CN115232372B - Sole composite material with wear resistance, wet skid resistance and high adhesive force performance and preparation method thereof - Google Patents
Sole composite material with wear resistance, wet skid resistance and high adhesive force performance and preparation method thereof Download PDFInfo
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- CN115232372B CN115232372B CN202110446053.6A CN202110446053A CN115232372B CN 115232372 B CN115232372 B CN 115232372B CN 202110446053 A CN202110446053 A CN 202110446053A CN 115232372 B CN115232372 B CN 115232372B
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- sole
- isoprene
- parts
- wet skid
- acrylonitrile
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- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- CFJYNSNXFXLKNS-UHFFFAOYSA-N trans-p-menthane Natural products CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
Abstract
The invention discloses a sole composite material with wear resistance, wet skid resistance and high adhesive force performance and a preparation method thereof. The sole composite material comprises the following raw materials: the polar isoprene-acrylonitrile-vinyl pyridine random copolymer, the sole general rubber and auxiliary materials have good physical and mechanical properties and slip resistance, have excellent adhesive property with the existing upper fabric, integrate the slip resistance, stripping resistance, wear resistance and other properties, and are suitable for manufacturing high-end sport brand shoes.
Description
Technical Field
The invention relates to a sole material, in particular to a polar isoprene-acrylonitrile-vinyl pyridine random copolymer modified sole material and a preparation method thereof, and belongs to the technical field of sole material preparation.
Background
How to improve the adhesion of shoe soles such as general rubber like Butadiene Rubber (BR), natural Rubber (NR), styrene-butadiene rubber (SBR) and vamp material nylon (PA), polyester (PET) fabric, leather and the like is not firm, the peeling strength of the shoe soles and vamp material is only 50-90N/cm, and the peeling strength is difficult to be improved again. Polyurethane (TPU) has good adhesion to PA, but is limited in hardness and cannot be softened; the general rubber can be filled with rubber oil to soften the rubber, but the polarity of the cross-linked macromolecules is low due to the non-polar groups in the rubber molecules, so that the adhesive property of the shoe outsole and the vamp material is poor. To improve the problem of poor adhesion of materials, a better path is taken from the aspect of materials.
The existing Nitrile Butadiene Rubber (NBR) is prepared by initiating and copolymerizing acrylonitrile and butadiene in emulsion at low temperature under the action of additives such as peroxide and the like, for example, the mass fraction of the acrylonitrile combined in the molecules of the commercially available NBR is 20-42%, the polarity of the polymer is higher, and the compatibility with general rubber is poor. For example, in the "study of acrylonitrile-butadiene-isoprene ternary emulsion polymerization", ancient text, university of great company, 6 th 2011, it is disclosed that acrylonitrile-butadiene-isoprene ternary emulsion polymerization is synthesized under the actions of sodium dodecyl benzene sulfonate, potassium oleate, ferrous sulfate, EDTA disodium salt, cumene peroxide and the like at a low temperature, and the conversion rate of monomers is 78%. Both Chinese patent (CN 103665265A) and (CN 104628955A) relate to the emulsion polymerization technology of NBR, and Chinese patent (CN 110066481A) relates to sealing products of NBR oil resistance. Chinese patent (CN 106366246B) discloses a butadiene-styrene-pyridine latex and a preparation method thereof, and specifically discloses a butadiene-styrene-pyridine latex which is prepared by taking mixed monomers, an emulsifying agent, an initiator, inorganic salt, a molecular weight regulator, desalted water, a terminator and a pH regulator as raw materials, and is prepared through five working procedures of water phase preparation, initiator solution preparation, feeding and polymerization initiation, continuous feeding and ending reaction and post-treatment. An initiation system composed of persulfate-alcohol amine reducing agents is adopted, and a quaternary composite emulsification system composed of anionic emulsifier sodium alkyl sulfonate, anionic carboxylate emulsifier fatty acid potassium, disproportionated abietic acid potassium and nonionic emulsifier alkylphenol polyoxyethylene is synthesized, so that the chemical stability and mechanical stability of the butadiene-styrene-pyridine latex are improved; and the preparation is performed by a semi-continuous process under the medium temperature condition, so that the improvement of the binding force of the styrene-butadiene-pyridine latex is facilitated. None of the above techniques describe the use of a polar rubber as an athletic sole.
The prior sports shoes such as marathon running shoes, ball shoes and the like require that the sole material has high wear resistance, wet skid resistance and tearing resistance, and the sole material has excellent affinity and cohesiveness with shoe upper materials such as leather with strong polarity, polyester, nylon, cotton fiber fabrics and the like, polyurethane adhesives are generally used for the sole and the shoe upper materials, and the polyurethane adhesives are adhered with rubber with lower polarity and the shoe upper materials to prepare the shoe products which belong to first generation or second generation products, and are mainly characterized in that the peel strength of the sole and the shoe upper materials is low, and the root of the peel strength is that the polarity of the sole material is low. However, the formula of the sports shoe outsole material produced by Kunshan sports goods Co., ltd.m. in China is composed of 10-30% by mass of brominated butyl rubber (BIIR), BR, NR, solution polymerized styrene-butadiene rubber (SSBR) and the like, and the shoe outsole is prepared by a vulcanization method, but the existing commercially available NBR with high bound acrylonitrile content is not selected as a modified material, and the existing NBR has poor compatibility with BR, NR and styrene-butadiene rubber, so that the adhesive strength of the vulcanized composite material, a polyurethane adhesive and an upper fabric is enhanced by adding a certain amount of the strong-polarity BIIR into the shoe outsole material, and the peeling resistance and the tearing strength are improved. In the "application of bromobutyl in shoe material", china International society of rubber oil industry-market analysis and application trend Forum of rubber oil downstream, 2019 (tenth world)), a composite material composed of BIIR224455 parts, SSBR2003 25 parts, NR 20 parts and related fillers, auxiliaries and the like is introduced, and the composite material is subjected to mixing and vulcanization to prepare an application formula in the sole of the marathon running shoe, and the prepared running shoe can be run for more than 1000km by athletes, and shows good wear resistance and wet skid and grip performance. The introduction of BIIR into the traditional rubber sole formulation was studied in the "application study of BIIR in sole anti-slip materials", liu Yang et al, chinese leather, 2019, 10. The results show that the BIIR promotes significant anti-slip of sole materials, wherein the dry friction coefficient is 0.98, the wet friction coefficient is 0.78, and the sole comprehensive performance is optimal when the BIIR is 20 parts. The behavior of the polymer is beneficial to improving the compatibility of the polymer and unsaturated rubber, improving the self-adhesion, mutual adhesion and co-crosslinking capacity of the polymer, and is also beneficial to the result that BIIR molecules contain a certain amount of side branches and vulcanized network molecules contain polarities. Chinese patent (application No. 20161045111. X) discloses a sole anti-skid rubber composite material and a preparation method thereof, wherein the sole material consists of 90-100 parts of NR, 40-50 parts of carbon black, organic accelerator, auxiliary accelerator, sulfur and the like, and has the characteristics of good wear resistance, walking stability and comfort, and the disadvantage of unsatisfactory anti-skid effect. Chinese patent (application number 201710008926.9) discloses an anti-skid rubber sole and a preparation method thereof, wherein the sole comprises the following raw materials: NBR/PVC emulsion co-precipitation alloy, low-melting polyamide, NR, SSBR, BIIR, white carbon black and small vulcanization auxiliary agent, wherein the vulcanization temperature is 170 ℃, and the vulcanization time is 210-250 s. Chinese patent (CN 107629341 a) discloses a low elastic anti-slip rubber and its preparation method, the composition of 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 adhesive consists of 10-15 parts by weight of NR, 45-65 parts by weight of BIIR, 5-15 parts by weight of SBR and 15-25 parts by weight of BR, and has the characteristics of ultralow elasticity and excellent anti-slip capability. That is, the above documents all describe the production of athletic soles from BIIR modified general purpose nonpolar rubbers.
The relationship between the structure and the bonding strength of the TPU solution synthesized in the organic solvent was studied in the "Structure and bonding Property of TPU solution", the sixth academy of sciences of Beijing bonding, 1997-10-06). The process route and formulation of the solution process to synthesize the TPU solution are discussed. By changing the types and amounts of polyester polyol, glycol, isocyanate and solvent in the formulation, various TPU solutions were synthesized. Physical properties of various TPU films and bonding properties (mainly peeling strength) of various materials are tested, and the conclusion that the bonding properties are influenced by the factors such as isocyanate, polyester polyol, dihydric alcohol and the like is obtained.
The conventional adhesive materials for shoe soles and shoe linings generally use polar adhesives, such as adhesives with polyurethane (TPU) as a main body (such as commercially available Nanji resin), TPU is a branched linear polymer, and the molten state or the solution state of the TPU has adhesiveness to various materials, and the reason is that the TPU molecules contain urethane bonds and-NCO groups to form hydrogen bonds with adhered objects, so that the intermolecular acting force is increased and the adhesive strength is improved. In addition, the anti-slip coefficient of the soles made of general rubber such as the prior styrene-butadiene elastomer (SBS or TPE), styrene-butadiene elastomer hydride (SEBS), SBR, SSBR, NR, BR and the like is 0.5-0.7, which can not meet the anti-slip requirement of the soles of sports shoes.
In summary, the prior art does not see that NBR is used in the sole formulation of the sports shoes, and the rubber is a composite material composed of NR, SBR, BR and modified polar BIIR, but the anti-skid effect and the anti-stripping performance can not meet the requirements of the sole material of the high-end sports shoes, so that the development of a sole rubber material which has excellent adhesive properties with polyurethane adhesive and high polar vamp materials or fabrics, and also has excellent anti-skid, anti-stripping and wear-resisting integrated functions is of great significance.
Disclosure of Invention
Aiming at the defects that the adhesive for soles in the prior art is polyurethane with strong polarity, the universal rubber without polarity is used for soles, and fabrics such as polyester, nylon, cotton and hemp and natural leather belong to materials with strong polarity, and the interface between the sole, the adhesive and the vamp fabric (upper) has uncoordinated polarity, and the prior materials have poor anti-slip performance, so that the improvement of the anti-slip performance of the soles is particularly necessary for the high-speed movement and rapid stopping.
The invention aims to provide a sole composite material with wear resistance, wet skid resistance and high adhesive force performance, which modifies general rubber by adopting polar isoprene-acrylonitrile-vinyl pyridine random copolymer (E-IAPR), ensures that the sole material has better physical and mechanical properties, ageing resistance, low deformation, wear resistance and the like, and mainly improves the peel strength of the existing sole and vamp material from 50-90N/cm to 130-140N/cm, and simultaneously improves the sole skid resistance once more, thereby being suitable for preparing middle-high-end sports shoe soles.
The invention provides a preparation method of a sole composite material with wear resistance, wet skid resistance and high adhesive force performance, which has the characteristics of simple operation and low cost and is beneficial to industrial production.
The endpoints of the ranges and any values disclosed in this summary are not limited to the precise range or value, and such range or value should be understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in this summary.
In order to achieve the technical aim, the invention provides a sole composite material with wear resistance, wet skid resistance and high adhesive force performance, which comprises the following raw materials in parts by weight: polar isoprene-acrylonitrile-vinyl pyridine random copolymer, sole general rubber and auxiliary materials.
As a preferred embodiment, the polar isoprene-acrylonitrile-vinylpyridine random copolymer is a polar isoprene-acrylonitrile-vinylpyridine random copolymer mixture comprising a straight chain, a single branching and a plurality of branches, the average branching degree is 3 to 4, and the molecular mass distribution index is 3.0 to 4.0.
As a preferred embodiment, the polar isoprene-acrylonitrile-vinylpyridine random copolymer has a mass ratio of the trans 1, 4-addition structural unit of the isoprene unit of 30 to 40%, and a mass ratio of the 1, 2-addition structural unit and the 3, 4-addition structural unit of 15 to 30%.
As a preferred embodiment, the polar isoprene-acrylonitrile-vinylpyridine random copolymer has a mass ratio of isoprene units to acrylonitrile units of (90-95)/(10-5), and a mass ratio of isoprene units to vinylpyridine units of (98-99.5)/(2.0-0.5).
As a preferred embodiment, the mass ratio of the polar isoprene-acrylonitrile-vinylpyridine random copolymer to the sole general rubber is (40-50)/(60-50).
The polar isoprene-acrylonitrile-vinyl pyridine random copolymer (E-IAPR) of the invention has a small amount of nitrogen-containing polar groups distributed uniformly in the molecular chain, the general rubber mainly belongs to nonpolar rubber, the vulcanized rubber formed by blending and modifying the general rubber by the E-IAPR is a polar vulcanized crosslinked network body, the vulcanized rubber is easy to be bonded with fabrics such as polyester, nylon, cotton and hemp and leather, the shearing resistance and tearing resistance of shoe soles and vamp materials are improved, and meanwhile, the blended rubber of the E-IAPR and the general rubber of the shoe soles also has good wear resistance.
The E-IAPR (E is marked as emulsion polymerization, R is marked as rubber) is prepared by random and alternating copolymerization of isoprene monomer, vinyl pyridine monomer and acrylonitrile monomer by free radical initiation in an emulsion system consisting of water and an emulsifier at low temperature.
The E-IAPR of the present invention is a ternary random rubber having a straight chain, single branching and a mixture of multiple branched molecular chains similar to the "molecular chain segment" composition of (formula 1), preferably having an average degree of branching of 3.0 to 4.0.
-[I x -A y -P z -I m -P n -A o -I s -A t ]-
1 (1)
Wherein "I" in formula 1 is an isoprene polymerization unit, "A" is an acrylonitrile polymerization unit, and "P" is a vinylpyridine polymerization unit; x, y, z, m, n, O, s and t are polymerization degrees, and are positive integers greater than or equal to O.
Wherein, P in E-IAPR can be at least one of 2-vinyl pyridine, 4-vinyl pyridine and 2-methyl-5-ethyl pyridine; the purpose of introducing a small amount of P and A in E-IAPR molecules is to improve the polarity of the polymer, increase the adhesion performance of the polymer to fiber fabrics such as polyester, nylon, cotton and hemp and leather, and improve the shearing resistance and the tearing resistance of soles and vamp materials.
In the E-IAPR, if the mass fraction of the combined A is too high and the mass fraction of the combined I is low, the polarity of the E-IAPR is increased, and the compatibility with other non-polar general rubber is poor; the adhesive property of the copolymer can be further improved by introducing a small amount of P molecular units into the E-IAPR molecules, and in addition, the E-IAPR molecules contain higher isoprene units, so that the compatibility of the E-IAPR and the conjugated diene rubber is improved.
In the E-IAPR emulsion polymerization according to the present invention, isoprene thereof generates cis-1, 4-addition structural units, trans-1, 4-addition structural units, 1, 2-addition structural units, 3, 4-addition structural units, and the like. Wherein the polymer of isoprene containing a part of trans 1, 4-addition structural units is advantageously compatible with BR, SBR and NR, preferably the E-IAPR molecule has a trans 1, 4-addition unit content of 30 to 40%; the copolymer of the isoprene unit with the side-branched 1, 2-addition structure and the 3, 4-addition structure and the side-branched ' -CN ' and the pyridine ' group is beneficial to improving the anti-slip performance of the composite vulcanized rubber, and the content of the 1, 2-addition structure and the 3, 4-addition structure in the preferred E-IAPR molecule is 15-30%, so that the better anti-slip performance can be obtained.
The E-IAPR has Mooney viscosity (ML) =30-60 (raw rubber), the preferable E-IAPR molecular mass distribution index is 3.0-4.0 (raw rubber), and the conversion rate of the monomer is 95-98%.
As a preferable scheme, the auxiliary materials comprise white carbon black, light calcium powder, softening oil, a coupling agent, zinc oxide, stearic acid, microcrystalline wax, a colorant, an anti-aging agent, an accelerator and sulfur.
As a preferable scheme, the composition comprises the following components in parts by mass: 100 parts of polar isoprene-acrylonitrile-vinyl pyridine random copolymer and general rubber for soles, 20-30 parts of white carbon black, 20-30 parts of light calcium powder, 15-20 parts of softening oil, 4-6 parts of coupling agent, 3-5 parts of zinc oxide, 1-2 parts of stearic acid, 0.5-1.0 part of microcrystalline wax, 5-8 parts of colorant, 0.5-1.0 part of anti-aging agent, 1.0-1.5 parts of accelerator and 1.5-1.8 parts of sulfur.
As a more preferable embodiment, at least one of the softening oil TDAE, NAP-10, KN-4010, no. 26 white oil and No. 32 white oil. The preferred softening oil is at least one of aromatic hydrocarbon-containing TDAE, NAP-10, KN-4010, no. 26 white oil and No. 32 white oil known to those skilled in the industry, and can regulate the flexibility of the sole and improve the affinity and comfort between the sole and human body.
As a more preferred embodiment, the coupling agent is at least one of KH-550, silicon 75 and silicon 69. The coupling agent is preferably at least one of organosilane compounds such as commercially available coupling agent KH-550 for glass fibers, coupling agent silicon 75 or silicon 69 for white carbon black for high-performance tire tread rubber "silicon formula", and the like; the coupling agent in the composite material has the function of coupling the hydroxyl groups on the surface of the white carbon black with strong polarity and the light calcium carbonate on one hand and the surface of the rubber on the other hand, and simultaneously, the rapid compatibility of the inorganic filling material and the rubber (also called rapid powder feeding) is also increased.
The white carbon black and the light calcium powder in the formula of the sole composite material are mainly used as reinforcing agents (also called inorganic filling materials), and can reduce the cost of the composite sole material, and the white carbon black is preferably selected to have the specific surface area of 280-350 m 2 Per g, such as commercially available silica for high performance tires "tread band" such as NodeB 175, etc. The calcium carbonate powder is preferably precipitated light calcium powder with the mesh number of not less than 1000 mesh, and the light calcium powder is cheaper than white carbon black. In addition, polar E-IAPR has better affinity with polar inorganic fillers.
As a more preferred embodiment, the accelerator is at least one of accelerator TBBS, accelerator CZ and accelerator DM, and/or at least one of accelerator TMTM and accelerator TMTD. Preferred accelerators include at least one of the general benzothiazole sulfenamide accelerators TBBS, CZ, DM, etc., and/or at least one of the thiuram quick vulcanization accelerators TMTM, TMTD, etc. The preferred benzothiazole sulfenamide accelerator and the thiuram accelerator are combined, and the interaction of the two accelerators has a synergistic effect, so that the synergistic effect accelerates the vulcanization rate of the compound rubber compound, shortens the vulcanization time and improves the preparation efficiency of the product. Further preferably, the weight ratio of the benzothiazole sulfenamide accelerator to the thiuram accelerator is 0.7-1.0: 0.5 to 0.8. The composite type efficient and rapid vulcanization system is selected, so that the preparation time is shortened, and the preparation efficiency of the sole is improved.
As a more preferable scheme, the colorant is at least one of titanium white, a brightening agent, carbon black, ultramarine, malachite blue and iron oxide red.
As a more preferable embodiment, the sole general purpose rubber is at least one of SSBR, NR, SBR and BR. As SBR, commercially available emulsion ESBR-1500 or anionic polymerized SSBR can be used.
The invention also provides a preparation method of the sole composite material with wear resistance, wet skid resistance and high adhesive force performance, which comprises the following steps:
1) Mixing polar isoprene-acrylonitrile-vinyl pyridine random copolymer, sole general rubber and auxiliary materials except sulfur and sulfosalt in an internal mixer to obtain master batch;
2) Placing the masterbatch on an open mill, adding sulfur, and tabletting to obtain tabletting adhesive;
3) And carrying out compression molding vulcanization molding on the tabletting glue.
As a preferable scheme, the temperature of the mixing is not higher than 140 ℃ and the time is 120-150 s.
As a preferable scheme, the vulcanizing temperature is 155-165 ℃ and the vulcanizing time is 3-4 min. The preparation method of the E-IAPR provided by the invention comprises the following steps: adding quantitative deionized water for polymerization, an emulsifying agent, a dispersing agent, an electrolyte, a molecular chain transfer agent, a deoxidizing agent, an oxidizing agent, a reducing agent and an activating agent into a polymerization kettle respectively, stirring, circulating chilled water into a cooling pipe of the polymerization kettle, cooling materials in the polymerization kettle to 4-8 ℃, adding a set amount of vinyl pyridine monomers, acrylonitrile monomers and isoprene monomers at the moment, maintaining the polymerization temperature at 5-8 ℃ for reacting for 5-6 hours, discharging the polymerized latex when the monomer conversion rate reaches over 95%, adding a small amount of antioxidant into the discharged latex, stirring uniformly, pouring the prepared latex into a condensing aqueous solution composed of dilute sulfuric acid/a condensing agent, condensing to obtain milky raw rubber, and finally extruding and dehydrating the milky raw rubber at 110 ℃ to obtain pale yellow E-IAPR raw rubber with the mass fraction of ash not higher than 0.5%.
Deionized water, an emulsifying agent, a dispersing agent, an electrolyte, a molecular chain transfer agent, a deoxidizing agent, an oxidizing agent, a reducing agent and an activating agent adopted in emulsion polymerization are all commonly used raw materials for preparing nitrile rubber and emulsion polymerized styrene butadiene rubber (E-SBR) known to a person skilled in the art. Specifically, deionized water is preferably used in an amount of 1700 to 1800g/kg of monomer. The emulsifier is hydrogenated rosin potassium and potassium oleate, and the dosage of the emulsifier is 15-25 g/kg of monomer; the mass ratio of the hydrogenated rosin potassium to the potassium oleate is 9-15:6-10. The dispersant is methylene dinaphthyl sodium sulfonate (NF) with the dosage of 1.2-1.6 g/kg monomer. The electrolyte is preferably at least one of sodium phosphate, potassium chloride and sodium carbonate, and the amount thereof is 3.5 to 7.0g/kg of monomer. The molecular chain transfer agent is tert-dodecyl mercaptan, and the dosage of the molecular chain transfer agent is 5-8 g/kg of monomer; the deoxidizer is sodium dithionite, and the dosage of the deoxidizer is 0.4-0.5 g/kg of monomer. The oxidant is at least one of p-menthane peroxide (PMHP), pinane Hydroperoxide (PHP) and the like, and the dosage of the oxidant is 0.8-1.2 g/kg of monomer. The reducing agent is white suspended block, and the dosage of the reducing agent is 0.8-1.0 g/kg of monomer. The activator is EDTA-sodium iron, and the preferable dosage is 0.2-0.3 g/kg monomer. The condensation aqueous solution consists of dicyandiamide formaldehyde Condensate (CA) and sulfuric acid, wherein the sulfuric acid controls the pH value of the solution to be 3-4, and the mass fraction of the CA in the solution is 0.20-0.25%.
The preparation method of the sole material comprises the steps of material mixing, thin-pass tabletting of masterbatch, vulcanization molding of tabletting adhesive 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.
Vulcanization molding of the tabletting glue (shoe outsole molding): adding the tabletting glue into a die according to the weight of the shoe outsole as a metering standard, and then performing compression molding vulcanization molding; the preferred vulcanization temperature is 160 ℃, the vulcanization time is 3-4 min, and the shoe outsole can be obtained after the vulcanization time is up.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
compared with the existing NBR which is commercially available and cannot be used for modifying general rubber as sole material and soles made of general rubber such as SBR, SSBR, NR and BR, the anti-slip coefficient of the sole is only 0.5-0.7, and the sole has the advantages of low adhesive force between the sole material and vamp material, easy degumming and the like.
The E-IAPR rubber is used as modified general rubber and is applied to main rubber materials of shoe soles, and the composite material has higher slip resistance due to the fact that polyisoprene units in vulcanized rubber contain higher side branched chains under the condition that the basic physical properties of the conventional general rubber are not affected; meanwhile, the proper nitrogen atom contained in the vulcanized rubber network macromolecule not only increases the polarity of the composite material, but also is a catalyst for crosslinking isocyanate-NCO active groups in polyurethane adhesive molecules, so that the adhesive cohesive force of the adhesive, the shoe outsole and the vamp material is activated; in addition, the modified polar outsole-polyurethane adhesive-vamp material for shoes has excellent compatibility and affinity. Finally, the composite sizing material of the outsole, polar chemical fiber, cotton fabric and natural and artificial leather have excellent adhesive force, the peel strength of the existing sole material and vamp material is improved from 50-90N/cm to 130-140N/cm, and the requirements of the middle and high-end sports sole material can be completely met, namely, the invention surprisingly finds that the composite material formed by matching E-IAPR with general rubber and vulcanizing has the characteristic of 'integrated material', and integrates the physical and mechanical properties, high anti-slip property, high adhesion and the like.
The formula of the shoe sole material containing the E-IAPR is particularly suitable for soles of sport brands, such as marathon running shoes, blueballs, volleyballs, table tennis shoes and the like; can also be used as middle and high-end leisure and military soles.
The sole material provided by the invention has a simple preparation method, 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; determining the Mooney viscosity ML (100 ℃/1+4) of the polymer gel sample by using a Mooney viscosimeter; 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; right angle tear Strength (N/mm) was measured according to the DW-22GT-TCS2000 (500+ -mm/min); the peel strength (N/mm) was measured according to GB/T3903.3-2011 (100.+ -. Mm/min); DIN abrasion (mm) 3 ) Measured according to a DW-15GT-7012-D rotary (40+/-1) r/min (10+/-0.2) N method; the slip resistance coefficient is measured according to a DW-09BL-312 dry method and a wet method; measuring 0 ℃/tan by dynamic viscoelastometer&The values characterize the wet skid resistance of the vulcanizate.
E-IAPR-1 synthesis:
1.70L of deionized water is added into a 5L polymerization kettle, 15.0 weight percent potassium oleate solution 55mL,25.0 weight percent disproportionated rosin potassium solution 50mL,1.8 weight percent ferric EDTA sodium salt solution 12.5mL,10.2 weight percent methylene dinaphthyl sodium sulfonate aqueous solution 12mL,5 weight percent sodium carbonate and 10.0 weight percent potassium chloride aqueous solution are respectively added into 22mL and 45mL,5 weight percent sodium dithionite aqueous solution 8mL and 6.5 weight percent sodium metabisulfite aqueous solution 12mL are respectively added into a polymerization kettle, the auxiliary agent is pressed into the polymerization kettle by nitrogen, stirring is started, and circulating cooling water at 5 ℃ is introduced, dissolving 7.0mL of dodecyl mercaptan dissolved in 50g of acrylonitrile, 12g of 2-methyl-5-ethylpyridine and 850g of isoprene, uniformly mixing, pressing the mixed material into a polymerization kettle at one time, adding 1.10mL of PMHP into a sight glass of the polymerization kettle, pressing into the polymerization kettle, reacting for 5 hours, discharging, respectively adding 3.0g of antioxidant 1520 into latex, uniformly mixing, adding the latex into a solution which consists of 50g of dicyandiamide formaldehyde condensate, 30g of concentrated sulfuric acid and 20 liters of water in batches, condensing, and finally placing the condensed milky white aqueous gel on a two-roll mill at 110 ℃ for extrusion dehydration until the water content is 0.42%, thus obtaining the pale yellow E-IAPR raw rubber (marked as E-IAPR-1).
As a result, it was found that the yield of raw rubber was 95.8%, the Mooney viscosity of raw rubber was 48.8, the mass contents of the molecular mass distribution index 3.2,3,4-addition and trans-1, 4-addition units were 16.7% and 35.3%, respectively, and the glass transition temperature of raw rubber was-87.6 ℃.
E-IAPR-2 synthesis:
the relevant process conditions and auxiliary amounts in the synthesis of E-IAPR-1 were not changed significantly, except that 6.5mL of dodecylmercaptan was dissolved in a mixed monomer consisting of 60g of acrylonitrile, 15g of 2-ethylpyridine and 850g of isoprene, and the amount of initiator PMHP was 1.15mL.
As a result, it was found that the yield of raw rubber was 97.3%, the Mooney viscosity of raw rubber was 54.6, the mass contents of the molecular mass distribution index 3.8,3,4-addition unit and the trans-1, 4-addition unit were 18.9% and 34.8%, respectively, the glass transition temperature of raw rubber was-82.3℃and the prepared raw rubber was designated as E-IAPR-2.
E-IAPR-3 synthesis:
the relevant process conditions and the dosage of auxiliary agents in the synthesis of E-IAPR-1 are not changed greatly, but only 5.8mL of dodecyl mercaptan is dissolved in a mixed monomer consisting of 40g of acrylonitrile, 6g of 4-ethylpyridine and 850g of isoprene, and the initiator is changed into 1.25mL of PHP.
As a result, it was found that the yield of raw rubber was 98.2%, the Mooney viscosity of raw rubber was 58.4, the mass contents of the molecular mass distribution index 3.6,3,4-addition unit and the trans-1, 4-addition unit were 28.3% and 32.4% respectively, the glass transition temperature of raw rubber was-79.6℃and the prepared raw rubber was designated as E-IAPR-3.
Application examples:
the E-IAPR-1, E-IAPR-2, E-IAPR-3 raw rubber and the comparison brominated butyl rubber BIIR2224 and the half-functionalized solution polymerized styrene-butadiene rubber HPR-850 prepared in the above way are respectively matched with general rubber, the sole is prepared according to the method of the invention, the corresponding formulas are shown in table 1, and the corresponding physical properties are shown in tables 2 and 3.
Table 1 example formulation (parts by weight)
Note that: HPR-850 is a solution polymerized styrene-butadiene rubber blocked with a functional group composed of nitrogen atoms, manufactured by Asahi chemical Co., ltd.
TABLE 2 physical Properties of the vulcanizates of examples 1-5 and comparative examples 1-2
The sole vulcanized rubber prepared by the invention has better anti-slip and anti-wear properties, and the comprehensive properties of the sole vulcanized rubber are superior to those of brominated butyl rubber and semi-functionalized solution polymerized styrene-butadiene rubber.
TABLE 3 adhesion Properties of the vulcanizates of examples 1-5 and comparative examples 1-2 to the fabrics (materials) to be bonded
Note that: the adhesive is polyurethane resin (Nanji resin adhesive).
The sole vulcanized rubber prepared by the invention has excellent bonding performance with shoe upper surface materials, and is superior to the existing brominated butyl and functionalized SSBR modified rubber.
Claims (12)
1. A sole composite material with wear resistance, wet skid resistance and high adhesive force performance is characterized in that: comprises the following raw materials: polar isoprene-acrylonitrile-vinyl pyridine random copolymer, sole general rubber and auxiliary materials; the sole general rubber is at least one of SSBR, NR, SBR and BR;
the mass ratio of the trans-1, 4-addition structural units of the isoprene units in the polar isoprene-acrylonitrile-vinyl pyridine random copolymer accounts for 30-40%, and the mass ratio of the 1, 2-addition structural units and the 3, 4-addition structural units is 15-30%;
the mass ratio of the isoprene unit to the acrylonitrile unit in the polar isoprene-acrylonitrile-vinyl pyridine random copolymer is (90-95)/(10-5), and the mass ratio of the isoprene unit to the vinyl pyridine unit is (98-99.5)/(2.0-0.5).
2. A sole composite having wear, wet skid and high adhesion properties as claimed in claim 1, wherein: the polar isoprene-acrylonitrile-vinyl pyridine random copolymer is a polar isoprene-acrylonitrile-vinyl pyridine random copolymer mixture containing straight chains, single branches and multiple branches, the average branching degree is 3-4, and the molecular mass distribution index is 3.0-4.0.
3. A sole composite having wear, wet skid and high adhesion properties as claimed in claim 1, wherein: the mass ratio of the polar isoprene-acrylonitrile-vinyl pyridine random copolymer to the sole general rubber is (40-50)/(60-50).
4. A sole composite having wear, wet skid and high adhesion properties as claimed in claim 1, wherein: the auxiliary materials comprise white carbon black, light calcium powder, softening oil, a coupling agent, zinc oxide, stearic acid, microcrystalline wax, a colorant, an anti-aging agent, an accelerator and sulfur.
5. A sole composite material with wear resistance, wet skid resistance and high adhesion properties according to any one of claims 1 to 4, characterized in that: comprises the following components in parts by mass: 100 parts of polar isoprene-acrylonitrile-vinyl pyridine random copolymer and general rubber for soles, 20-30 parts of white carbon black, 20-30 parts of light calcium powder, 15-20 parts of softening oil, 4-6 parts of coupling agent, 3-5 parts of zinc oxide, 1-2 parts of stearic acid, 0.5-1.0 part of microcrystalline wax, 5-8 parts of colorant, 0.5-1.0 part of anti-aging agent, 1.0-1.5 parts of accelerator and 1.5-1.8 parts of sulfur.
6. A sole composite having wear, wet skid and high adhesion properties as claimed in claim 5, wherein: at least one of the softening oil TDAE, NAP-10, KN-4010, no. 26 white oil and No. 32 white oil.
7. A sole composite having wear, wet skid and high adhesion properties as claimed in claim 5, wherein: the coupling agent is at least one of KH-550, silicon 75 and silicon 69.
8. A sole composite having wear, wet skid and high adhesion properties as claimed in claim 5, wherein: the accelerator is at least one of accelerator TBBS, accelerator CZ and accelerator DM, and/or at least one of accelerator TMTM and accelerator TMTD.
9. A sole composite having wear, wet skid and high adhesion properties as claimed in claim 5, wherein: the colorant is at least one of titanium white, a brightening agent, carbon black, ultramarine blue, malachite blue and iron oxide red.
10. The method for preparing the sole composite material with wear resistance, wet skid resistance and high adhesive force performance as claimed in claims 1 to 9, which is characterized in that: the method comprises the following steps:
1) Mixing polar isoprene-acrylonitrile-vinyl pyridine random copolymer, sole general rubber and auxiliary materials except sulfur and sulfosalt in an internal mixer to obtain master batch;
2) Placing the masterbatch on an open mill, adding sulfur, and tabletting to obtain tabletting adhesive;
3) And carrying out compression molding vulcanization molding on the tabletting glue.
11. The method for preparing the sole composite material with wear resistance, wet skid resistance and high adhesion performance according to claim 10, wherein the method comprises the following steps: the temperature of the mixing is not higher than 140 ℃ and the time is 120-150 s.
12. The method for preparing the sole composite material with wear resistance, wet skid resistance and high adhesion performance according to claim 10, wherein the method comprises the following steps: the temperature of the vulcanization is 155-165 ℃ and the time is 3-4 min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3993847A (en) * | 1974-09-14 | 1976-11-23 | Honny Chemicals Company, Ltd. | Silica in adhesive |
| CN1050725A (en) * | 1989-06-12 | 1991-04-17 | 斯塔米卡本公司 | Improved adhesive latex |
| US5162425A (en) * | 1985-06-24 | 1992-11-10 | The Goodyear Tire & Rubber Company | Fast curing rubber blend |
| JP2004204147A (en) * | 2002-12-26 | 2004-07-22 | Nippon A & L Kk | Copolymer latex for adhesive between rubber and fiber |
| JP2005162777A (en) * | 2003-11-28 | 2005-06-23 | Nippon Zeon Co Ltd | Rubber composition for shoe sole |
| CN101638453A (en) * | 2008-07-31 | 2010-02-03 | 于景东 | Modified pyridine styrene butadiene rubber latex and preparation method and application thereof |
-
2021
- 2021-04-25 CN CN202110446053.6A patent/CN115232372B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3993847A (en) * | 1974-09-14 | 1976-11-23 | Honny Chemicals Company, Ltd. | Silica in adhesive |
| US5162425A (en) * | 1985-06-24 | 1992-11-10 | The Goodyear Tire & Rubber Company | Fast curing rubber blend |
| CN1050725A (en) * | 1989-06-12 | 1991-04-17 | 斯塔米卡本公司 | Improved adhesive latex |
| JP2004204147A (en) * | 2002-12-26 | 2004-07-22 | Nippon A & L Kk | Copolymer latex for adhesive between rubber and fiber |
| JP2005162777A (en) * | 2003-11-28 | 2005-06-23 | Nippon Zeon Co Ltd | Rubber composition for shoe sole |
| CN101638453A (en) * | 2008-07-31 | 2010-02-03 | 于景东 | Modified pyridine styrene butadiene rubber latex and preparation method and application thereof |
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