CN106117638A - A kind of wear-resisting Antiskid rubber and preparation method thereof - Google Patents
A kind of wear-resisting Antiskid rubber and preparation method thereof Download PDFInfo
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- CN106117638A CN106117638A CN201610481780.5A CN201610481780A CN106117638A CN 106117638 A CN106117638 A CN 106117638A CN 201610481780 A CN201610481780 A CN 201610481780A CN 106117638 A CN106117638 A CN 106117638A
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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
- C08L7/00—Compositions of natural rubber
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
-
- 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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention discloses a kind of wear-resisting Antiskid rubber and preparation method thereof.The method comprises the steps: 1) utilize silane coupler that chopped fiber is modified, obtain modified short fiber；Chopped fiber is at least one in carbon fiber, glass fibre and basalt fibre；The consumption of silane coupler is the 0.1%～1.5% of described chopped fiber quality；2) natural rubber, suitable butadiene rubber, nitrile rubber and modified short fiber are weighed as crude green body；Part crude green body is carried out mixing；3) in the crude green body of surplus, add magnesium oxide, silane, stearic acid, accelerator and activating agent, be subsequently adding to step 2) mixing after material in carry out mixing；Accelerator and activating agent are sequentially added into described crude green body；4) step 3) described mixing after material carry out sulfidization molding, obtain wear-resisting Antiskid rubber.The wear-resisting non-skid property in the footwear big end that the present invention uses high abrasion high slip preventing rubber to prepare is good, it is adaptable to as the tennis shoes big end and other footwear big end higher to the requirement of wear-resisting non-skid property.
Description
Technical field
The present invention relates to a kind of wear-resisting Antiskid rubber and preparation method thereof, belong to field of rubber technology.
Background technology
Current most rubber can only be used in the footwear big end that wear-resisting non-skid property requirement is relatively low, it is impossible to stops for wear-resisting
The footwear big end that sliding performance requirement is higher, it is impossible to tackle the on-slip demand under the complex environments such as wet and slippery, oil stain, ice face.
Accordingly, it would be desirable to a kind of, there is the most wear-resisting and non-skid property rubber, the wear-resisting on-slip in the footwear big end being made from
Property is good, is applicable to as the wear-resisting non-skid property requirement higher footwear big end.
Summary of the invention
It is an object of the invention to provide a kind of wear-resisting Antiskid rubber and preparation method thereof, high abrasion high slip preventing rubber of the present invention
Having excellent wear-resisting non-skid property, the wear-resisting antiskid property in the footwear big end being made from is good, is applicable to as wear-resisting non-skid property
Require the higher footwear big end.
The preparation method of the wear-resisting Antiskid rubber that the present invention provides, comprises the steps:
1) utilize silane coupler that chopped fiber is modified, obtain modified short fiber；
Described chopped fiber is at least one in carbon fiber, glass fibre and basalt fibre；
A diameter of 10～100 μm of described chopped fiber, a length of 1～10mm；
The consumption of described silane coupler is the 0.1%～1.5% of described chopped fiber quality；
2) natural rubber, suitable butadiene rubber, nitrile rubber and described modified short fiber are weighed as crude green body；By part institute
State crude green body and carry out mixing；
3) in the described crude green body of surplus, add magnesium oxide, silane, stearic acid, accelerator and activating agent, be subsequently adding to
Step 2) described mixing after material in carry out mixing；Described accelerator and described activating agent are sequentially added into described crude green body；
4) step 3) described mixing after material carry out sulfidization molding, obtain described wear-resisting Antiskid rubber.
In above-mentioned preparation method, described accelerator can be sulfur；Described activating agent can be ZnO, polyvinyl alcohol and poly-second
In alkene at least one；
Described silane coupler can be vinyl trichlorosilane, VTES, vinyl three (beta-methoxy second
Epoxide) silane, γ-glycidylpropyl-trimethoxy silane, γ-methacryloxypropyl-trimethoxy silane, N-
(β-aminoethyl)-γ-aminopropyl-trimethoxy silane, N-(β-aminoethyl)-γ-aminopropyl-Methyl-trimethoxy silane,
In γ-chloropropyl-trimethoxy silane, γ-mercapto propyl-trimethoxysilane and γ-aminopropyl-trimethoxy silane at least one
Kind；
Utilize described silane coupler that described chopped fiber is modified, with new modified to the surface of described chopped fiber,
So that chopped fiber is more tight with the combination at the interface of rubber, form a good bonding interface；
The consumption of described silane coupler can be the 1% of described chopped fiber quality.
In above-mentioned preparation method, described natural rubber, described suitable butadiene rubber, described nitrile rubber, described tristearin
Magnesium oxide sour, described, described modified short fiber, described silane, described activating agent can be 400 with the mass ratio of described accelerator:
400:200:15:40～50:100～250:20～40:93～103:6.4～9, concretely 400:400:200:15:40:
100:20:93:6.4,400:400:200:15:45:150:30:103:9,400:400:200:15:45:180:30:103:9,
400:400:200:15:45:210:30:103:9 or 400:400:200:15:45:250:40:103:9.
In above-mentioned preparation method, step 2) described in mixing temperature be 95 DEG C～105 DEG C, the time is 68～112s,
Such as 90s；
Step 3) described in mixing temperature be 120 DEG C～130 DEG C, the time is 88～132s, such as 120s.
In above-mentioned preparation method, step 4) described in the temperature of sulfidization molding can be 145～155 DEG C, the time of sulfuration
Can be 5～10min.
In above-mentioned preparation method, step 2) and step 3) described in the amount of crude green body there is no concrete requirement, can be according to tool
The situation of body is adjusted.
The wear-resisting Antiskid rubber that the present invention provides has stronger wear-resisting non-skid property, it is possible to be used for making footwear outer bottom.
There is advantages that
1, the present invention uses the method modifying surface to chopped fiber of short fiber pretreating, so that chopped fiber and rubber
The combination at the interface of glue is more tight, forms a good bonding interface, forms the structure of hairbrush shape on the surface of rubber, from
And reach and improve anti-skidding effect.
2, the present invention uses natural rubber synthetic rubber to be main body sizing material, only makes high abrasion height through mixing, sulfuration compacting
Sliding rubber, wear-resisting general is amenable to wear away for a long time below 0.05, dry on-slip more than 1.0, wet on-slip more than 0.8. because of
This, the high abrasion high slip preventing rubber wear-resisting on-slip of the present invention；
3, the present invention by raw material by limit proportioning mixing after put into vulcanizer sulfidization molding, curing temperature 145～155 DEG C,
Cure time 5～10 minutes, preparation is simple, quickly；
4, the wear-resisting non-skid property in the footwear big end that the present invention uses high abrasion high slip preventing rubber to prepare is good, it is adaptable to as tennis
The footwear big end and other footwear big end higher to the requirement of wear-resisting non-skid property.
Accompanying drawing explanation
Fig. 1 is that (basalt fibre coheres with rubber for the electromicroscopic photograph of wear-resisting Antiskid rubber of the embodiment of the present invention 1 preparation
Form is inserted).
Fig. 2 is that (basalt fibre coheres with rubber for the electromicroscopic photograph of wear-resisting Antiskid rubber of the embodiment of the present invention 1 preparation
Form is electric welding formula).
Fig. 3 is the electromicroscopic photograph of basalt fibre shown in Fig. 2 and the electric welding formula bond edge of rubber.
Fig. 4 is that (basalt fibre coheres with rubber for the electromicroscopic photograph of wear-resisting Antiskid rubber of the embodiment of the present invention 1 preparation
Form is complete fixed by adhesive).
Detailed description of the invention
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
Embodiment 1～5,
Formula in employing table 1 is prepared the wear-resisting Antiskid rubber of the present invention, and preparation process is as follows:
(1) modified short fiber is prepared
Spray VTES carries out pre-place to basalt (a diameter of 10～100 μm, a length of 1～10mm)
Reason, the consumption of coupling agent is the 1% of basalt quality, stores, dries and make uniform modified short fiber.
(2) mixing
1) first by mixing for part (50%) crude green body (natural rubber, butadiene rubber, nitrile rubber and pretreated short fibre)
Temperature is 100 ± 5 DEG C, after be laid in charging tray, the time is 90s；
2) in another part crude green body (natural rubber, butadiene rubber, nitrile rubber and pretreated short fibre), oxygen is added
Change magnesium, silane, stearic acid, sulfur and ZnO, sulfur and ZnO are sequentially added into, and are subsequently adding step 1) material in carry out mixing temperature
Degree is 125 ± 5 DEG C, and the time is 120s:
In mixing process, start upender, add mixing less than 13.5kg/ hands reclaimed materials in the process, then will
Luntai, away from being adjusted to 0.9～1.1mm, thins three times, about 720 seconds time, and then wheelspan is adjusted to 8-10mm, and bundled tube sends into 14 " Luntais
Slice, time 60～120 seconds；Slice comparison ordinary material mode, sets thickness calibration slice according to PFC, and sheet stock is sent into be checked
District.
(3) sulfidization molding
All raw materials are put into vulcanizer sulfidization molding, curing temperature 145 DEG C, sulfuration by proportioning after said method is mixing
8 minutes time.
In above-mentioned preparation process, should be noted that following problem:
Before A, dnockout below Luntai temperature 50 C, dnockout controls below 80 DEG C；
Only water when B, material slice, takes cool material mode to carry out cooling operations；
C, sheet stock can carry out next processing procedure after inspection.
Molding production specification:
1) board temperature standard is: 100 DEG C～200 DEG C；
2) board pressure criteria: 140kg/cm2～150kg/cm2。
Composition of raw materials (mass ratio) in table 1 embodiment 1-5 and comparative example 1
Embodiment 1 preparation rubber electromicroscopic photograph as shown in Figure 1, Figure 2, Figure 3 and Figure 4, the wherein times magnification of Fig. 1 (a)
Number is 5000, and the amplification of Fig. 1 (b) is 15000, as seen from Figure 1, still has gap between basalt fibre and rubber, belongs to
In not exclusively binding, this bonding form is inserted.
Wherein the amplification of Fig. 2 (a) is 6000, and the amplification of Fig. 2 (b) is 17000, as seen from Figure 2, the Black Warrior
Still having gap between rock fiber and rubber, belong to not exclusively bonding, this bonding form is electric welding formula.
The electromicroscopic photograph of the electric welding formula bond edge of basalt fibre shown in Fig. 2 and rubber is as it is shown on figure 3, wherein Fig. 3 (a)
Amplification be 5000, the amplification of Fig. 3 (b) is 15000.
The amplification of Fig. 4 (a) is 100, and the amplification of Fig. 4 (b) is 1000, and Fig. 4 (b) is that the local of Fig. 4 (a) is put
Greatly, as seen from Figure 4, there is no gap between basalt fibre and rubber, belong to and bind completely.
After measured, the physical property of the wear-resisting Antiskid rubber prepared by embodiment 1～6 shows as shown in table 2 and table 3.
The physicochemical property of wear-resisting Antiskid rubber prepared by table 2 embodiment 1-6
The density of wear-resisting Antiskid rubber, non-skid property and wear volume prepared by table 3 embodiment 1-6
Data in contrast table 2 and table 3 understand, and high abrasion high slip preventing rubber of the present invention has excellent wear-resisting antiskid property
Can, the highest also below 0.15, it is amenable to wear away for a long time, dry on-slip is more than 1.0, and wet on-slip is more than 0.80；And not
Add the wear-resisting of chopped fiber and dry and wet on-slip and all decline a lot in data；The footwear big end energy prepared by this high abrasion high slip preventing rubber
It is applicable to the tennis shoes big end and other footwear big end higher to wear-resisting non-skid property requirement.
The present invention passes through General Purpose Rubber main body sizing material, adds pretreated short fibre, through mixing, hot pressing and the demoulding, preparation
The common rubber of high abrasion high slip preventing rubber ratio to have the most wear-resisting skid-proof function.
In sum, the high abrasion high slip preventing rubber of the present invention has excellent wear-resisting non-skid property, the footwear being made from
The big wear-resisting antiskid property in the end is good, is applicable to as the higher footwear outer bottom of wear-resisting non-skid property requirement.It is possible not only to overall as big
The end, uses, it is also possible to be used in conjunction with General Purpose Rubber as the wear-resisting position of part.
It should be noted that all documents mentioned in the present invention are incorporated as reference, the most in this application just as often
One document is individually recited as with reference to like that.It is specific embodiment and the institute of the present invention in addition, it is to be understood that above-described
The know-why used, after the above-mentioned teachings having read the present invention, the present invention can be made by those skilled in the art
Various changes or amendment are without departing from spirit and scope of the invention, and these equivalent form of values also fall within the scope of the present invention.
Claims (8)
1. a preparation method for wear-resisting Antiskid rubber, comprises the steps:
1) utilize silane coupler that chopped fiber is modified, obtain modified short fiber；
Described chopped fiber is at least one in carbon fiber, glass fibre and basalt fibre；
A diameter of 10～100 μm of described chopped fiber, a length of 1～10mm；
The consumption of described silane coupler is the 0.1%～1.5% of described chopped fiber quality；
2) natural rubber, suitable butadiene rubber, nitrile rubber and described modified short fiber are weighed as crude green body；By described for part slightly
Base carries out mixing；
3) in the described crude green body of surplus, add magnesium oxide, silane, stearic acid, accelerator and activating agent, be subsequently adding to step
2) described mixing after material in carry out mixing；Described accelerator and described activating agent are sequentially added into described crude green body；
4) step 3) described mixing after material carry out sulfidization molding, obtain described wear-resisting Antiskid rubber.
Preparation method the most according to claim 1, it is characterised in that: described accelerator is sulfur；Described activating agent is
In ZnO, polyvinyl alcohol and polyethylene at least one；
Described silane coupler is vinyl trichlorosilane, VTES, vinyl three (beta-methoxy ethyoxyl)
Silane, γ-glycidylpropyl-trimethoxy silane, γ-methacryloxypropyl-trimethoxy silane, N-(β-ammonia
Ethyl)-γ-aminopropyl-trimethoxy silane, N-(β-aminoethyl)-γ-aminopropyl-Methyl-trimethoxy silane, γ-chlorine third
In base-trimethoxy silane, γ-mercapto propyl-trimethoxysilane and γ-aminopropyl-trimethoxy silane at least one.
Preparation method the most according to claim 1 and 2, it is characterised in that: described natural rubber, described suitable butadiene rubber
Glue, described nitrile rubber, described stearic acid, described magnesium oxide, described modified short fiber, described silane, described activating agent and institute
The mass ratio stating accelerator is 400:400:200:15:40～50:100～250:20～40:93～103:6.4～9.
4. according to the preparation method according to any one of claim 1-3, it is characterised in that: step 2) described in mixing temperature
Being 95 DEG C～105 DEG C, the time is 68～112s；
Step 3) described in mixing temperature be 120 DEG C～130 DEG C, the time is 88～132s.
5. according to the preparation method according to any one of claim 1-4, it is characterised in that: step 4) described in sulfidization molding
Temperature is 145～155 DEG C, and the time of sulfuration is 5～10min.
6. the wear-resisting Antiskid rubber that prepared by method according to any one of claim 1-5.
7. the application in making footwear outer bottom of the wear-resisting Antiskid rubber described in claim 6.
8. a footwear outer bottom, it is made up of Antiskid rubber wear-resisting described in claim 6.
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| CN201610481780.5A CN106117638A (en) | 2016-06-27 | 2016-06-27 | A kind of wear-resisting Antiskid rubber and preparation method thereof |
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| CN201610481780.5A CN106117638A (en) | 2016-06-27 | 2016-06-27 | A kind of wear-resisting Antiskid rubber and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189122A (en) * | 2017-06-22 | 2017-09-22 | 河北科技大学 | A kind of carbon fiber-based puncture resistant rubber composite and preparation method thereof |
| CN107383467A (en) * | 2017-07-28 | 2017-11-24 | 扬州健步鞋业有限公司 | One kind is anti-to pound acid and alkali-resistance anti-skid multifunctional safety shoe |
| CN109054114A (en) * | 2018-06-25 | 2018-12-21 | 安踏（中国）有限公司 | A kind of Antiskid rubber product, preparation method and its application |
| CN110467753A (en) * | 2019-08-21 | 2019-11-19 | 深圳市大毛牛新材料科技有限公司 | A kind of environmental protection microporous foam non-slip mat and preparation method thereof |
| CN110698733A (en) * | 2019-10-14 | 2020-01-17 | 福建五持恒科技发展有限公司 | Graphene natural rubber polymer ice top-slip mixed foam material and preparation method thereof |
| KR20230101327A (en) * | 2021-12-29 | 2023-07-06 | 문민경 | Outsole containing carbon fiber and manufacturing method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189122A (en) * | 2017-06-22 | 2017-09-22 | 河北科技大学 | A kind of carbon fiber-based puncture resistant rubber composite and preparation method thereof |
| CN107189122B (en) * | 2017-06-22 | 2018-10-12 | 河北科技大学 | A kind of carbon fiber-based puncture resistant rubber composite material and preparation method thereof |
| CN107383467A (en) * | 2017-07-28 | 2017-11-24 | 扬州健步鞋业有限公司 | One kind is anti-to pound acid and alkali-resistance anti-skid multifunctional safety shoe |
| CN107383467B (en) * | 2017-07-28 | 2019-01-25 | 扬州健步鞋业有限公司 | One kind is anti-to pound acid and alkali-resistance anti-skid multifunctional safety shoe |
| CN109054114A (en) * | 2018-06-25 | 2018-12-21 | 安踏（中国）有限公司 | A kind of Antiskid rubber product, preparation method and its application |
| CN110467753A (en) * | 2019-08-21 | 2019-11-19 | 深圳市大毛牛新材料科技有限公司 | A kind of environmental protection microporous foam non-slip mat and preparation method thereof |
| CN110698733A (en) * | 2019-10-14 | 2020-01-17 | 福建五持恒科技发展有限公司 | Graphene natural rubber polymer ice top-slip mixed foam material and preparation method thereof |
| CN110698733B (en) * | 2019-10-14 | 2021-10-01 | 福建五持恒科技发展有限公司 | Graphene natural rubber polymer ice top-slip mixed foam material and preparation method thereof |
| KR20230101327A (en) * | 2021-12-29 | 2023-07-06 | 문민경 | Outsole containing carbon fiber and manufacturing method thereof |
| KR102625739B1 (en) * | 2021-12-29 | 2024-01-15 | 문민경 | Outsole containing carbon fiber and manufacturing method thereof |
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Application publication date: 20161116 |
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