CN112480504B - Wear-resistant high-wet-skid-resistance composite material for soles and preparation method thereof - Google Patents
Wear-resistant high-wet-skid-resistance composite material for soles and preparation method thereof Download PDFInfo
- Publication number
- CN112480504B CN112480504B CN201910861943.6A CN201910861943A CN112480504B CN 112480504 B CN112480504 B CN 112480504B CN 201910861943 A CN201910861943 A CN 201910861943A CN 112480504 B CN112480504 B CN 112480504B
- Authority
- CN
- China
- Prior art keywords
- resistant
- rubber
- composite material
- wear
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a wear-resistant and high-wet-skid-resistance composite material for soles and a preparation method thereof, wherein the composite material for soles comprises the following component raw materials: polystyrene-b-butadiene/isoprene/divinylbenzene random copolymer, natural rubber, polar rubber containing double bonds and auxiliary materials. Compared with the traditional SBS, SEBS, SSBR, ESBR, BR and brominated butyl rubber composite materials, the composite sizing material has the characteristics of good physical and mechanical properties, strong ageing resistance, low deformation, wear resistance, fatigue resistance and high bonding strength, and is particularly suitable for preparing middle-and high-end sports shoe soles.
Description
Technical Field
The invention relates to a sizing material for soles, in particular to a composite material for soles with wear resistance and high wet skid resistance, and a preparation method thereof, belonging to the technical field of sizing material preparation for soles.
Background
The traditional commercial styrene-conjugated diene copolymer has the emulsion polymerized styrene-butadiene rubber ESBR system with lower vinyl content, anionic polymerized styrene-butadiene rubber SSBR, SIBR and the like, and the sequence distribution of the polymer has random copolymerization and block copolymerization. Such as styrene-butadiene rubber ESBR and SSBR series for tire tread rubber are randomly distributed. As SSBR for vulcanizable shoe materials, for example, the SSBR has a partially block linear structure of 1205 and 2003 types, and the content of side chain groups (such as vinyl groups or 3, 4-addition) of conjugated diene segments in polymer molecules is not more than 20%, so that the vulcanized shoe sole product has poor wet skid resistance. In addition, the wear resistance, the flexing resistance and the aging resistance of the sole made of the thermoplastic styrene-butadiene elastomer SBS are lower than those of vulcanized rubber, and the wet skid grip is lower.
Chinese patent (CN 101747543 a) discloses a styrene-butadiene copolymer chemical foaming composition containing polystyrene micro-block and its preparation and application method, the method uses styrene-butadiene copolymer mixed with random structure and block structure as base material, and adds flow modifier and softening agent to regulate the fluidity of rubber, the rubber composition produced by using the method has good fluidity, and can be directly formed by injection molding; the chemical foaming agent is added to reduce the density of the product, so that the aim of lightening the material is effectively fulfilled, but the sole prepared by the material and the method has light weight, but the wear resistance and the strength are obviously insufficient, and the sole belongs to a low-end material. Chinese patent (CN 107629341A) discloses a low-elasticity anti-slip rubber and a preparation method thereof, and specifically discloses the low-elasticity anti-slip rubber which comprises 100 parts by weight of main rubber; 2-4 parts of coupling agent; 5-10 parts by weight of softening oil; 50-65 parts of white carbon black; 3-5 parts of zinc oxide; 1-2 parts by weight of stearic acid; 0.5-1 parts by weight of microcrystalline wax; 5-10 parts by weight of uniform resin; an anti-aging agent, an active agent, an accelerator and sulfur in proper amounts; the main rubber consists of 10-15 parts by weight of natural rubber, 45-65 parts by weight of brominated butyl rubber, 5-15 parts by weight of styrene-butadiene rubber and 15-25 parts by weight of cis-butadiene rubberThe rubber has the advantages of ultra-low elasticity and excellent anti-slip capability, and has wide application prospect in outdoor exercises such as rock climbing, mountain climbing, hiking and the like. Chinese patent (CN 103570992A) describes a sole material of sports shoes for body building and mountain climbing and a preparation method thereof, wherein the sole material comprises the following components in percentage by mass: 25-30% of natural rubber, 25-35% of styrene-butadiene rubber, 1-3% of short fiber, 8-15% of carbon black and white carbon black (SiO) 2 ) 10 to 12 percent, 2 to 2.5 percent of stearic acid, 3 to 5 percent of zinc oxide, 3 to 3 percent of Si-692 and 3 to 6 percent of sulfur. After the formulation is proportioned, the rubber compound is prepared by mixing by a special internal mixer for mixing short fiber rubber, then is sliced by an open mill or a calender, is extruded by a pin cold feed extruder with a short fiber directional orientation machine head, and finally is vulcanized in a sole die to obtain the sports shoe sole product for body-building and mountain climbing, and the prepared sole has better elasticity, better wear resistance and puncture resistance, improves the comfort and safety of mountain climbing and body-building exercises, and prolongs the service life of the shoe to a certain extent.
The use of oil-extended 1, 2-polybutadiene rubber in rubber soles is also described in "elastomer, 1995, 02", and the oil-extended amount of polybutadiene rubber with a high vinyl content of 79% in molybdenum series, the amount of oil-extended rubber in the material, and the vulcanization and reinforcement system are discussed. The result shows that the oil filling in molybdenum BR can improve the processability of the material, improve the wet skid resistance and facilitate the dispersion of the reinforcing agent in the blending material, the processing physical properties of the rubber are similar to those of the oil filling styrene-butadiene rubber, and the rubber is filled with oil and white carbon black and then has good physical properties under the action of sulfur/promoters CZ and TT, so that the high-grade anti-skid sport shoe made of the 1, 2-polybutadiene oil filling rubber is feasible.
In addition, in (application of bromobutyl in shoe material [ C ]. China International rubber oil industry peak meeting-rubber oil downstream market analysis and application trend forum, 2019 (tenth boundary)), a composite material composed of 2244 55 parts of BIIR, 2003 25 parts of SSBR, 20 parts of NR and related fillers, auxiliaries and the like is mixed and vulcanized into an application formula in the outsole of the marathon running shoe, and the manufactured running shoe can be run for athletes for more than 1000Km, shows good wear resistance and has the defects of insufficient wet skid grip.
Chinese patent (CN 103804602 a) discloses a solution polymerized butadiene-styrene random copolymer, a preparation method thereof and application of a compound regulator. The polymer is designed according to the tread rubber of the radial tire, but the polymer prepared by the method has narrow molecular mass distribution, low green strength, molecular fraction and intermolecular entanglement degree, and poor processability. In (synthetic rubber industry, 2010-11-15, synthesis of tin-coupled oil-extended styrene-isoprene-butadiene terpolymer [ SIBR ]) it is described to initiate polymerization of styrene-isoprene-butadiene with butyllithium in cyclohexane with asymmetric ether as regulator, followed by coupling with tin tetrachloride. As a result, the polymer 1,2 addition units and 3,4 addition units are not described, and show a bimodal narrow distribution, and the low green strength results in poor roll-to-roll performance in processing, and the low degree of entanglement between molecular chains results in small reduction in shear thinning viscosity. DMA analysis SIBR vulcanized rubber has better wet skid resistance than SSBR2305, ESBR1502 and other general styrene butadiene rubber. Also in (elastomer, 2012-2-25, study of basic properties of domestic integrated rubber SIBR) a tread band made of polystyrene-butadiene-isoprene rubber is described with respect to its wet skid resistance 2.5 times that of emulsion polymerized styrene-butadiene rubber, but the microstructure of such SIBR is not described, nor is the application of such a material to sports shoes.
In summary, the conventional anionic styrene-conjugated diene polymer has the disadvantages of low melt elasticity, poor processability and poor slip resistance of vulcanized rubber, while the preparation method of the high-end or sports shoes with the rubber materials with good processability and good wet slip resistance and the composite materials with high strength, high wear resistance and good bonding performance has not been reported yet.
Disclosure of Invention
Aims at the defects of the prior art that the synthetic rubber material is used as a middle-end, high-end or sports shoe material. The invention aims to provide a composite sizing material which is formed by taking polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer as a main sizing material (SIBR) and matching natural rubber and high-polarity rubber containing double bonds as auxiliary rubber, filling materials and auxiliary agents, wherein the composite sizing material has the characteristics of good physical and mechanical properties, strong ageing resistance, low deformation, wear resistance, fatigue resistance and high bonding strength compared with the traditional composite materials such as SBS, SEBS, SSBR, ESBR, BR and brominated butyl rubber after being vulcanized, and is particularly suitable for preparing middle-high-end sports shoe soles.
The invention also aims at providing a method for preparing the sole with high wet skid resistance and high wear resistance by adopting a mixing and vulcanizing method for the composite sizing material, and the method has the characteristics of simple operation and low cost, and is beneficial to industrial production.
In order to achieve the technical aim, the invention provides a composite material for a wear-resistant and high-wet-skid-resistance sole, which comprises the following raw materials in parts by weight: polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer, natural rubber, polar rubber containing double bonds and auxiliary materials.
In a preferred embodiment, the polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer has a number average molecular weight of 10 to 20X 10 4 The mass ratio of the styrene unit to the total mass of the butadiene unit and the isoprene unit is (20-40)/(80-60), and the molecular weight distribution index is not less than 1.65; the mass of the divinylbenzene unit is 0.02 to 0.03 percent of the total mass of the butadiene unit and the isoprene unit.
In a preferred embodiment, the 1,2 structural proportion of the butadiene units and the 3,4 structural proportion of the isoprene units in the polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer are not less than 58%.
In a preferred embodiment, the mass ratio of the butadiene units to the isoprene units in the polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer is (10 to 90)/(90 to 10).
Preferably, the natural rubber is 3# and/or 5# standard rubber. The purpose of the NR in the composite material is to improve the strength and wear resistance of the composite material, but the excessive use of NR leads to the reduction of the wet skid resistance of the composite material.
In a preferred embodiment, the polar rubber containing double bonds is at least one of allyl glycidyl ether binary or ternary copolymerized chlorohydrin rubber (EPICHLOMER CG), brominated butyl rubber (BIIR 2224), chloroprene rubber (CR 121) and the like. The polar rubber is selected in the formula to improve the affinity between the composite material sole and the vamp material such as fiber cloth or leather material, and the like, and to improve the adhesive force and tearing strength between the sole and the vamp material.
In a preferred scheme, the auxiliary materials comprise filling materials, whitening agents, softening filling oil, pigments, coupling agents, auxiliary accelerators, main accelerators, paraffin wax, anti-aging agents and vulcanizing agents.
The preferable scheme comprises the following raw materials in parts by mass: 70-90 parts of polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer; 35-45 parts of natural rubber; 35-45 parts of polar rubber containing double bonds; 90-110 parts of filler; 0.04 to 0.08 portion of whitening agent; 35-45 parts of softening filling oil; pigment 0-0.4 weight portions; 0-12 parts of coupling agent; 5-8 parts of auxiliary accelerator; 4-6 parts of a main accelerator; 1.5 to 2.0 portions of paraffin; 0.35-0.40 part of anti-aging agent; 2.5 to 3.0 portions of vulcanizing agent.
Preferably, the filler is carbon black or white carbon black. The filler selected for the white sole composite material is white carbon black, and is preferably one of the commercially available rotunda 175MP, H810 and the like. For black sole composite materials, one of commercially available N234 or N330 is preferred.
Preferably, the whitening agent is an optical whitening agent. For the selected whitening agent in white shoe composites, commercially available fluorescent whitening agents such as OB and the like are preferred.
Preferably, the softening filling oil is NAP rubber oil or naphthenic white oil KN4010.NAP rubber oil or naphthenic white oil KN4010 is environment-friendly rubber oil, has no toxic or side effect, but NPA series rubber oil is prepared by hydrofining heavy aromatic oil, and has a light yellow appearance. Thus, cycloalkyl white oil may be further preferred as for example in the preparation of white soles.
Preferably, the pigment is an inorganic or organic colorant, such as ultramarine blue or a disperse dye.
Preferably, the coupling agent is at least one of KH-550, silicon-69 or silicon-75. It is worth noting that if white soles are prepared, silica coupling agents which are required to be used for filling white fillers such as white carbon black and the like are selected; if carbon black is used as the filler reinforcing material throughout the formulation, it may not be necessary to use a coupling agent.
Preferably, the auxiliary accelerator comprises zinc oxide and stearic acid. The more preferable auxiliary accelerator consists of zinc oxide and stearic acid according to the mass ratio of 3.5-4.8: 2.0 to 2.5.
Preferably, the main accelerator comprises DM and TS. The preferable main accelerator is prepared from DM and TS according to the mass ratio of 2.3-2.7: 2.5 to 3.2. The accelerator TS has the characteristic of post-effect vulcanization, namely the formed sole can be vulcanized slowly by itself at room temperature until the crosslinking is complete, and a vulcanizing system is selected and used for accelerating the vulcanization of the compound rubber compound, shortening the vulcanization time and improving the preparation efficiency.
Preferably, the anti-aging agent is 4020 or 1076. These antioxidants may be selected from conventional amine antioxidants for polyolefin or rubber.
Preferably, the vulcanizing agent comprises elemental sulfur.
The invention also provides a preparation method of the composite material for the wear-resistant and high-wet-skid-resistance sole, which comprises the steps of mixing the component raw materials except the vulcanizing agent to obtain master batch, and carrying out open mill on the master batch and the vulcanizing agent to obtain the open mill, and extruding, vulcanizing and molding the open mill.
In a preferred scheme, the control temperature of the mixing process is not higher than 140 ℃, and the mixing time is 120-150 s.
In a preferred scheme, the extrusion temperature is controlled to be 120-140 ℃, the vulcanization temperature is 160 ℃, and the vulcanization time is 10-14 min in the extrusion vulcanization molding process.
The composite material for the wear-resistant and high-wet-skid-resistant sole can be made into white, black or other colored soles.
The formula of the white or colored sole material is as follows: 80 parts of SIBR, 35-45 parts of NR, 35-45 parts of unsaturated polar rubber, 90-110 parts of white carbon black, 0.04-0.08 part of whitening agent, 35-45 parts of environment-friendly rubber oil, 8-12 parts of coupling agent, 3.5-4.8 parts of zinc oxide, 2.0-2.5 parts of stearic acid, 0-0.4 part of pigment, 2.5-3.2 parts of accelerator TS, 2.3-2.7 parts of accelerator DM, 1.5-2.0 parts of paraffin, 2.5-3.0 parts of sulfur and 0.35-0.40 part of anti-aging agent.
The formula of the black or dark color shoe sole material is as follows: 80 parts of SIBR, 35-45 parts of NR, 35-45 parts of unsaturated polar rubber, 90-110 parts of carbon black, 35-45 parts of environment-friendly rubber oil, 3.5-4.8 parts of zinc oxide, 2.0-2.5 parts of stearic acid, 2.5-3.2 parts of accelerator TS, 2.3-2.7 parts of accelerator DM, 0-0.4 part of coloring material, 1.5-2.0 parts of paraffin, 2.5-3.0 parts of sulfur and 0.35-0.40 part of anti-aging agent.
The polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer (SIBR) adopted in the formula of the invention is prepared by initiating styrene by butyl lithium in a traditional solvent system, then adding a butadiene-isoprene-divinylbenzene ternary mixed monomer for molecular active chain slow growth to obtain the SIBR with high vinyl and high 3, 4-adduct content, wide molecular mass distribution and high green strength as a main sizing material, wherein the preferable raw rubber Mooney viscosity is 35-65, the molecular weight distribution index is not less than 1.65, and the molecular side chain group content is not less than 58%. The purpose is to improve the processing performance and the wet skid resistance and the safety performance of the composite material, and meanwhile, the SIBR has good compatibility, cracking resistance and ageing resistance with natural rubber.
The preparation method of the polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer comprises the following steps: firstly, placing a styrene monomer polymerized in a first section into a steel polymerization kettle filled with a solvent and an activation regulator, adding quantitative n-butyllithium to initiate styrene polymerization at a set temperature under the protection of nitrogen, slowly and continuously adding a divinylbenzene, butadiene and isoprene mixed monomer to perform second-section polymerization, discharging after polymerization, adding a small amount of water, introducing carbon dioxide gas to terminate active lithium, adding an antioxidant into a glue solution, stirring and mixing uniformly, condensing the glue solution into colloidal particles through water vapor, and finally drying the colloidal particles. Wherein the activation regulator is at least one of tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl amine and tetrahydrofurfuryl alcohol hexyl ether; the concentration of the activation regulator in the polymerization system is 280-400 mg/L. The temperature of the first-stage polymerization reaction is 50-55 ℃ and the time is 10-15 min. The two-stage polymerization reaction process comprises the following steps: uniformly and continuously adding the divinylbenzene and conjugated diene mixed monomer into a polymerization system within 50-60 min, maintaining the temperature within 50-75 ℃, and reacting for 15-25 min after the mixed monomer is added. The slow continuous feeding mode can lead the divinylbenzene to participate in the growth and branching of the molecular chain in the process of chain growth of the polymer, and the molecular mass distribution of the polymer is widened while the weight average molecular mass (Mw) of the polymer is improved. The polymerization termination process is as follows: adding water into the polymerization system, and introducing carbon dioxide gas into the polymerization system under normal pressure to ensure that the pH value of the water phase is not higher than 8. The mass of the added water is 0.5-2% of the total mass of the glue solution. The solvent is cyclohexane, and the solvent is used in an amount to ensure that the mass concentration of the total mass of the polymerized monomer in the solvent is 10-15%.
The preparation method of the sole comprises the steps of material mixing in a formula, thin-pass tabletting of a masterbatch, extrusion vulcanization molding of tabletting adhesives and the like.
The mixing is carried out in an internal mixer: firstly, starting a motor, putting filling oil, filling materials, other auxiliary agent small materials except sulfur and the like in raw rubber and a formula into an internal mixer, wetting raw rubber and oil materials and 'eating' the powder materials under the shearing action of a rotor in the internal mixer, and meanwhile, compounding the raw rubber and the oil materials to form a masterbatch of non-Newtonian fluid, wherein the preferable mixing time is 120-150 s, and the temperature of the masterbatch is not higher than 140 ℃ under the shearing action and the friction action.
Masterbatch sizing material thin-pass tabletting: placing the masterbatch on a two-roll cooling open mill, adding sulfur after the rubber material is wrapped on a roll, then respectively carrying out rubber three times at the left and right 3/4 of the roll, then carrying out thin pass six times, and then pressing the composite rubber material into a rubber sheet with 110 multiplied by 3 mm.
Extrusion vulcanization molding of the tabletting adhesive: the tabletting glue is added into an inlet of an extruder in a cold feeding mode, and then extruded and injected into a sole die cavity to carry out mould pressing sulfurForming; among them, the extrusion temperature of 120 is preferable ～ 140 ℃; the vulcanization temperature of the sole die cavity is 160 ℃ and the vulcanization time is 10 ～ 14min。
And the physical property analysis of the needed glue sample is carried out according to the national standard, wherein the vulcanization temperature is 160 ℃, and the vulcanization time is 12min.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
compared with the existing natural rubber, emulsion polymerized styrene-butadiene rubber, SSBR (T2003), dyansol 1205, SSBR3216, SSBR2605 produced by the synthetic rubber industry department of Baling petrochemical company and the like, the compound material has the defects of low side branch content, poor slip resistance, low adhesive force and peeling strength between the sole and polar materials caused by non-polar groups in the polymer network of the compound material, easy degumming of the adhesive coating of the sole and the like; and the existing solution polymerized styrene-butadiene rubber has the defects of narrow molecular weight distribution, low melt elasticity, poor processability caused by no long branched chain of a molecular chain, and easy cracking of vulcanized rubber caused by poor compatibility with natural rubber. The formula system of the invention adopts the polystyrene-b-conjugated diene/divinylbenzene copolymer (or SIBR) and natural rubber as well as unsaturated strong polar rubber as the main sole rubber for the first time, the SIBR endows the composite material with the processing performance and the wet skid resistance and the safety performance, and simultaneously, the SIBR and the natural rubber have good compatibility, tear resistance, wear resistance, crack resistance and ageing resistance; the unsaturated strong polar rubber gives the sole and vamp materials adhesion and tear strength in vulcanized rubber network macromolecules. In addition, the compound quick-acting accelerator is selected in the formula to accelerate the vulcanization of the rubber compound, so that the preparation time is shortened, and the preparation efficiency is improved. Based on the above, the preparation method of the invention is particularly suitable for soles of sport brands, such as marathon running shoes, basketball, volleyball, table tennis shoes and the like; can also be used as middle and high-end leisure and military soles.
The technology of the invention has simple preparation, can be completed by utilizing the existing mature technology, and is easy to control and industrialize.
Detailed Description
The following examples illustrate the invention and are not to be construed as limiting the scope or practice of the invention.
The number average molecular weight and the molecular mass distribution index of the polymer were measured by Gel Permeation Chromatography (GPC) in the following examples; measuring physical properties of vulcanized rubber by using an INSTRON tensile machine; quantitatively determining the microstructure content of the polymer by using an H-NMR spectrum by adopting AacendTM 400; the tan & value at 0 ℃ is measured by adopting a DMTS instrument of GABO company to characterize the wet skid resistance of the composite material; right angle tear Strength (N/mm) was measured according to the DW-22GT-TCS2000 (500+ -mm/min); the adhesive strength (N/mm) was measured according to the DW-22GT-TCS2000 (100.+ -. Mm/min); DIN abrasion (mm 3) was determined by the DW-15GT-7012-D spin (40.+ -. 1) r/min (10.+ -. 0.2) N method; the slip resistance was measured by the DW-09BL-312 dry and wet methods.
Example 1
3500mL cyclohexane, 1.0mL tetrahydrofurfuryl alcohol ethyl ether and 100mL styrene are added into a 5L polymerization kettle under the protection of nitrogen, stirring is started, the temperature of the materials is raised to 50 ℃, then 0.6mol/L n-butyllithium 10.4mL is added for initiating polymerization for 15min, then homogeneous liquid consisting of 0.10mL divinylbenzene, 183mL butadiene and 300mL isoprene under the protection of nitrogen is continuously and slowly added into a reaction liquid for polymerization, wherein the continuous feeding time is controlled to be not less than 50min, the mixed monomers are the same after being added, the reaction is continued for 20min, and the highest polymerization temperature is not higher than 75 ℃. Then, discharging the polymerized glue solution, placing the glue solution in a 5-liter steel dissolver, adding 8mL of water into the glue solution, then introducing carbon dioxide gas into the glue solution until the PH value of the glue solution is 7, standing for 20min, adding 1.0g of antioxidant 1076 into the glue solution, stirring uniformly, condensing the glue solution into colloidal particles through water vapor, and finally drying the colloidal particles to obtain the colorless transparent raw rubber.
Number average molecular weight mn=13.6x10 of the measured polymer raw rubber 4 The molecular mass distribution index was 1.66, the mooney viscosity ml=36.8, and the mass content in the vinyl and 3, 4-structure in the polydiene block was 60.2%.
Example 2
The relevant process conditions in example 1 were kept unchanged except that 1.2mL of tetrahydrofurfuryl ether, 10.0mL of n-butyllithium, a homogeneously mixed monomer consisting of 0.1mL of divinylbenzene with 350mL of butadiene and 100mL of isoprene were added, and the continuous addition time was 55min.
The colorless transparent raw rubber (polymer) obtained had a number average molecular weight mn=14.5×10 4 The molecular mass distribution index was 1.80 mooney viscosity ml=42.7 and the total mass content of vinyl and 3, 4-addition units in the diene segment was 61.4%.
Example 3
The relevant process conditions in example 1 were kept unchanged except that 1.2mL of tetrahydrofurfuryl ethyl ether, 8.0mL of n-butyllithium, and a homogeneously mixed monomer consisting of 0.12mL of divinylbenzene, 200mL of butadiene and 200mL of isoprene were added, with a continuous addition time of 60min.
The colorless transparent raw rubber (polymer) obtained had a number average molecular weight mn=17.2×10 4 The molecular mass distribution index was 1.92, the mooney viscosity ml=55.6, and the total mass content of vinyl groups and 3, 4-addition units in the diene segment was 61.6%.
Example 4
The relevant process conditions in example 1 were kept unchanged except that 1.0mL of tetrahydrofurfuryl ethyl ether was added, the monomer mixture consisted of 0.12mL of divinylbenzene, 40mL of butadiene and 270mL of isoprene, and the continuous addition time was 60min.
The colorless transparent raw rubber (polymer) obtained had a number average molecular weight mn=16.3×10 4 The molecular mass distribution index was 1.95, the mooney viscosity ml=46.3, and the total mass content of vinyl and 3, 4-addition units in the diene segment was 59.3%.
Application examples:
soles prepared according to the method of the present invention were prepared by using SIBR prepared in examples 1 to 4 described above and commercially available SSBR3216 (comparative example 1) and SSBR1205 (comparative example 2), and their corresponding formulations are shown in Table 1, and their corresponding physical properties are shown in Table 2.
Table 1 formulations (parts by weight) in examples
Table 2 physical properties of examples 1 to 4 and comparative examples 1 to 2
Note that: the adhesive strength is the peel strength of the vulcanized rubber and the leather; the slip resistance was measured by dry and wet methods.
From the examples it was found that: compared with NR, SIBR shows excellent dry-wet skid resistance, better physical property and ageing resistance compared with the traditional SSBR; the addition of small amounts of allyl chloride rubber to the formulation results in a vulcanizate exhibiting excellent adhesion properties.
Claims (11)
1. A wear-resistant and high-wet-skid-resistance composite material for soles is characterized in that: the material comprises the following components: polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer, natural rubber, polar rubber containing double bonds and auxiliary materials; the polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer has a number average molecular weight of 10 to 20X 10 4 The ratio of the mass of the styrene unit to the total mass of the butadiene unit and the isoprene unit is (20-40)/(80-60), and the molecular weight distribution index is not less than 1.65; the mass of the divinylbenzene unit is 0.02-0.03% of the total mass of the butadiene unit and the isoprene unit; the 1,2 structure proportion of butadiene units and the 3,4 structure proportion of isoprene in the polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer are not lower than 58%; the mass ratio of butadiene units to isoprene units in the polystyrene-b-butadiene-isoprene-divinylbenzene random copolymerIs (10-90)/(90-10).
2. A composite material for a wear resistant, highly resistant to wet skid as set forth in claim 1, wherein: the natural rubber is 3# and/or 5# standard rubber.
3. A composite material for a wear resistant, highly resistant to wet skid as set forth in claim 1, wherein: the polar rubber containing double bonds is at least one of allyl glycidyl ether binary or ternary copolymer chlorohydrin rubber, brominated butyl rubber and chloroprene rubber.
4. A composite material for a wear resistant, highly resistant to wet skid as set forth in claim 1, wherein: the auxiliary materials comprise filling materials, whitening agents, softening filling oil, pigments, coupling agents, auxiliary accelerators, main accelerators, paraffin wax, anti-aging agents and vulcanizing agents.
5. A composite material for a wear resistant, highly moisture and slip resistant sole according to any one of claims 1 to 4, characterized in that: comprises the following raw materials in parts by mass:
70-90 parts of polystyrene-b-butadiene-isoprene-divinylbenzene random copolymer;
35-45 parts of natural rubber;
35-45 parts of polar rubber containing double bonds;
90-110 parts of filler;
0.04 to 0.08 portion of whitening agent;
35-45 parts of softening filling oil;
pigment 0-0.4 weight portions;
0-12 parts of coupling agent;
5-8 parts of auxiliary accelerator;
4-6 parts of a main accelerator;
1.5 to 2.0 portions of paraffin;
0.35-0.40 part of anti-aging agent;
2.5 to 3.0 portions of vulcanizing agent.
6. The composite material for the wear-resistant and high-wet-skid-resistant sole according to claim 5, wherein:
the filler is white carbon black or carbon black;
the brightening agent is a fluorescent brightening agent;
the softening filling oil is NAP rubber oil or naphthenic white oil KN4010;
the pigment is ultramarine or disperse dye;
the coupling agent is at least one of KH-550, silicon-69 or silicon-75;
the auxiliary accelerator comprises zinc oxide and stearic acid;
the primary accelerator comprises DM and TS;
the anti-aging agent is 4020 or 1076;
the sulfiding agent comprises elemental sulfur.
7. The composite material for the wear-resistant and high-wet-skid-resistant sole according to claim 6, wherein: the auxiliary accelerator is prepared from zinc oxide and stearic acid according to a mass ratio of 3.5-4.8: 2.0 to 2.5.
8. The composite material for the wear-resistant and high-wet-skid-resistant sole according to claim 6, wherein: the main accelerator is prepared from DM and TS according to the mass ratio of 2.3-2.7: 2.5 to 3.2.
9. The method for producing a composite material for a wear-resistant, highly wet-slip resistant sole according to any one of claims 1 to 8, characterized in that: mixing the raw materials except the vulcanizing agent to obtain a master batch, and carrying out open mill on the master batch and the vulcanizing agent to obtain an open mill, and extruding, vulcanizing and molding the open mill.
10. The method for preparing the composite material for the wear-resistant and high-wet-skid-resistant sole, according to claim 9, which is characterized in that: the temperature is controlled to be not higher than 140 ℃ in the mixing process, and the mixing time is 120-150 s.
11. The method for preparing the composite material for the wear-resistant and high-wet-skid-resistant sole, according to claim 9, which is characterized in that: the extrusion temperature is controlled to be 120-140 ℃, the vulcanization temperature is 160 ℃ and the vulcanization time is 10-14 min in the extrusion vulcanization molding process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910861943.6A CN112480504B (en) | 2019-09-12 | 2019-09-12 | Wear-resistant high-wet-skid-resistance composite material for soles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910861943.6A CN112480504B (en) | 2019-09-12 | 2019-09-12 | Wear-resistant high-wet-skid-resistance composite material for soles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112480504A CN112480504A (en) | 2021-03-12 |
| CN112480504B true CN112480504B (en) | 2023-07-18 |
Family
ID=74920574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910861943.6A Active CN112480504B (en) | 2019-09-12 | 2019-09-12 | Wear-resistant high-wet-skid-resistance composite material for soles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112480504B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702737B (en) * | 2022-04-12 | 2023-10-31 | 达州市嘉源体育用品有限公司 | Wear-resistant shoe outsole and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945559B (en) * | 2014-03-26 | 2018-11-20 | 中国石油化工股份有限公司 | A kind of hydrogenated polystyrene-b- phenylethylene/butadiene/isoprene random copolymer and its preparation method and application |
| EP2952538A1 (en) * | 2014-06-03 | 2015-12-09 | LANXESS Deutschland GmbH | Rubber compositions free of diphenylguanidine comprising short-chained alkyl esters of glycerol |
| JP5944964B2 (en) * | 2014-08-25 | 2016-07-05 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| CN105820383B (en) * | 2016-05-24 | 2018-01-02 | 宁波市中迪鞋业有限公司 | A kind of composite-material abrasive sole |
| JP6897366B2 (en) * | 2017-06-29 | 2021-06-30 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
-
2019
- 2019-09-12 CN CN201910861943.6A patent/CN112480504B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112480504A (en) | 2021-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9279025B2 (en) | Neodymium-catalyzed polybutadienes | |
| US11505683B2 (en) | Resin modified oil extended rubber | |
| CN104910487A (en) | High-wearability sole material and preparation method thereof | |
| CN111718454B (en) | Partially hydrogenated styrene-b-conjugated diene/divinylbenzene random copolymer, preparation and application thereof | |
| KR20120129981A (en) | Bimodal neodymium-catalyzed polybutadiene | |
| CN110577680A (en) | A kind of light-weight non-slip rubber sole material and its manufacturing method | |
| CN108997701A (en) | A kind of solid tread mix, preparation and its application | |
| CN113563685B (en) | Formula sizing material of all-steel truck radial tire and preparation method thereof | |
| CN112480504B (en) | Wear-resistant high-wet-skid-resistance composite material for soles and preparation method thereof | |
| CN102234384B (en) | IPN crosslink-structure compound of tire crown rubber, mixing method and application thereof | |
| WO2020011009A1 (en) | Rubber composition, and tire using the same | |
| CN115232372B (en) | Sole composite material with wear resistance, wet skid resistance and high adhesive force performance and preparation method thereof | |
| CN103570992B (en) | A kind of body-building mountain-climbing sport shoe sole material and preparation method thereof | |
| CN111718555B (en) | Sealing strip material based on partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer and preparation thereof | |
| CN112210129B (en) | Anti-cracking anti-aging rubber for radial tire tread base and preparation method | |
| CN112210053B (en) | Polybutadiene-isoprene rubber containing micro-blocks and long-chain blocks simultaneously and preparation method thereof | |
| JPH0326732A (en) | Rubber composition | |
| CN116987236A (en) | Dendritic styrene-butadiene block copolymer and preparation method and application thereof | |
| CN113736149B (en) | All-steel radial tire sidewall rubber material for truck tire and preparation method thereof | |
| CN112480341B (en) | Branched polystyrene-b-conjugated diene diblock copolymer, and preparation method and application thereof | |
| CN112210128B (en) | Tire sidewall rubber material based on gradient block lithium BIR and preparation method thereof | |
| JPH0621189B2 (en) | Improved conjugated diene rubber composition for tires | |
| CN112210127B (en) | High-performance rubber for radial tire tread base and preparation method thereof | |
| CN111718453B (en) | Partially hydrogenated styrene-b-butadiene-divinylbenzene/isoprene random copolymer, and preparation and application thereof | |
| CN113736020B (en) | Semi-functionalized asymmetric long-chain branched styrene-butadiene-isoprene random copolymer, and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |