CN110845785A - Light sole material and preparation method thereof - Google Patents
Light sole material and preparation method thereof Download PDFInfo
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- CN110845785A CN110845785A CN201911150147.8A CN201911150147A CN110845785A CN 110845785 A CN110845785 A CN 110845785A CN 201911150147 A CN201911150147 A CN 201911150147A CN 110845785 A CN110845785 A CN 110845785A
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- sole material
- accelerator
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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 relates to the field of rubber, and particularly discloses a light sole material and a preparation method thereof. The preparation raw materials at least comprise the following components in parts by weight: 5-20 parts of natural rubber, 5-15 parts of styrene butadiene rubber, 20-40 parts of ethylene-vinyl acetate copolymer, 2-10 parts of filler, 2-10 parts of plasticizer, 0.1-0.5 part of polysulfide rubber, 0.5-3 parts of activator, 0.1-0.6 part of antifogging agent, 0.1-1 part of accelerator, 0.3-3 parts of antioxidant, 0.1-1 part of tackifying resin, 0.1-1 part of silane coupling agent and 0.5-2 parts of neutralizer. The light sole material prepared by the invention has the characteristics of light weight, long service life, high elasticity and the like, and the sole made of the light rubber material provided by the invention has very long service life and extremely high comfort and commercial value.
Description
Technical Field
The invention relates to the field of rubber, in particular to a light sole material and a preparation method thereof.
Background
With the improvement of living standard, the requirements of people on shoes are continuously improved, and the shoes are changed from the functions of pure cold protection, protection and the like to fashionable, portable, comfortable and the like. The continuous emergence of novel functional materials for shoes provides a plurality of useful materials for the traditional shoe industry, not only initiates a new fashion trend, but also provides guarantee for the development of the performances of the functionality, comfort and the like of the shoes. The rubber has excellent wear resistance, corrosion resistance, aging resistance and good shock absorption performance, the rubber sole is light and comfortable to wear, the rubber sole can be developed quickly in the sole material, and the rubber sole has wide market prospect.
The rubber product is widely applied to the production and manufacture of soles due to good elasticity, but the traditional vulcanized rubber soles generally have the defect of large specific gravity, if the specific gravity of the soles is high, the sole can bear heavy load when being worn on feet, fatigue is easy to generate, and the light weight is an important direction for the development of the soles at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides a light sole material, which is prepared from the following raw materials in parts by weight: 5-20 parts of natural rubber, 5-15 parts of styrene butadiene rubber, 20-40 parts of ethylene-vinyl acetate copolymer, 2-10 parts of filler, 2-10 parts of plasticizer, 0.1-0.5 part of polysulfide rubber, 0.5-3 parts of activator, 0.1-0.6 part of antifogging agent, 0.1-1 part of accelerator, 0.3-3 parts of antioxidant, 0.1-1 part of tackifying resin, 0.1-1 part of silane coupling agent and 0.5-2 parts of neutralizer.
As a preferable technical scheme, the preparation raw material also comprises 10-30 parts of butadiene rubber in parts by weight.
In a preferred embodiment of the present invention, the filler is one or more selected from white smoke, china clay, calcium carbonate, silicon carbide, and boron nitride.
As a preferred embodiment of the present invention, the active agent is selected from one or more of zinc oxide, stearic acid, zinc stearate, calcium oxide, calcium chloride, and barium chloride.
In a preferred embodiment of the present invention, the accelerator is one or more selected from the group consisting of 2,2' -dibenzothiazyl disulfide, tetramethylthiuram monosulfide, 2-mercaptobenzothiazole, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and dipentamethylenethiuram tetrasulfide.
According to a preferable technical scheme of the invention, the accelerator is 2,2 'dibenzothiazyl disulfide and 2-mercaptobenzothiazole, wherein the mass ratio of the 2,2' dibenzothiazyl disulfide to the 2-mercaptobenzothiazole is 1: (0.1-0.5).
In a preferred embodiment of the present invention, the plasticizer is white oil.
As a preferred technical scheme of the invention, the silane coupling agent is selected from one or more of bis (triethoxypropyl) tetrasulfide, bis- (3-triethoxysilylpropyl) -disulfide, 3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane and 3-isocyanatopropyltriethoxysilane.
As a preferable technical scheme of the invention, the antioxidant is selected from one or more of phenolic antioxidant, phosphite antioxidant and thioether antioxidant.
The second aspect of the invention provides a preparation method of a light sole material, which at least comprises the following steps:
(1) mixing natural rubber, butadiene styrene rubber, butadiene rubber, ethylene-vinyl acetate copolymer and polysulfide rubber, and plasticating on a double-roll mill;
(2) then sequentially adding the antifogging agent, the antioxidant, the tackifying resin, the silane coupling agent, the active agent and the antioxidant, finally adding the plasticizer, the filler and the accelerator, mixing uniformly, and taking out the tablets to obtain the finished product.
Has the advantages that: the invention provides a light sole material and a preparation method thereof, wherein the light sole material with good wear resistance, comfortable wearing and long service life is obtained by combining natural rubber, butadiene rubber, styrene-butadiene rubber, ethylene-vinyl acetate copolymer (EVA) and polysulfide rubber and controlling the proportion thereof, mixing antifogging agent, antioxidant, tackifying resin, silane coupling agent, active agent and antioxidant on the basis, and finally adding plasticizer, filler and accelerator; the invention has simple process and low cost, and can meet the requirements of novel shoe materials in large environments.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to solve the technical problems, the first aspect of the invention provides a lightweight sole material, which at least comprises the following raw materials in parts by weight: 5-20 parts of natural rubber, 5-15 parts of styrene butadiene rubber, 20-40 parts of ethylene-vinyl acetate copolymer, 2-10 parts of filler, 2-10 parts of plasticizer, 0.1-0.5 part of polysulfide rubber, 0.5-3 parts of activator, 0.1-0.6 part of antifogging agent, 0.1-1 part of accelerator, 0.3-3 parts of antioxidant, 0.1-1 part of tackifying resin, 0.1-1 part of silane coupling agent and 0.5-2 parts of neutralizer.
In a more preferred embodiment, the light sole material of the present invention is prepared from at least the following raw materials in parts by weight: 8-15 parts of natural rubber, 7-10 parts of styrene-butadiene rubber, 25-35 parts of ethylene-vinyl acetate copolymer, 4-8 parts of filler, 5-9 parts of plasticizer, 0.2-0.35 part of polysulfide rubber, 1-2.5 parts of activator, 0.2-0.4 part of antifogging agent, 0.5-0.8 part of accelerator, 0.5-2 parts of antioxidant, 0.5-0.9 part of tackifying resin, 0.2-0.5 part of silane coupling agent and 0.8-1.5 parts of neutralizer.
In a most preferred embodiment, the light sole material of the present invention is prepared from at least the following raw materials in parts by weight: 10 parts of natural rubber, 8 parts of styrene-butadiene rubber, 30 parts of ethylene-vinyl acetate copolymer, 6 parts of filler, 6 parts of plasticizer, 0.25 part of polysulfide rubber, 2 parts of active agent, 0.3 part of antifogging agent, 0.75 part of accelerator, 1.3 parts of antioxidant, 0.8 part of tackifying resin, 0.3 part of silane coupling agent and 1 part of neutralizer.
Natural rubber
The Natural Rubber (NR) is a natural high molecular compound which takes cis-1, 4-polyisoprene as a main component, and 91-94 percent of the Natural Rubber (NR) is rubber hydrocarbon (cis-1, 4-polyisoprene), and the balance is non-rubber substances such as protein, fatty acid, ash, saccharide and the like.
In a preferred embodiment, the natural rubber of the present invention is standard rubber 3L, which is commercially available from a manufacturer including, but not limited to, Dry and composite materials science and technology, Inc., Guangzhou.
Styrene butadiene rubber
The Styrene Butadiene Rubber (SBR) of the present invention is also known as a polystyrene butadiene copolymer. The physical and mechanical properties, the processing property and the product use performance of the rubber are close to those of natural rubber, some properties such as wear resistance, heat resistance, aging resistance and vulcanization speed are better than those of the natural rubber, the rubber can be used together with the natural rubber and various synthetic rubbers, and can be widely applied to the fields of production of tires, adhesive tapes, rubber tubes, electric wires and cables, medical appliances, various rubber products and the like, is the largest general synthetic rubber variety and is one of rubber varieties which are firstly realized in industrial production.
In a preferred embodiment, the styrene-butadiene rubber of the present invention is styrene-butadiene rubber SBR1502, which is commercially available from a manufacturer including, but not limited to, the Camphor wood Hengtai plastics materials Canning section of Dongguan, model 1502, cat # 5652.
Ethylene-vinyl acetate copolymer
The ethylene-vinyl acetate copolymer is a general high polymer, is EVA for short, has a code of 1314 and has a molecular formula of (C2H4) x. (C4H6O2) y. It is combustible and has no irritation to combustion smell.
In a preferred embodiment, the ethylene-vinyl acetate copolymer of the present invention has an ethylene-acetic acid content of 5 to 40% by mass.
In a most preferred embodiment, the ethylene-vinyl acetate copolymers of the present invention are commercially available from commercial sources including, but not limited to, Shenghao Plastic materials, Inc., of Dongguan, under the designation EF 18002.
Filler material
The filler of the invention generally refers to materials filled in other objects; in chemical products, the filler is also called filler, which is a solid material for improving processability and mechanical properties of products and/or reducing cost.
In a preferred embodiment, the filler of the present invention is selected from one or more of white smoke, china clay, calcium carbonate, silicon carbide and boron nitride.
In a most preferred embodiment, the filler of the present invention is white smoke.
The white carbon black is a general name of white powdery X-ray amorphous silicic acid and silicate products, mainly refers to precipitated silica, fumed silica and superfine silica gel, and also includes powdery synthetic aluminum silicate, calcium silicate and the like. The white carbon black is porous material, and its composition can be SiO2·nH2O represents, wherein nH2O is present in the form of surface hydroxyl groups; has the characteristics of high temperature resistance, non-combustion, tastelessness, no smell and excellent electrical insulation.
In a preferred embodiment, the particle size of the white smoke is 1000-5000 meshes.
In a most preferred embodiment, the white smoke of the present invention has a particle size of 3000 mesh and is commercially available from a manufacturer including, but not limited to, Shandong Rihua New materials, Inc.
Plasticizer
The plasticizer is a substance which can increase the plasticity of the polymer when added into the polymer material, and the use of the plasticizer can improve the performance of the high polymer material, reduce the production cost and improve the production benefit. The plasticizer mainly has the effects of weakening the secondary valence bonds among resin molecules, increasing the mobility of the molecular bonds of the resin, reducing the crystallinity of the resin molecules, increasing the plasticity of the resin molecules, enhancing the flexibility of the resin molecules, being easy to process, being legally applicable to industrial application, and being widely existed in food packaging, cosmetics, medical devices and environmental water.
In a preferred embodiment, the plasticizer of the present invention is a white oil.
Examples of the white oil include 2# white oil, 5# white oil, 7# white oil, 10# white oil, 15# white oil and 22# white oil.
In a preferred embodiment, the white oil of the present invention is 5# white oil, which is commercially available from a manufacturer including, but not limited to, Jining Sanshou lube oil Co., Ltd, having a product number of SP 0018.
Polysulfide rubber
The polysulfide rubber of the present invention is a synthetic rubber obtained by polycondensation of a dihaloalkane and a polysulfide of an alkali metal or an alkaline earth metal. Has excellent oil resistance and solvent resistance, but has low strength, poor aging resistance, poor processing performance and odor. It is often used in combination with nitrile rubber. Industrial products include solid polysulfide rubber, liquid polysulfide rubber and polysulfide latex. The epoxy resin curing agent is mainly used as a sealing material for buildings, laminated glass and other industries and a curing agent for epoxy resin.
In a preferred embodiment, the molecular weight of the polysulfide rubber of the invention is 1500-.
In a more preferred embodiment, the polysulfide rubber of the present invention has a molecular weight of 1500 and is commercially available from commercial suppliers including, but not limited to, Zhengzhou Bengtai chemical Co., Ltd., model number LP-2.
Active agent
The invention relates to a substance which can increase the activity of an organic accelerator and fully exert the effect, thereby reducing the dosage of the accelerator or shortening the vulcanization time.
In a preferred embodiment, the active agent according to the invention is selected from one or more of zinc oxide, stearic acid, zinc stearate, calcium oxide, calcium chloride, barium chloride.
In a more preferred embodiment, the active agent of the present invention is zinc oxide.
Antifogging agent
The antifogging agent is a low-molecular-weight dispersing agent containing hydrophilic groups, consists of molecules with determined molecular weight, can form a coating when coated on the surface of a transparent object, and the hydrophilic groups in the coating can adsorb water molecules in the air and form a water film (instead of water beads) by wetting and diffusing on the surface of the transparent object, so that light rays penetrating through the object cannot be scattered, and the fogging phenomenon is avoided. The main components are surfactants, such as xylitol ester, sorbitol monopalmitate, lauric acid or hard resin acid monoglyceride and the like, the anti-fog agent is an instant anti-fog agent, the anti-fog duration is short, the adhesive force is poor, and the anti-fog effect disappears immediately after being wiped or washed by water generally for only a few days or a dozen days, so the agent cannot be used as a long-acting anti-fog agent.
In a preferred embodiment, the antifogging agent of the present invention is selected from one or more of the group consisting of an anti-emetic cream SK, an antifogging agent 1956.
In a most preferred embodiment, the antifogging agent of the present invention is antifogging agent 1956.
Accelerator
The accelerator of the present invention, when used in combination with a catalyst or fixing agent, provides a relatively small amount of material that increases the rate of reaction.
In a preferred embodiment, the accelerator according to the invention is selected from one or more of the group consisting of 2,2' dibenzothiazyl disulfide, tetramethylthiuram monosulfide, 2-mercaptobenzothiazole, tetramethylthiuram disulfide, tetraethylthiuram disulfide, dipentamethylenethiuram tetrasulfide.
In a more preferred embodiment, the accelerator of the present invention is 2,2 'dibenzothiazole disulfide and 2-mercaptobenzothiazole, wherein the mass ratio of 2,2' dibenzothiazole disulfide to 2-mercaptobenzothiazole is 1: (0.1-0.5).
In a most preferred embodiment, the accelerator of the present invention is 2,2 'dibenzothiazole disulfide and 2-mercaptobenzothiazole, wherein the mass ratio of 2,2' dibenzothiazole disulfide to 2-mercaptobenzothiazole is 1: 0.25.
tackifying resins
The tackifying resin of the invention is a small molecular compound capable of improving the viscosity, especially the surface viscosity, of a rubber material. Typically, these small molecule species have a relative molecular mass of between about a few hundred and ten thousand, and have relatively high glass transition temperatures.
In a preferred embodiment, the tackifying resin of the present invention is selected from one or more of hydrogenated rosin resin, α -terpene resin, β -terpene resin, C9 petroleum resin, dicyclopentadiene resin, alkyl phenol resin.
In a most preferred embodiment, the tackifying resin of the present invention is a C9 petroleum resin.
Silane coupling agent
The molecule of the silane coupling agent of the invention has more than two organosilicon monomers with different reactive groups, which can be chemically bonded with organic materials and inorganic materials.
In a preferred embodiment, the silane coupling agent of the present invention is selected from one or more of bis (triethoxypropyl) tetrasulfide, bis- (3-triethoxysilylpropyl) -disulfide, 3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane.
In a more preferred embodiment, the silane coupling agent of the present invention is bis (triethoxypropyl) silane tetrasulfide (CAS: 40372-72-3).
Neutralizing agent
The neutralizing agent is a substance for adjusting the pH value of the medium.
In a preferred embodiment, the neutralizing agent of the present invention is polyethylene glycol, and the molecular weight is 3500-4400.
In a more preferred embodiment, the polyethylene glycol of the present invention is commercially available from a source including, but not limited to, Nantong Chen Runji chemical Co., Ltd, with the specification PEG-4000.
The polyethylene glycol PEG-4000 plays a role in activating white carbon black and adjusting PH in rubber mixing.
Cis-polybutadiene rubber
The butadiene rubber is short for cis-1, 4-polybutadiene rubber, and the molecular formula of the butadiene rubber is (C4H6) n. The cis-butadiene rubber is a synthetic rubber with a regular structure and polymerized by butadiene, and the cis-structure content of the cis-butadiene rubber is more than 95 percent. The butadiene rubber is especially suitable for manufacturing automobile tires and cold-resistant products, and can also be used for manufacturing buffer materials, various rubber shoes, adhesive tapes, sponge rubbers and the like.
In a preferred embodiment, the preparation raw material also comprises 10-30 parts of butadiene rubber by weight.
In a more preferred embodiment, the preparation raw material of the invention further comprises 15 to 25 parts by weight of butadiene rubber.
In a more preferred embodiment, the preparation raw material of the present invention further includes 20 parts by weight of butadiene rubber.
In a most preferred embodiment, the butadiene rubber of the present invention is commercially available, including but not limited to, from Qianyuan synthetic materials technology, Inc., Guangzhou, model No. butadiene rubber BRVCR 617.
Antioxidant agent
The antioxidants of the present invention are a class of chemicals which, when present in only small amounts in a polymer system, retard or inhibit the progress of the polymer oxidation process, thereby retarding polymer aging and extending its useful life.
In a preferred embodiment, the antioxidant of the present invention is selected from one or more of phenolic antioxidants, phosphite antioxidants, and thioether antioxidants.
Examples of the phenolic antioxidant include triethylene glycol bis [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] (antioxidant 245), 2, 6-di-tert-butyl-4-methylphenol (BHT), 2 '-methylenebis (4-ethyl-6-tert-butylphenol) (antioxidant 425), 2' -methylenebis (4-methyl-6-tert-butylphenol) (antioxidant 2246), 2 '-methylenebis (4, 6-di-tert-butylphenol), 2' -ethylenebis (4, 6-di-tert-butylphenol), pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), and styrenated phenol (antioxidant SP).
As examples of the phosphite antioxidant, there may be mentioned: tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (nonylphenyl) phosphite (antioxidant TNPP), pentaerythritol distearate diphosphite (antioxidant 619), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626).
Examples of the thioether antioxidant include: bis (3-methyl-5-tert-butyl-4-hydroxybenzyl) sulfide, bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4 '-thiobis (2-methyl-6-tert-butylphenol), 2' -thiobis (4-methyl-6-tert-butylphenol), 4 '-thiobis (2, 6-di-tert-butylphenol), 4' -thiobis (6-tert-butyl-m-cresol), dilauryl thiodipropionate (DLTDP), diisotridecyl thiodipropionate (DTDTDTP), dioctadecyl thiodipropionate (DSTDP).
In a more preferred embodiment, the antioxidant of the present invention is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) and styrenated phenol (antioxidant SP), wherein the mass ratio of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) to styrenated phenol (antioxidant SP) is 1 (0.1-0.5).
In a most preferred embodiment, the antioxidant of the present invention is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) and styrenated phenol (antioxidant SP), wherein the mass ratio of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) to styrenated phenol (antioxidant SP) is 1: 0.3.
The second aspect of the invention provides a preparation method of a light sole material, which at least comprises the following steps:
(1) mixing natural rubber, butadiene styrene rubber, butadiene rubber, ethylene-vinyl acetate copolymer and polysulfide rubber, and plasticating on a double-roll mill;
(2) then sequentially adding the antifogging agent, the antioxidant, the tackifying resin, the silane coupling agent, the active agent and the antioxidant, finally adding the plasticizer, the filler and the accelerator, mixing uniformly, and taking out the tablets to obtain the finished product.
The inventor of the application finds in experiments that the sole material provided by the invention has the advantages of light weight, good wear resistance, wearing comfort, difficult deformation and long wearing life, and the probable reason is that the invention blends natural rubber, styrene butadiene rubber, ethylene-vinyl acetate copolymer and polysulfide rubber, sequentially adds an antifogging agent, an antioxidant, tackifying resin, a silane coupling agent, an active agent and an antioxidant, finally adds a plasticizer, a filler and an accelerator, and uniformly mixes, so that the natural rubber and the synthetic rubber are fully grafted, the wear resistance, plasticity and aging resistance of the sole are enhanced, the elasticity of the sole material is effectively improved, and the overall density of the sole material is reduced.
According to the invention, white smoke is selected as the filler, the particle size of the white smoke is controlled, the wear resistance and the anti-aging performance of the material are further improved, but the compatibility of the filler and other inorganic materials with the polymer in the system is poor, and the inventor discovers unexpectedly in experiments that when Si69 is selected as the silane coupling agent to be added into the system, the wear resistance, the cutting resistance and the pressure resistance of the sole material are improved, the processing performance of the process is improved, and the compatibility between the inorganic materials and the polymer in the system is also effectively improved.
It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Examples
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
Embodiment 1 provides a light sole material, which comprises the following preparation raw materials in parts by weight: 10 parts of natural rubber, 8 parts of styrene-butadiene rubber, 30 parts of ethylene-vinyl acetate copolymer, 6 parts of filler, 6 parts of plasticizer, 0.25 part of polysulfide rubber, 2 parts of active agent, 0.3 part of antifogging agent, 0.75 part of accelerator, 1.3 parts of antioxidant, 0.8 part of tackifying resin, 0.3 part of silane coupling agent and 1 part of neutralizer.
The natural rubber is standard rubber 3L, and is commercially available from Guangzhou dry and Yuan synthetic materials science and technology company.
The styrene butadiene rubber is styrene-butadiene rubber SBR1502 which can be obtained commercially, and the manufacturer is Zhangguan Hentai plastic raw material Ministry of Shangguan city, model 1502 and product number 5652.
Ethylene-vinyl acetate copolymers are commercially available from Shanghai Plastic materials Co., Ltd, Dongguan, under the trade designation EF 18002.
The filler is white smoke.
The particle size of the white smoke is 3000 meshes, and the purchase manufacturer is Shandong Li Hua New Material Co.
The plasticizer is white oil, the white oil is 5# white oil, the purchasing manufacturer is Jining Sanpin lubricating oil Co., Ltd, and the product number is SP 0018.
The molecular weight of the polysulfide rubber is 1500, and the purchasing manufacturer is Zhengzhou Bengtai chemical industry Co., Ltd, and the model is LP-2.
The active agent is zinc oxide.
The antifogging agent is an antifogging agent 1956.
The accelerator is 2,2 '-dibenzothiazyl disulfide and 2-mercaptobenzothiazole, wherein the mass ratio of the 2,2' -dibenzothiazyl disulfide to the 2-mercaptobenzothiazole is 1: 0.25.
the tackifying resin is C9 petroleum resin.
The silane coupling agent is bis (triethoxypropyl) tetrasulfide (CAS: 40372-72-3).
The polyethylene glycol can be obtained commercially, and the purchase manufacturer comprises but is not limited to Nantong Chen Runju chemical industry Co., Ltd, and the specification is PEG-4000.
The preparation raw materials also comprise 20 parts of butadiene rubber.
The butadiene rubber is commercially available, including but not limited to, from Qianyuan synthetic materials technology, Inc., Guangzhou, under the model of butadiene rubber BRVCR 617.
The antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) and styrenated phenol (antioxidant SP), wherein the mass ratio of the pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) to the styrenated phenol (antioxidant SP) is 1: 0.3.
The preparation method of the light sole material comprises the following steps:
(1) mixing natural rubber, butadiene styrene rubber, butadiene rubber, ethylene-vinyl acetate copolymer and polysulfide rubber, and plasticating on a double-roll mill;
(2) then sequentially adding the antifogging agent, the antioxidant, the tackifying resin, the silane coupling agent, the active agent and the antioxidant, finally adding the plasticizer, the filler and the accelerator, mixing uniformly, and taking out the tablets to obtain the finished product.
Example 2
Embodiment 2 provides a light sole material, which comprises the following preparation raw materials in parts by weight: 5 parts of natural rubber, 5 parts of styrene-butadiene rubber, 20 parts of ethylene-vinyl acetate copolymer, 2 parts of filler, 2 parts of plasticizer, 0.1 part of polysulfide rubber, 0.5 part of active agent, 0.1 part of antifogging agent, 0.1 part of accelerator, 0.3 part of antioxidant, 0.1 part of tackifying resin, 0.1 part of silane coupling agent and 0.5 part of neutralizer.
The natural rubber is standard rubber 3L, and is commercially available from Guangzhou dry and Yuan synthetic materials science and technology company.
The styrene butadiene rubber is styrene-butadiene rubber SBR1502 which can be obtained commercially, and the manufacturer is Zhangguan Hentai plastic raw material Ministry of Shangguan city, model 1502 and product number 5652.
Ethylene-vinyl acetate copolymers are commercially available from Shanghai Plastic materials Co., Ltd, Dongguan, under the trade designation EF 18002.
The filler is white smoke.
The particle size of the white smoke is 3000 meshes, and the purchase manufacturer is Shandong Li Hua New Material Co.
The plasticizer is white oil, the white oil is 5# white oil, the purchasing manufacturer is Jining Sanpin lubricating oil Co., Ltd, and the product number is SP 0018.
The molecular weight of the polysulfide rubber is 1500, and the purchasing manufacturer is Zhengzhou Bengtai chemical industry Co., Ltd, and the model is LP-2.
The active agent is zinc oxide.
The antifogging agent is an antifogging agent 1956.
The accelerator is 2,2 '-dibenzothiazyl disulfide and 2-mercaptobenzothiazole, wherein the mass ratio of the 2,2' -dibenzothiazyl disulfide to the 2-mercaptobenzothiazole is 1: 0.25.
the tackifying resin is C9 petroleum resin.
The silane coupling agent is bis (triethoxypropyl) tetrasulfide (CAS: 40372-72-3).
The polyethylene glycol can be obtained commercially, and the purchase manufacturer comprises but is not limited to Nantong Chen Runju chemical industry Co., Ltd, and the specification is PEG-4000.
The preparation raw materials also comprise 10 parts of butadiene rubber.
The butadiene rubber is commercially available, including but not limited to, from Qianyuan synthetic materials technology, Inc., Guangzhou, under the model of butadiene rubber BRVCR 617.
The antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) and styrenated phenol (antioxidant SP), wherein the mass ratio of the pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) to the styrenated phenol (antioxidant SP) is 1: 0.3.
The preparation method of the light sole material comprises the following steps:
(1) mixing natural rubber, butadiene styrene rubber, butadiene rubber, ethylene-vinyl acetate copolymer and polysulfide rubber, and plasticating on a double-roll mill;
(2) then sequentially adding the antifogging agent, the antioxidant, the tackifying resin, the silane coupling agent, the active agent and the antioxidant, finally adding the plasticizer, the filler and the accelerator, mixing uniformly, and taking out the tablets to obtain the finished product.
Example 3
Embodiment 3 provides a light sole material, which comprises the following preparation raw materials in parts by weight: 20 parts of natural rubber, 15 parts of styrene-butadiene rubber, 40 parts of ethylene-vinyl acetate copolymer, 10 parts of filler, 10 parts of plasticizer, 0.5 part of polysulfide rubber, 3 parts of active agent, 0.6 part of antifogging agent, 1 part of accelerator, 3 parts of antioxidant, 1 part of tackifying resin, 1 part of silane coupling agent and 2 parts of neutralizer.
The natural rubber is standard rubber 3L, and is commercially available from Guangzhou dry and Yuan synthetic materials science and technology company.
The styrene butadiene rubber is styrene-butadiene rubber SBR1502 which can be obtained commercially, and the manufacturer is Zhangguan Hentai plastic raw material Ministry of Shangguan city, model 1502 and product number 5652.
Ethylene-vinyl acetate copolymers are commercially available from Shanghai Plastic materials Co., Ltd, Dongguan, under the trade designation EF 18002.
The filler is white smoke.
The particle size of the white smoke is 3000 meshes, and the purchase manufacturer is Shandong Li Hua New Material Co.
The plasticizer is white oil, the white oil is 5# white oil, the purchasing manufacturer is Jining Sanpin lubricating oil Co., Ltd, and the product number is SP 0018.
The molecular weight of the polysulfide rubber is 1500, and the purchasing manufacturer is Zhengzhou Bengtai chemical industry Co., Ltd, and the model is LP-2.
The active agent is zinc oxide.
The antifogging agent is an antifogging agent 1956.
The accelerator is 2,2 '-dibenzothiazyl disulfide and 2-mercaptobenzothiazole, wherein the mass ratio of the 2,2' -dibenzothiazyl disulfide to the 2-mercaptobenzothiazole is 1: 0.25.
the tackifying resin is C9 petroleum resin.
The silane coupling agent is bis (triethoxypropyl) tetrasulfide (CAS: 40372-72-3).
The polyethylene glycol can be obtained commercially, and the purchase manufacturer comprises but is not limited to Nantong Chen Runju chemical industry Co., Ltd, and the specification is PEG-4000.
The preparation raw materials also comprise 30 parts of butadiene rubber.
The butadiene rubber is commercially available, including but not limited to, from Qianyuan synthetic materials technology, Inc., Guangzhou, under the model of butadiene rubber BRVCR 617.
The antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) and styrenated phenol (antioxidant SP), wherein the mass ratio of the pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) to the styrenated phenol (antioxidant SP) is 1: 0.3.
The preparation method of the light sole material comprises the following steps:
(1) mixing natural rubber, butadiene styrene rubber, butadiene rubber, ethylene-vinyl acetate copolymer and polysulfide rubber, and plasticating on a double-roll mill;
(2) then sequentially adding the antifogging agent, the antioxidant, the tackifying resin, the silane coupling agent, the active agent and the antioxidant, finally adding the plasticizer, the filler and the accelerator, mixing uniformly, and taking out the tablets to obtain the finished product.
Example 4
Example 4 differs from example 1 in that the starting materials for the preparation do not comprise natural rubber.
Example 5
Example 5 differs from example 1 in that the starting material does not comprise styrene-butadiene rubber.
Example 6
Example 6 differs from example 1 in that the starting material for the preparation does not comprise butadiene rubber.
Example 7
Example 7 differs from example 6 in that the starting material also comprises ethylene propylene diene monomer.
Example 8
Example 8 differs from example 1 in that the filler is white smoke, has a particle size of 325 mesh and is purchased from Shandong today chemical Co., Ltd.
Example 9
Example 9 differs from example 1 in that the silane coupling agent is anilinomethyltrimethoxysilane (CAS: 77855-73-3).
Example 10
Example 10 differs from example 1 in that the accelerators are 2,2 'dibenzothiazole disulfide and 2-mercaptobenzothiazole, wherein the mass ratio of 2,2' dibenzothiazole disulfide to 2-mercaptobenzothiazole is 1: 1.
evaluation of Performance
1. DIN abrasion (mm) according to GB9867 using a DIN abrasion tester3) And the densities (g/cm) of the light shoe sole materials prepared in examples 1 to 10 were measured3) The results are shown in Table 1 below.
2. The light weight sole materials prepared in examples 1 to 10 were left at room temperature of 22.0 ℃ for 24 hours and tested for hardness (shore a), the results of which are shown in table 1 below.
| DIN abrasion (mm)3) | Density (g/cm)3) | Hardness (ShoreA) | |
| Example 1 | 150 | 0.98 | 56 |
| Example 2 | 155 | 0.99 | 57 |
| Example 3 | 161 | 1.00 | 58 |
| Example 4 | 190 | 1.35 | 65 |
| Example 5 | 200 | 1.43 | 67 |
| Example 6 | 215 | 1.57 | 69 |
| Example 7 | 220 | 1.60 | 70 |
| Example 8 | 170 | 1.10 | 61 |
| Example 9 | 176 | 1.2 | 63 |
| Example 10 | 173 | 1.15 | 62 |
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The light sole material is characterized by comprising the following preparation raw materials in parts by weight: 5-20 parts of natural rubber, 5-15 parts of styrene butadiene rubber, 20-40 parts of ethylene-vinyl acetate copolymer, 2-10 parts of filler, 2-10 parts of plasticizer, 0.1-0.5 part of polysulfide rubber, 0.5-3 parts of activator, 0.1-0.6 part of antifogging agent, 0.1-1 part of accelerator, 0.3-3 parts of antioxidant, 0.1-1 part of tackifying resin, 0.1-1 part of silane coupling agent and 0.5-2 parts of neutralizer.
2. The lightweight sole material according to claim 1, wherein the preparation raw material further comprises 10 to 30 parts by weight of butadiene rubber.
3. The lightweight sole material according to claim 1, wherein said filler is selected from one or more of white smoke, china clay, calcium carbonate, silicon carbide, boron nitride.
4. The lightweight sole material of claim 1, wherein said active agent is selected from one or more of zinc oxide, stearic acid, zinc stearate, calcium oxide, calcium chloride, barium chloride.
5. The light sole material according to claim 1, wherein the accelerator is selected from one or more of 2,2' dibenzothiazyl disulfide, tetramethylthiuram monosulfide, 2-mercaptobenzothiazole, tetramethylthiuram disulfide, tetraethylthiuram disulfide, dipentamethylenethiuram tetrasulfide.
6. The lightweight sole material according to claim 5, wherein said accelerator is 2,2 'dibenzothiazyl disulfide and 2-mercaptobenzothiazole, wherein the mass ratio of 2,2' dibenzothiazyl disulfide to 2-mercaptobenzothiazole is 1: (0.1-0.5).
7. The lightweight sole material of claim 1, wherein said plasticizer is white oil.
8. The lightweight sole material according to claim 1, wherein said silane coupling agent is selected from one or more of bis (triethoxypropyl) silane tetrasulfide, bis- (3-triethoxysilylpropyl) -disulfide, 3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane.
9. The light weight sole material of claim 1, wherein the antioxidant is selected from one or more of phenolic antioxidants, phosphite antioxidants, and thioether antioxidants.
10. The method for preparing a lightweight sole material according to any one of claims 1 to 9, comprising at least the steps of:
(1) mixing natural rubber, butadiene styrene rubber, butadiene rubber, ethylene-vinyl acetate copolymer and polysulfide rubber, and plasticating on a double-roll mill;
(2) then sequentially adding the antifogging agent, the antioxidant, the tackifying resin, the silane coupling agent, the active agent and the antioxidant, finally adding the plasticizer, the filler and the accelerator, mixing uniformly, and taking out the tablets to obtain the finished product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911150147.8A CN110845785A (en) | 2019-11-21 | 2019-11-21 | Light sole material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911150147.8A CN110845785A (en) | 2019-11-21 | 2019-11-21 | Light sole material and preparation method thereof |
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| CN110845785A true CN110845785A (en) | 2020-02-28 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112946797A (en) * | 2021-02-19 | 2021-06-11 | 晋江联兴反光材料有限公司 | Reflective film of composite metal layer and preparation method thereof |
| CN115286848A (en) * | 2022-09-08 | 2022-11-04 | 温州市宜和鞋材有限公司 | Three-dimensional glue-melting synthetic sole and preparation method thereof |
| CN115304833A (en) * | 2021-08-09 | 2022-11-08 | 温州市优联新材料有限公司 | Foaming sole material and preparation method thereof |
| CN115304837A (en) * | 2021-08-09 | 2022-11-08 | 温州市优联新材料有限公司 | Antiskid sole material and preparation method thereof |
-
2019
- 2019-11-21 CN CN201911150147.8A patent/CN110845785A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112946797A (en) * | 2021-02-19 | 2021-06-11 | 晋江联兴反光材料有限公司 | Reflective film of composite metal layer and preparation method thereof |
| CN112946797B (en) * | 2021-02-19 | 2023-10-31 | 晋江联兴反光材料有限公司 | Reflective film with composite metal layer and preparation method thereof |
| CN115304833A (en) * | 2021-08-09 | 2022-11-08 | 温州市优联新材料有限公司 | Foaming sole material and preparation method thereof |
| CN115304837A (en) * | 2021-08-09 | 2022-11-08 | 温州市优联新材料有限公司 | Antiskid sole material and preparation method thereof |
| CN115304833B (en) * | 2021-08-09 | 2024-03-22 | 温州市优联新材料有限公司 | Foaming sole material and preparation method thereof |
| CN115304837B (en) * | 2021-08-09 | 2024-03-26 | 温州市优联新材料有限公司 | Anti-skid sole material and preparation method thereof |
| CN115286848A (en) * | 2022-09-08 | 2022-11-04 | 温州市宜和鞋材有限公司 | Three-dimensional glue-melting synthetic sole and preparation method thereof |
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