CN108395608A - A kind of wear-resisting ternary EVA base rubber blends and preparation method thereof - Google Patents
A kind of wear-resisting ternary EVA base rubber blends and preparation method thereof Download PDFInfo
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- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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Abstract
The present invention relates to a kind of wear-resisting ternary EVA base rubber blends and preparation method thereof, it is characterized in that using 20 mass parts SEBS, 30 mass parts SBR, 50 mass parts EVA, the pre-dispersed glue of 40 mass parts dynamic vulcanizations, 57 mass parts of antioxidant, 34 mass parts of ZnO, 0.5 1 mass parts of Hst, 23 mass parts of accelerating agent, 0.5 1 mass parts of S, 12 mass parts of DCP, 35 mass parts of foaming agent.The wear-resisting ternary EVA base rubber blends that the present invention is prepared, wear-resisting property is excellent, and elasticity is high, resilience performance is good, dimensionally stable, mechanical property are good, can be used for the sole of sport footwear.
Description
Technical field
The invention belongs to rubber polymer composite material and preparation method, especially a kind of wear-resisting ternary EVA bases
Rubber blend and preparation method thereof.
Background technology
Currently, what Sports shoe sole was often foamed with EVA base rubber blends.After foaming, EVA base rubber plastic blends
Object has many advantages, such as that density is small, anti-skidding, resilience is good.But the wearability of EVA base rubber blends is low after foaming, and is always this
The fatal defects of Sports shoe sole.In order to improve EVA base rubber blend wearabilities, pass through frequently with following measures in the industry：（1）It will hair
Bubble EVA base materials are kept apart with rubbing surface, including are pasted one layer of abrasive rubber bottom on foaming EVA base materials and be added in filler normal
Opening powder --- the talcum powder of rule, but former approach increases production cost, later approach can increase the risk to slip；
（2）The polymer or abrasion-resistant polymer of compliance is added, but these polymer are mostly non-polar material, and polar
EVA matrix compatibilities are bad, and the comprehensive performance of blend is caused to reduce.Therefore, how shoes EVA base rubber blends to be improved
While wearability, holding even improves other performances, is one of the research direction of current footwear industry circle.
Invention content
The object of the present invention is to provide a kind of wear-resisting ternary EVA base rubber blends and preparation method thereof.
Realize technical solution of the invention：
A kind of preparation method of wear-resisting ternary EVA base rubber blends, it is characterised in that comprise the steps of：
Step 1：The calcium carbonate of 100 g is added in 500 mL ethanol solutions, 10 min are stirred by ultrasonic in 500 W, and 1-2 g are added
5 min are stirred by ultrasonic in Hst, 500 W, centrifuge, dry, and ball milling obtains modified calcium carbonate；
Step 2：20 mass parts SEBS are kneaded on 120 DEG C of open mill, the modification that 100 mass parts step 1 obtain is added
Calcium carbonate is kneaded 8 min, and the modified calcium carbonate that 50 mass parts EVA of addition and 100 mass parts step 1 obtain is kneaded 5 min,
Temperature is reduced to 80 DEG C, the SBR and the obtained modified calcium carbonate of 100 mass parts step 1 of 30 mass parts is added, is kneaded 8 min,
The maleic anhydride of 5 mass parts is added, is kneaded 3 min, 5 mass parts DCP are added, 80 DEG C are continued to be kneaded 10 min, are moved
State vulcanizes pre-dispersed glue；
Step 3：5 min are blended on 120 DEG C of open mills in 30 mass parts SBR and 20 mass parts SEBS, 80 DEG C is cooled to, adds
Enter the EVA of 50 mass parts and the pre-dispersed glue of dynamic vulcanization that 40 mass parts step 2 obtain, antioxidant 5-7 mass parts, ZnO is added
3-4 mass parts, Hst 0.5-1 mass parts, accelerating agent 1-2 mass parts, Sulfur 0.5-1 mass parts, DCP 1-2 mass parts, foaming
Agent 5-8 mass parts；Bao Tong obtains Blend rubber；
Step 4：After Blend rubber made from step 3 is parked for 24 hours, sulfurizing time and foamed time are measured with vulcameter, is used
Vulcanizing press moulded from foam, curing temperature are 160 DEG C, obtain wear-resisting ternary EVA base rubber blends.
The size of the calcium carbonate is 30-40 μm.
The SBR is SBR1502, and SEBS H1077, EVA are the EVA containing 15% Vinyl Acetate Monomer.
The antioxidant is any one in antioxidant 1010 and irgasfos 168, and accelerating agent is appointing in M and NOBS
Meaning is a kind of, and foaming agent is azodicarbonamide.
The invention also discloses the wear-resisting ternary EVA base rubber blends being prepared using the above method.
Compared with prior art, the present invention its remarkable advantage is：
（1）Since calcium carbonate can serve as the effect that nucleating agent and stearic acid can promote foaming agent to decompose in foaming process, this
Invention uses stearic acid modified calcium carbonate, and using stearic acid to the facilitation of foaming, bubble is improved around calcium carbonate
The formation rate in hole reduces the density of material, on the other hand, using the reinforcing effect of calcium carbonate, to the abscess that is formed around it into
Row reinforcement makes up the problem of foam composite material mechanical strength caused by being formed due to abscess declines, realizes light high-strength
Effect；
（2）In the compounding of the pre-dispersed collagen-based materials of dynamic vulcanization, SBR is added into EVA/SEBS systems, maleic of having arranged in pairs or groups
Dicarboxylic anhydride and stearic acid modified calcium carbonate are utilized respectively the graft modification of maleic anhydride, the interface of surface modified calcium carbonate
Technology of dissolving each other is forced in activity and crosslinking, while improving the compatibility of SBR, SEBS and EVA matrix, obtains the dynamic of good interface effect
State vulcanizes pre-dispersed glue；
（3）The pre-dispersed glue of dynamic vulcanization is used in ternary composite rubber-plastic material, is on the one hand utilized its pre-dispersed effect, is made
It obtains filler-calcium carbonate to be dispersed in ternary composite rubber-plastic material, on the other hand utilizes its good interfacial effect, solve
The compatibility of three-phase in ternary composite rubber-plastic material, to obtain, wear-resisting property is good, high comprehensive performance antiwear EVA base answers
Condensation material.
Present invention is further described in detail below in conjunction with the accompanying drawings.
Description of the drawings
The preparation process flow of ternary EVA base rubber blends wear-resisting Fig. 1.
Specific implementation mode
A kind of preparation method of wear-resisting ternary EVA base rubber blends, comprises the steps of：
Step 1：The calcium carbonate of 100 g is added in 500 mL ethanol solutions, 10 min are stirred by ultrasonic in 500 W, and 1-2 g are added
5 min are stirred by ultrasonic in Hst, 500 W, centrifuge, dry, and ball milling obtains modified calcium carbonate；
Step 2：20 mass parts SEBS are kneaded on 120 DEG C of open mill, the modification that 100 mass parts step 1 obtain is added
Calcium carbonate is kneaded 8 min, and the modified calcium carbonate that 50 mass parts EVA of addition and 100 mass parts step 1 obtain is kneaded 5 min,
Temperature is reduced to 80 DEG C, the SBR and the obtained modified calcium carbonate of 100 mass parts step 1 of 30 mass parts is added, is kneaded 8 min,
The maleic anhydride of 5 mass parts is added, is kneaded 3 min, 5 mass parts DCP are added, 80 DEG C are continued to be kneaded 10 min, are moved
State vulcanizes pre-dispersed glue；
Step 3：5 min are blended on 120 DEG C of open mills in 30 mass parts SBR and 20 mass parts SEBS, 80 DEG C is cooled to, adds
Enter the EVA of 50 mass parts and the pre-dispersed glue of dynamic vulcanization that 40 mass parts step 2 obtain, antioxidant 5-7 mass parts, ZnO is added
3-4 mass parts, Hst 0.5-1 mass parts, accelerating agent 1-2 mass parts, Sulfur 0.5-1 mass parts, DCP 1-2 mass parts, foaming
Agent 5-8 mass parts；Bao Tong obtains Blend rubber；
Step 4：After Blend rubber made from step 3 is parked for 24 hours, sulfurizing time and foamed time are measured with vulcameter, is used
Vulcanizing press moulded from foam, curing temperature are 160 DEG C, obtain wear-resisting ternary EVA base rubber blends.
The size of the calcium carbonate is 30-40 μm.
The SBR is SBR1502, and SEBS H1077, EVA are the EVA containing 15% Vinyl Acetate Monomer.
The antioxidant is any one in antioxidant 1010 and irgasfos 168, and accelerating agent is appointing in M and NOBS
Meaning is a kind of, and foaming agent is azodicarbonamide.
Wear-resisting ternary EVA base rubber blends obtained are subjected to following performance test.
（1）Tensile property
EVA base rubber blends are tested according to GB/T528-2009 standards, tensile speed 500mm/min.It records compound
Material determines to stretch 100% modulus（M 100）, tensile strength, elongation at break.Sample with bigger tensile strength is better.
（2）Tear resistance
Tear resistance test tests EVA base rubber blends according to GB/T529-2008 standards, speed 500mm/
Min records tearing strength.Sample with bigger tearing strength is better.
（3）Wear-resisting property
Wear-resisting property is tested according to GB/T9867-2001 standards on TaiWan, China high ferro GT-7912-D DIN abrasion testing machines,
Record wear volume.Sample with smaller wear volume is better.
（4）Hardness test
Hardness is tested using GS-701N hardometers, according to GB/T 531-1999.
（5）Bounce impact elasticity
Bounce impact elasticity records rebound value according to being tested on GB/T1681-1991 standard impulse resiliometers.With bigger time
The EVA base rubber blends of bullet value are better.
（6）Deformation rate
Compression deformation rate is compressed according to standard HG/T 2876-2009 in MZ-4020 to be tested on permanent variability exerciser, is remembered
Record deformation rate.EVA base rubber blends with smaller deformation rate are better.
（7）Dimensional contraction rate
It is tested according to standard GB/T3903.13, the EVA base rubber blends with smaller shrinking percentage are better.
Below by embodiment and comparative example, the invention will be further described.
Embodiment 1
Step 1：100 g, 40 μm of calcium carbonate is added in 500 mL ethanol solutions, 10 min are stirred by ultrasonic in 500 W, are added 1
5 min are stirred by ultrasonic in g Hst, 500 W, centrifuge, and dry, ball milling obtains modified calcium carbonate；
Step 2：20 mass parts SEBS H1077 are kneaded on 120 DEG C of open mill, 100 mass parts step 1 are added and obtain
Modified calcium carbonate, be kneaded 8 min, be added 50 mass parts contain 20% Vinyl Acetate Monomer EVA and 100 mass parts step 1
Obtained modified calcium carbonate is kneaded 5 min, reduces temperature to 80 DEG C, 30 mass parts of SBR of 30 mass parts are added
The modified calcium carbonate that SBR9000 and 100 mass parts step 1 obtain is kneaded 8 min, and the maleic anhydride of 5 mass parts is added,
3 min are kneaded, 5 mass parts DCP are added, 80 DEG C are continued to be kneaded 10 min, obtain the pre-dispersed glue of dynamic vulcanization；
Step 3：5 min are blended on 120 DEG C of open mills in 30 mass parts SBR9000 and 20 mass parts SEBS H1077, are cooled down
To 80 DEG C, the dynamic vulcanization that EVA and 40 mass parts step 2 of 50 mass parts containing 20% Vinyl Acetate Monomer are obtained is added and divides in advance
Glue is dissipated, 7 mass parts of antioxidant 1010,3 mass parts of ZnO, 1 mass parts of Hst, 1 mass parts of captax, 1 mass of S is added
Part, 2 mass parts of DCP, 8 mass parts of foaming agent；Bao Tong obtains Blend rubber；
Step 4：After Blend rubber made from step 3 is parked for 24 hours, sulfurizing time and foamed time are measured with vulcameter, is used
Vulcanizing press moulded from foam, curing temperature are 160 DEG C, obtain wear-resisting ternary EVA base rubber blends, preparation flow is as schemed
1, detailed performance such as table 1.
Embodiment 2
By the method that specified each component content repeats embodiment 1, but use in step 1 30 μm of calcium carbonate, Hst 2
G uses 5 mass parts of irgasfos 168,4 mass parts of ZnO, 0.5 mass parts of Hst, 2 mass of accelerant NOBS in step 3
Part, 0.5 mass parts of S, 1 mass parts of DCP, 5 mass parts of foaming agent azodicarbonamide, obtained wear-resisting ternary EVA base rubbers
Mould the detailed performance such as table 1 of blend.
Comparative example 1
By the method that specified each component content repeats embodiment 2, but 50 μm of calcium carbonate are used in formula, what is obtained is wear-resisting
Ternary EVA base rubber blends detailed performance such as table 1.
Comparative example 2
By the method that specified each component content repeats embodiment 2, but 10 μm of calcium carbonate are used in formula, what is obtained is wear-resisting
Ternary EVA base rubber blends detailed performance such as table 1.
Comparative example 3
By the method that specified each component content repeats embodiment 2, but 5 g stearic acid are added in formulation stage one, obtain
The detailed performance such as table 1 of wear-resisting ternary EVA base rubber blends.
Comparative example 4
By the method that specified each component content repeats embodiment 2, but it is added without stearic acid in formulation stage one, what is obtained is resistance to
The detailed performance such as table 1 of the ternary EVA base rubber blends of mill.
Comparative example 5
By the method that specified each component content repeats embodiment 2, but directly all raw materials in step 2 are pressed in formula
Ratio is mixed with raw material in step 3, the detailed performance such as table 1 of obtained wear-resisting ternary EVA base rubber blends.
Comparative example 6
By the method that specified each component content repeats embodiment 2, but DCP is not added in formulation stage two, what is obtained is wear-resisting
Ternary EVA base rubber blends detailed performance such as table 1.
Comparative example 7
By the method that specified each component content repeats embodiment 2, but in formulation stage two, it is added without maleic anhydride,
The detailed performance such as table 1 of obtained wear-resisting ternary EVA base rubber blends.
Comparative example 8
By the method that specified each component content repeats embodiment 2, but in formulation stage two, all raw materials are added at one time,
The detailed performance such as table 1 of obtained wear-resisting ternary EVA base rubber blends.
Comparative example 9
By the method that specified each component content repeats embodiment 2, but in formulation stage three, DCP is not added, what is obtained is wear-resisting
Ternary EVA base rubber blends detailed performance such as table 1.
Comparative example 10
By the method that specified each component content repeats embodiment 2, but in formulation stage three, Hst, ZnO, accelerating agent are not added
And S, the detailed performance such as table 1 of obtained wear-resisting ternary EVA base rubber blends.
Table 1
| Firmly Spend C | Density (g/ cm3) | Tensile strength (MPa) | Tearing strength (kN/m) | Dimensional contraction rate (%) | Resilience (%) | Compression deformation rate (%) | DIN is worn away (mm3) | |
| Embodiment 1 | 48 | 0.17 | 8.5 | 11.50 | 0.90 | 87 | 11 | 239 |
| Embodiment 2 | 48 | 0.18 | 9.1 | 12.00 | 0.80 | 90 | 12 | 229 |
| Comparative example 1 | 51 | 0.22 | 3.7 | 7.50 | 2.60 | 47 | 15 | 384 |
| Comparative example 2 | 51 | 0.23 | 3.5 | 7.60 | 2.50 | 49 | 13 | 379 |
| Comparative example 3 | 48 | 0.26 | 2.8 | 5.10 | 3.90 | 52 | 24 | 454 |
| Comparative example 4 | 52 | 0.24 | 3.8 | 8.00 | 2.30 | 55 | 19 | 359 |
| Comparative example 5 | 53 | 0.25 | 2.6 | 4.80 | 3.70 | 46 | 29 | 484 |
| Comparative example 6 | 52 | 0.26 | 3.8 | 7.40 | 3.30 | 50 | 21 | 439 |
| Comparative example 7 | 51 | 0.25 | 3.7 | 7.70 | 3.50 | 52 | 19 | 429 |
| Comparative example 8 | 53 | 0.24 | 3.5 | 7.60 | 3.20 | 52 | 20 | 434 |
| Comparative example 9 | 49 | 0.18 | 4.4 | 8.90 | 4.50 | 57 | 32 | 494 |
| Comparative example 10 | 52 | 0.17 | 5.1 | 7.20 | 3.00 | 45 | 12 | 424 |
The present invention provides a kind of wear-resisting ternary EVA base rubber blends and preparation method thereof.What is be prepared is wear-resisting
Ternary EVA base rubber blends, wear-resisting property is excellent, and elasticity is high, resilience performance is good, dimensionally stable, mechanical property are good, can be used for
The sole of sport footwear.
Claims (5)
1. a kind of preparation method of wear-resisting ternary EVA base rubber blends, it is characterised in that comprise the steps of：
Step 1：The calcium carbonate of 100 g is added in 500 mL ethanol solutions, 10 min are stirred by ultrasonic in 500 W, and 1-2 g are added
5 min are stirred by ultrasonic in Hst, 500 W, centrifuge, dry, and ball milling obtains modified calcium carbonate；
Step 2：20 mass parts SEBS are kneaded on 120 DEG C of open mill, the modification that 100 mass parts step 1 obtain is added
Calcium carbonate is kneaded 8 min, and the modified calcium carbonate that 50 mass parts EVA of addition and 100 mass parts step 1 obtain is kneaded 5 min,
Temperature is reduced to 80 DEG C, the modified calcium carbonate that the SBR of 30 mass parts and 100 mass parts step 1 obtain is kneaded 8 min, is added
The maleic anhydride of 5 mass parts is kneaded 3 min, 5 mass parts DCP is added, 80 DEG C are continued to be kneaded 10 min, obtain dynamic sulphur
Change pre-dispersed glue；
Step 3：5 min are blended on 120 DEG C of open mills in 30 mass parts SBR and 20 mass parts SEBS, 80 DEG C is cooled to, adds
Enter the EVA of 50 mass parts and the pre-dispersed glue of dynamic vulcanization that 40 mass parts step 2 obtain, antioxidant 5-7 mass parts, ZnO is added
3-4 mass parts, Hst 0.5-1 mass parts, accelerating agent 1-2 mass parts, Sulfur 0.5-1 mass parts, DCP 1-2 mass parts, foaming
Agent 5-8 mass parts；Bao Tong obtains Blend rubber；
Step 4：After Blend rubber made from step 3 is parked for 24 hours, sulfurizing time and foamed time are measured with vulcameter, is used
Vulcanizing press moulded from foam, curing temperature are 160 DEG C, obtain wear-resisting ternary EVA base rubber blends.
2. the preparation method of wear-resisting ternary EVA base rubber blends according to claim 1, which is characterized in that step
The size of calcium carbonate in one is 30-40 μm.
3. the preparation method of wear-resisting ternary EVA base rubber blends according to claim 1, which is characterized in that step
Two and step 3 in SBR be SBR1502, SEBS H1077, EVA are the EVA containing 15% Vinyl Acetate Monomer.
4. the preparation method of wear-resisting ternary EVA base rubber blends according to claim 1, which is characterized in that step
Antioxidant in four is any one in antioxidant 1010 and irgasfos 168, and accelerating agent is any one in M and NOBS,
Foaming agent is azodicarbonamide.
5. a kind of wear-resisting ternary EVA base rubber blends being prepared according to any one of claim 1-4 the methods.
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| CN201810109178.8A Pending CN108395608A (en) | 2018-02-05 | 2018-02-05 | A kind of wear-resisting ternary EVA base rubber blends and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1916055A (en) * | 2006-09-12 | 2007-02-21 | 北京化工大学 | Method for raising fluidity of thermoplastic cross-linked rubber |
| CN102532675A (en) * | 2011-12-16 | 2012-07-04 | 蔡龙源 | Foaming material for shoes |
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2018
- 2018-02-05 CN CN201810109178.8A patent/CN108395608A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1916055A (en) * | 2006-09-12 | 2007-02-21 | 北京化工大学 | Method for raising fluidity of thermoplastic cross-linked rubber |
| CN102532675A (en) * | 2011-12-16 | 2012-07-04 | 蔡龙源 | Foaming material for shoes |
Non-Patent Citations (1)
| Title |
|---|
| 郑永林: "《粉体表面改性 第3版》", 30 September 2011, 第26页 * |
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Application publication date: 20180814 |