
According to the modification technology, polar groups in the vulcanized tread rubber can be uniformly distributed at the middle end of a network molecular chain of SSBR and BR or close to the inert tail end of a rubber molecular chain, polar substances participating in grafting or vulcanizing can be properly controlled, the equivalent of functionalized groups is large, namely, free chain end chain links capable of being passivated are introduced, the Payne effect of the composite vulcanized tread rubber is reduced, and the chain links containing the polar groups can participate in the effective elastic recovery process of macromolecules, so that the energy generated in periodic deformation is converted into stored energy, the heat generation is avoided, the grip traction force of the tire tread rubber material manufactured by the conventional general SSBR can be kept unaffected, and the rolling resistance improvement rate of the tire can reach 40% at most. The aim is to reduce the rolling resistance of the tyre and the fuel consumption of the automobile to the maximum. The invention achieves the aim of saving fuel oil of the tire in the true sense, and is a good method for preparing the tread rubber material of the green, environment-friendly and ultrahigh-performance tire.
Detailed Description
The present invention is illustrated by the following examples, which are not intended to limit the scope or practice of the invention.
In the following examples, the physical properties of the vulcanizate were measured using an INSTRON tensile machine; the tan delta value at 0 ℃ is measured by a dynamic viscoelastometer to represent the wet skid resistance of the tire tread rubber, and the tan delta value at 60 ℃ is used to represent the rolling resistance and the improvement rate of the tire tread rubber; the dynamic heat generation of the vulcanizate was measured using a DUNLOP power loss meter.
Example 1
840g of SSBR2563 glue solution (the mass concentration of the glue solution is 15.2%) produced in a solution polymerized styrene-butadiene rubber workshop from the company, Baling, petrochemical company, is put into a 1000mL three-neck flask, and the glue solution is marked as A1. Adding 10g of tetrahydrofuran solution of 50 wt% octavinyl-POSS into an A1 glue solution bottle, strongly stirring for 30min at 40-60 ℃, condensing by steam, drying, and obtaining crude rubber A1 with Mooney viscosity of 62.5; in addition, 40g of BR-9000 was placed in a 1000mL three-necked flask, and 360g of hexane solvent was added thereto and dissolved at room temperature with stirring to obtain a dope solution designated as A2. And adding 5g of 50 wt% octavinyl-POSS tetrahydrofuran solution into the A2 glue solution, strongly stirring for 30min at 40-60 ℃, condensing by steam, and drying to obtain crude rubber A2.
Example 2
840g of SSBR2563 gum solution (gum solution mass concentration of 15.2%) from the solvent-polymerized styrene-butadiene rubber plant of the synthetic rubber division of the company Baling petrochemical company is taken and placed in three 1000mL three-neck flasks, and the gum solution is marked as B1. Adding 5g of tetrahydrofuran solution of 50 wt% octavinyl-POSS and 10g of dibutyl maleate into a B1 glue solution bottle, strongly stirring at 40-60 ℃ for 30min, condensing by steam, drying, and obtaining Mooney viscosity of 62.2 to obtain raw rubber B1; in addition, 40g of BR-9000 was placed in a 1000mL three-necked flask and 360g of hexane solvent was added thereto and dissolved therein under stirring at room temperature to obtain a dope denoted by B2. And adding 6g of vinyl-terminated polymethylvinylsiloxane with the vinyl content of 1.53 mol% into the B2 glue solution, strongly stirring for 30min at 40-60 ℃, condensing by steam, and drying to obtain the crude rubber B2.
Example 3
840g of SSBR2563 gum solution (15.2% gum solution mass concentration) produced in a solution polymerized styrene-butadiene rubber workshop from the company, Balin petrochemical company, was taken and placed in a 1000mL three-neck flask, and the gum solution was identified as C1. And adding 8g of diallyl maleate and 8g of cis-5, 8,11,14, 17-eicosapentaenoic acid ethyl ester into a C1 glue solution bottle, strongly stirring at 40-60 ℃ for 30min, and performing steam coagulation and drying to obtain the raw rubber C1 with the Mooney viscosity of 61.2. In addition, 40g of BR-9000 was placed in a 1000mL three-necked flask, and 360g of hexane solvent was added thereto and dissolved at room temperature with stirring to obtain a dope labeled as C2. Strongly stirring 4g of cis-4, 7,10,13,16, 19-docosahexaenoic acid and diallyl maleate in the C2 glue solution for 30min at 40-60 ℃, condensing by steam, and drying to obtain raw glue C2;
example 4
The modified SSBR prepared in examples 1-3 was combined with modified BR in the proportions of A1-A2, B1-B2 and C1-C2, and compared with a dry-filled compound rubber compound comprising 7 parts of octavinyl-POSS, 10 parts of diallyl maleate, 10 parts of SSBR 2563125, BR-900040 parts of a combination of related compounding agents, and the physical properties of the tread rubber prepared by mixing and vulcanizing according to the method of the present invention are shown in Table 1.
TABLE 1 physical Properties of modified and generic SSBR/BR for Tread rubber
Figure BDA0001787326560000111
Note:
(1) the formula comprises (by mass portions) SSBR 125, BR 40, white carbon black 175GR 110, environment-friendly rubber filling oil 55, sulfur 2.8, benzoyl peroxide 0.6, Si-6910, carbon black N3307.5, stearic acid 3, zinc oxide 4.5, anti-aging agent 40202.5, accelerator CZ 2.7 and accelerator D2.3.
(2) Blank composed of general SSBR/BR.
The results in table 1 show that the improvement rate of the high-performance tire rolling resistance of the polar modifier containing the multi-carbon double bond filled in the rubber by the wet method is obviously better than that of the dry filling technology directly added in the silicon formula, which is mainly benefited by the mutual compatible and intercommunicating homogeneous phase contact between the modifier molecules and the rubber molecules, so that the contact surface and collision probability between the molecules during vulcanization are accelerated, and the grafting or vulcanization rate is improved; in the dry filling, the filler and the modifier are isolated and dispersed, so that the contact concentration, the contact surface and the collision probability of the modifier and the rubber are reduced; in addition, SSBR and BR are both subjected to wet filling of polar modifiers containing multiple carbon-carbon double bonds, and particularly, wet filling of octavinyl-POSS is used as a modifier of rubber, so that the rolling resistance improvement effect is most obvious, and low dynamic heat generation is reflected.
Comparative example 1
Dry filling formula: 8.3 parts of octavinyl-POSS, 125 parts of SSBR2563 (crude rubber), BR-900040 parts, 175GR 110 parts of white carbon black, 55 parts of environment-friendly rubber filling oil, 2.8 parts of sulfur, 0.6 part of benzoyl peroxide (variable), Si-6910 part, 3307.5 parts of carbon black N, 3 parts of stearic acid, 4.5 parts of zinc oxide, 40202.5 parts of anti-aging agent, 2.7 parts of promoter CZ and 2.3 parts of promoter D. The tread rubber prepared by mixing and vulcanizing according to the method has the following physical properties: 300% tensile strength (M Pa): 9.7; tensile elongation (%): 424; hardness (shao a): 67; tg (. degree. C.): -18.3; tan delta (0 ℃): 0.3674; tan δ (60 ℃): 0.1532; rolling resistance improvement rate/%: 13.9 of; dynamic heat generation (. degree. C.): 7. from comparative example 1 it can be seen that the rolling resistance improvement of the composite tread compound using dry-filled octavinyl-POSS is only 13.9%.

Claims (11)

1. A multi-double-bond polar compound modified semi-steel radial tire tread rubber composition is characterized in that: comprises a double-bond polar compound modified SSBR, a double-bond polar compound modified BR and an initiator;
the SSBR is obtained by dissolving, mixing and steam condensing SSBR glue solution and a multi-double-bond polar compound;
the BR is obtained by dissolving, mixing and steam condensing BR glue solution and a multi-double-bond polar compound;
the multi-double bond polar compound at least comprises two carbon-carbon double bonds and at least one polar group;
the polar group is a polar group containing at least one of oxygen, silicon, nitrogen, sulfur and tin.
2. The multi-double bond polar compound modified semi-steel radial tire tread rubber composition according to claim 1, characterized in that: the polar group comprises at least one of carboxyl, ester group and silicon oxygen group.
3. The multi-double bond polar compound modified semi-steel radial tire tread rubber composition according to claim 1 or 2, characterized in that: the multi-double-bond polar compound comprises at least one of conjugated diene acid, conjugated diene acid esters, organic silicon compounds containing multiple vinyl groups and organic silicon oligomers containing multiple vinyl groups.
4. The multi-double bond polar compound modified semi-steel radial tire tread rubber composition according to claim 3, characterized in that: the multi-double-bond polar compound comprises at least one of octavinyl-pos, maleic acid diallyl ester, cis-4, 7,10,13,16, 19-docosahexaenoic acid, cis-5, 8,11,14, 17-eicosapentaenoic acid ester, vinyl-terminated polymethylvinylsiloxane, vinyl-terminated polydimethylsiloxane, methyl vinyl silicone rubber or resin and 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane.
5. The multi-double bond polar compound modified semi-steel radial tire tread rubber composition according to claim 4, characterized in that: the multiple double bond polar compound includes octavinyl-pos.
6. The multi-double bond polar compound modified semi-steel radial tire tread rubber composition according to claim 1, characterized in that:
the BR comprises at least one of Nd-45, CB-24 or BR-9000;
the mass ratio S/B of the styrene block to the butadiene block in the SSBR is 20-40/80-60, and the content of vinyl units in the polybutadiene block is 40-65%.
7. The multi-double bond polar compound modified semi-steel radial tire tread rubber composition according to any one of claims 1,2 and 4 to 6, which is characterized in that:
the mass of the multi-double-bond polar compound in the SSBR modified by the multi-double-bond polar compound accounts for 2-15% of the mass of the SSBR;
the mass of the multiple double-bond polar compound in the BR modified by the multiple double-bond polar compound accounts for 10-40% of the mass of the BR.
8. The multi-double bond polar compound modified semi-steel radial tire tread rubber composition according to claim 7, characterized in that:
the mass of the multi-double-bond polar compound in the SSBR modified by the multi-double-bond polar compound accounts for 5-15% of the mass of the SSBR;
the mass of the multiple double-bond polar compound in the BR modified by the multiple double-bond polar compound accounts for 15-35% of the mass of the BR.
9. The multi-double bond polar compound modified semi-steel radial tire tread rubber composition according to any one of claims 1,2 and 4 to 6, which is characterized in that: comprises double-bond polar compound modified SSBR, double-bond polar compound modified BR, white carbon black, extender oil, sulfur, an initiator, carbon black, Si-69 or Si-75, stearic acid, zinc oxide, an anti-aging agent and a promoter.
10. The multi-double bond polar compound modified semi-steel radial tire tread rubber composition according to claim 9, characterized in that: the adhesive comprises the following components in parts by mass: SSBR modified by multi-double-bond polar compound100~130Part, multi-double bond polar compound modified BR30~45Parts of white carbon black 175GR100~120Portion, filling oil50~60Sulfur, sulfur2.7~3.0Part(s) of an initiator0.1 ~1.0Part of Si-69 or Si-75 8~12Carbon black N330 6~8Part(s) stearic acid2~4Zinc oxide4~6Part of anti-aging agent 40202~3Portion of accelerator CZ2~3Part(s) of an accelerator D 2~3And (4) portions.
11. The multi-double bond polar compound modified semi-steel radial tire tread rubber composition as claimed in claim 10, wherein: the initiator comprises benzoyl peroxide and/or azodiisobutyronitrile.
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JP2014172957A (en) * 2013-03-07 2014-09-22 Toyo Tire & Rubber Co Ltd Process for producing modified polymer and diene polymer

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