CN105820383B - A kind of composite-material abrasive sole - Google Patents
A kind of composite-material abrasive sole Download PDFInfo
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- CN105820383B CN105820383B CN201610346021.8A CN201610346021A CN105820383B CN 105820383 B CN105820383 B CN 105820383B CN 201610346021 A CN201610346021 A CN 201610346021A CN 105820383 B CN105820383 B CN 105820383B
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- 239000002131 composite material Substances 0.000 title claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229920001971 elastomer Polymers 0.000 claims abstract description 69
- 239000005060 rubber Substances 0.000 claims abstract description 69
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 52
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011787 zinc oxide Substances 0.000 claims abstract description 42
- 239000006229 carbon black Substances 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 24
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 24
- 229920001194 natural rubber Polymers 0.000 claims abstract description 24
- 230000003213 activating effect Effects 0.000 claims abstract description 18
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005864 Sulphur Substances 0.000 claims abstract description 13
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 19
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 235000021355 Stearic acid Nutrition 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 13
- 239000008117 stearic acid Substances 0.000 claims description 13
- 229920000459 Nitrile rubber Polymers 0.000 claims description 12
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940069744 2,2'-dithiobisbenzothiazole Drugs 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims description 3
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000005442 diisocyanate group Chemical group 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 230000008093 supporting effect Effects 0.000 abstract description 4
- 230000001976 improved effect Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000004513 sizing Methods 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 2
- 235000006708 antioxidants Nutrition 0.000 description 41
- 235000019241 carbon black Nutrition 0.000 description 29
- 230000000694 effects Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- -1 wherein Polymers 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 7
- 239000003292 glue Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 230000002079 cooperative effect Effects 0.000 description 3
- 239000013536 elastomeric material Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000010058 rubber compounding Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- 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
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—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
A kind of composite-material abrasive sole, include following raw material according to parts by weight：60~100 parts of natural rubber；10~50 parts of butadiene-styrene rubber；5~20 parts of polar rubber；10~60 parts of modified white carbon black；1~10 part of zinc oxide；1~4 part of accelerator；0.1~0.5 part of antioxidant；2.5~4.5 parts of activating agent；5~20 parts of filler；1~10 part of sulphur, the filler is four acicular type zinc oxide crystal whisker, the present invention is by natural rubber and a small amount of polar rubber collectively as main body sizing material, the white carbon by toluene di-isocyanate(TDI) graft modification be with the addition of as supporting material, the four acicular type zinc oxide crystal whisker regular using structure height is used as filling skeleton, accelerator, composite antioxidant, activating agent are sequentially added, prepares the composite-material abrasive sole that resistance to wet and slippery characteristic is high, tearing strength is big, coefficient of friction is obviously improved.
Description
Technical field
The present invention relates to material for sole of shoe technical field, more particularly to a kind of composite-material abrasive sole.
Background technology
Today's society, the lifting of living standard cause outdoor exercise to be increasingly becoming rather well received salubrity with remote walking
It is healthy and strong one of mode, and the security moved proposes harsh requirement to the material for preparing sole with comfortableness, should have
Standby high resiliency, needs wear-resisting antiskid again and suitable large-scale processing manufactures, and is needed so as to tackle complicated and in changeable environment walking
Will.
In numerous characteristics, the anti-wear performance of sole is particularly subject to pay close attention to, and existing test data shows, in use state
Under, sole contact people's pin and sole are 0.4~0.7Mpa to average pressure caused by ground, and some individual sites of step are applied
For the pressure added more than 1.5Mpa, the frictional force that sole undertakes is quite big, and need walking medium-high frequency, for a long time repeat by
The process of extruding.
At present, motion or mountaineering shoe sole are prepared using bipeltate as raw material more, application publication number CN
102863663A Chinese patent discloses high abrasion bipeltate footwear, and the raw material of the sole is by weight ratio：Natural rubber
50-70 parts；Butadiene-styrene rubber 80-90 parts；Stearic acid 5-10 parts；Pigment 10-20 parts；Filler 30-50 parts；Foaming agent 5-10 parts；
Blowing promotor 2-3 parts；Plasticizer 2-5 parts, the preparation principle of such a material for sole of shoe is simple, production cost is relatively low, oeverall quality compared with
Gently, however, the composition mechanism of action between rubber, compounding ingredient and filler in the material for sole of shoe is single, sole it is overall strong
Degree, hardness and resilience are extremely limited, and elongation at break is very undesirable with the coefficient of friction under drying regime, it is difficult to meet complicated
Use demand in environment.
The content of the invention
First purpose of the present invention is to provide a kind of composite-material abrasive sole.
The present invention first technical purpose technical scheme is that：
A kind of composite-material abrasive sole, the sole include following raw material according to parts by weight：
The filler is four acicular type zinc oxide crystal whisker.
By using above-mentioned technical proposal, the present invention relates to rubber compounding in, the primary raw material of rubber employs day
T PNR, butadiene-styrene rubber and polar rubber, wherein, natural rubber (NR) is the natural polymer using polyisoprene as main component
Sub- compound, unsaturated double-bond present in molecular structure assign natural rubber very high chemical reaction ability, possessed outstanding
Mechanical strength and processing characteristics, elasticity is good under normal temperature, and alkali resistance is good, but intolerant to strong acid, is accounted at present in global rubber consumption
40%, distribution is extremely wide；The physical and mechanical properties of butadiene-styrene rubber is also equipped with certain wearability, heat-resisting close to natural rubber
Property, can be with other rubber blendings.
Add compounding ingredient in the rubber compounding of above-mentioned mixing, including zinc oxide, accelerator, antioxidant, activating agent, fill out
Fill agent, sulphur.Wherein, sulphur to be cross-linked into network structure, the addition energy of accelerator between rubber macromolecule as vulcanizing agent
Enough reaction rates effectively shortened between sulphur and rubber macromolecule, accelerate cross-linking reaction therebetween；Antioxidant can delay
Or suppress the progress of polymer oxidizing process, so as to prevent the aging of polymer and extend its service life so that material for sole of shoe
It is difficult to be oxidized, it is more durable；Activating agent has cooperative effect with accelerator, and its presence can increase the activity of accelerator, subtract
Dosage of few accelerator in reaction system and shorten the time of vulcanization reaction process progress；The presence of zinc oxide on the one hand can
Used using the colouring agent as white sizing material and filler, make sole not easy to change, activated zinc oxide, rubber tool are added in sizing material
There are good wearability, resistance to tearing and elasticity, sole is comfortable and easy to wear, earth-grasping force enhancing, disclosure satisfy that changeable and complicated row
Walk environment, resistance to wet and slippery positive effect, in addition, zinc oxide be also used as natural rubber, the reinforcing agent of synthetic rubber, activating agent and
Vulcanizing agent plays synergy.
In addition, modified white carbon black is additionally added in above-mentioned formula as interstitital texture, reinforcing material of the white carbon as rubber
Material, existing mechanism show, between carbon black aggregate enters the cross-linked network of vulcanizate, and rubber molecule absorption is in carbon black particle
Surface, the two strong bonded, strengthening action is played, white carbon is as filler, for manufacturing transparent or opaque sole
During material, the wearability of elastomeric material can be improved, the tear-resistant intensity and hardness of product can all increase.
The further setting of the present invention is that the polar rubber is neoprene, nitrile rubber, hydrogenated nitrile-butadiene rubber, carboxylic
Base nitrile rubber, fluorubber, polyurethane rubber, polyether rubber, polysulfide rubber, ACM, chlorinated polyethylene rubber, chlorine
One or more in sulfonated polyethylene rubber are combined.
By using above-mentioned technical proposal, polar rubber is added in rubber formula of the invention, when possessing pole on main chain
During property substituent, the rubber of polar structure has bigger intermolecular force compared to non-polar rubber, intermolecular regular
Property it is high, easily carry out stretch crystallization, the intensity of rubber can also improve therewith.
The further setting of the present invention is that the preparation method of the modified white carbon black is as follows：
In the case where being passed through the reaction condition of nitrogen and condensing reflux, by toluene di-isocyanate(TDI) and nano silicon and
Appropriate anhydrous propanone, magnetic agitation is first carried out at room temperature and obtains more uniform dispersion, reacts and drops under suitable condition
Temperature, by ethanol centrifuge washing, vacuum drying, prepare the modified white carbon black by toluene di-isocyanate(TDI) grafting.
By using above-mentioned technical proposal, silica-filled natural rubber possesses excellent anti-skidding in a moistened state
Performance, the present invention is with toluene di-isocyanate(TDI) (TDI) and nano silicon (nano-SiO2) reaction, obtain modified white carbon black.
Graft reaction principle is：By high activity-NCO group and nano-SiO present in TDI molecular structures2- OH the reactions on surface,
General-NCO group is incorporated into nano-SiO2Surface, white carbon surface will be introduced by the larger TDI molecules of modified polarity, it is real
Now to the modification of packing material, and pass through the white carbon that isocyanate groups are modified, rubber significantly anti-skidding spy can be assigned
Property, so as to realize the outstanding crocking resistance of sole.
The further setting of the present invention is the weight of toluene di-isocyanate(TDI) and nano silicon in the modified white carbon black
Amount is than being 0.9: 1~1.2: 1.
By using above-mentioned technical proposal, in the preparation process of modified white carbon black, it is found through experiments that, when toluene two is different
When cyanate and nano silicon carry out graft reaction according to weight ratio for 0.9: 1~1.2: 1, the product obtained is resistance to wet and slippery
Performance is optimal.
The further setting of the present invention is that the four acicular type zinc oxide crystal whisker is surface-treated by silane coupler, specifically
Process is：Four acicular type zinc oxide crystal whisker is cleaned and is dried, the two is carried out blending reaction after adding coupling agent, the time is
0.5~1 hour, reaction was washed to product, filtered, drying and processing successively after terminating, and is obtained through four coupling agent modified pins
Shape ZnOw.
By using above-mentioned technical proposal, during the non-reinforcement of elastomeric material, mechanical property and processing performance are poor, and filler has
To the reinforcing function of elastomeric material, its tensile strength, tearing strength, wearability are improved, in addition, filler is also equipped with improving processability
The effect of cost, can be reduced.However, the compatibility of filler and rubber surface is poor, it is necessary to is surface-treated.
In the rubber compounding of the present invention, four acicular type zinc oxide crystal whisker is as a kind of new supporting material, and structure is almost
Zero defect, belong to rare ideal crystal, its whisker intensity is also extremely close to the theoretical value of perfect crystal, the unique solid of whisker
Four needle-like three-dimensional structures, can be uniformly distributed in matrix material, and isotropically improve the physical property of material, simultaneously
The a variety of unique functional characteristics of material are assigned, using surface treatment of the KH550 silane couplers as four acicular type zinc oxide crystal whisker
Agent uses, by increasing capacitance it is possible to increase the interface cohesion degree between packing material and polymer, in addition, the relatively low coupling agent of molecular weight can
Viscosity is reduced, the good fluidity of paste system, following process is convenient for, makes four acicular type zinc oxide crystal whisker energy in rubber matrix
Enough play maximum strengthening action.
The further setting of the present invention is that the activating agent is stearic acid and/or zinc stearate.
By using above-mentioned technical proposal, stearic acid and/or zinc stearate are added with formula of the invention, on the one hand,
Stearic acid or zinc stearate can play the effect of plasticizer and softening agent in natural rubber and synthetic rubber, possess reduction body
Be the effect of viscosity, can increase mobility, reduce the hardness of vulcanization rubber, contribute to the scattered of filler, be also convenient for extruding and into
Type technique is smoothed out, and on the other hand, such activating agent can also play the effect of vulcanizing activator.
The further setting of the present invention is that the antioxidant includes primary antioxidant and auxiliary antioxidant, the primary antioxidant
Including hindered amines and/or Hinered phenols antioxidant, including antioxidant 1010, antioxidant 1076, antioxidant 1790 and antioxygen
Any one or more in agent BHT, the auxiliary antioxidant are phosphite ester kind antioxidant, and the auxiliary antioxidant includes anti-
One or more in oxygen agent 168, triphenyl phosphite (TPP) are combined.
By using above-mentioned technical proposal, in the present invention using primary antioxidant by the way of auxiliary antioxidant is combined, lead
Antioxidant is hindered amines and/or Hinered phenols antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant, and the two is added simultaneously
In polymer, cooperative effect is notable, can effectively suppress the thermal degradation and oxidative degradation of polymer, extends the use of polymer
Life-span.
The further setting of the present invention is that the accelerator includes accelerant N-cyclohexyl -2-[4-morpholinodithio sulfenamide
With accelerator 2,2 '-dithio-bis-benzothiazole, N cyclohexyl 2 benzothiazole sulfenamide and 2,2 '-two thio dibenzo
Thiazole is combined according to mass ratio for 0.8: 1~1.1: 1.
By using above-mentioned technical proposal, two kinds of accelerator, respectively N- cyclohexyl -2- benzo thiophenes are employed in the present invention
Azoles sulfenamide (accelerant CZ) and 2,2 '-dibenzothiazyl disulfide (altax), accelerant CZ is delayed action accelerator,
Altax is universal accelerator, when the two coordinated is applied, has complementation, can increase the promotion effect of accelerator
Power, promote the progress of rubber vulcanization process process.
The further setting of the present invention is that the polar rubber is hydrogenated nitrile-butadiene rubber, ACM, chlorosulfonation are gathered
Ethylene rubber coordinates according to 1: 1: 1~1: 1.2: 1.2 mass ratio to be formed.
By using above-mentioned technical proposal, the polar rubber in the present invention includes hydrogenated nitrile-butadiene rubber (HNBR), acrylic acid
Ester rubber (ACM), CSM (CSM), three make according to certain proportioning with natural rubber collectively as rubber
With, wherein, HNBR glue has HI SA highly saturated structure, possesses heat resistance, excellent resistance to chemical corrosion and ozone resistance,
Higher incompressible permanent deformation performance, HNBR glue also have high intensity, and high tear energy, anti-wear performance is excellent, combination property
It is extremely outstanding；ACM glue main chain is saturated carbon chains, and side base is polar ester groups, heat-resisting, ageing-resistant, oil resistant, resistance to ozone, uvioresistant；
CSM glue belongs to specific rubber, contains chlorine sulphonyl active group in molecular structure, possesses high activity, resistant to chemical media burn into resists smelly
Oxygen aoxidizes and resistance to oil corrosion, fire resistance protrude, and also becomes with anti-time, be heat-resisting, anti-ionizing radiation, low temperature resistant, anti scuffing and electricity
Insulating properties and excellent mechanical performance.
In the present invention, three kinds of polar rubbers use as rubber simultaneously with natural rubber, form a multicomponent blending
System, on the one hand, complementation is realized in performance, the advantages of being advantageous to give full play to each component rubber so that final molding
Shoe sole article possesses rub resistance, high tear, high-strength characteristic, can also anti-oxidant, high temperature resistant, anticorrosion, fire-retardant, greatly lifted
Combination property of the sole in environment complicated and changeable, meets the needs of user is to high-performance sole, simultaneously as polarity rubber
Glue ratio shared in the overall weight of rubber is in a less scope, when several components mix progress jointly
During vulcanization, curingprocess rate is easy to control with sulfidation, does not interfere with technological process.
Second technical purpose of the present invention is to provide a kind of preparation method of composite-material abrasive sole.
Second technical purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of composite-material abrasive sole, its processing step and process conditions include：
(1) natural rubber, butadiene-styrene rubber, polar rubber are positioned in mill and plasticated；
(2) modified white carbon black, zinc oxide, age resistor, antioxidant, activating agent are sequentially added, slice is simultaneously shredded, continuously added
Four acicular type zinc oxide crystal whisker, mixing action is carried out in banbury, uniformly after discharge, melting temperature is 70~85 DEG C, during mixing
Between be 6~10 minutes；
(3) it is placed in after the mixed material obtained by mixing step is placed 15~20 hours in mill, adds and promote
Agent, sulphur, vulcanize simultaneously bottom sheet using vulcanizer, obtain vulcanizate sample.
In summary, the invention has the advantages that：
1st, in rubber of the invention formula, a small amount of polar rubber and the non-polar rubbers such as natural rubber, butadiene-styrene rubber are total to
It is mixed, cooperative compensating is realized in performance, the advantages of giving full play to each component rubber, final shoe sole article is possessed antifriction
Wipe, high tear, high-strength characteristic, can also anti-oxidant, high temperature resistant, anticorrosion, fire-retardant, significant increase sole is in ring complicated and changeable
Performance in border, meets the needs of user is to high-performance sole, simultaneously as polar rubber is shared in rubber overall weight
Ratio is smaller, and curingprocess rate is easy to control with sulfidation, does not interfere with technological operation, has product excellent comprehensive
Energy.
2nd, further, in the system based on above-mentioned blended rubber, add by modified inorganic nano material, warp
Cross TDI and nano-SiO2React and obtain modified white carbon black, high activity-NCO group and nano-SiO in TDI2- the OH on surface is anti-
Should, TDI molecules are incorporated into white carbon surface by chemical graft, and modified white carbon black assigns rubber and significantly prevents wet and slippery spy
Property, in dry conditions, the coefficient of friction of composite has very big lifting.
3rd, by above-mentioned graft reaction, a variety of synergies are generated between modified white carbon black and matrix material, first, in vain
Carbon blacksurface introduces TDI, and-OH quantity is reduced, and its structure is changed into hydrophobic from hydrophilic, increases its interface phase between polymer
Capacitive, secondly, three kinds of polar rubbers HNBR, ACM, CSM are added in rubber, and modified white carbon black surface is larger with polarity
TDI, there is good compatibility between the polar rubber in modified white carbon black and rubber, be advantageous in polymer between each component
Well mixed, supporting material can be good at being scattered among matrix, play splendid rub resistance effect.
4th, in above-mentioned rubber formula and supporting material system, four acicular type zinc oxide crystal whisker is continuously added as filling material
Material, its unique three-dimensional structure form the skeleton of mixed system, and the tearing strength and tensile strength for making product significantly increase, product
The characteristic of high-strength and high ductility can be had concurrently simultaneously.
5th, compounding ingredient of the invention also includes antioxidant, using primary antioxidant by the way of auxiliary antioxidant is combined, when
The two is made an addition in polymer simultaneously, is possessed cooperative effect, can effectively be suppressed the thermal degradation and oxidative degradation of polymer, is extended
The service life of polymer.
6th, the addition of stearic acid and/or zinc stearate, on the one hand, stearic acid or zinc stearate are in natural rubber and synthesis rubber
The effect of plasticizer and softening agent is played in glue, reduces system viscosity, increases mobility, vulcanization rubber hardness is reduced, contributes to
Filler disperses, and is easy to extrude the progress with moulding process, on the other hand, such activating agent is applied can also in rubbery system
Play the effect of vulcanizing activator.
Embodiment
The present invention is described in further detail by herein below.
Embodiment one
A kind of composite-material abrasive sole, sole include following raw material according to parts by weight：
100 parts of natural rubber
10 parts of butadiene-styrene rubber
5 parts of polar rubber, wherein hydrogenated nitrile-butadiene rubber, ACM, CSM are according to 1: 1: 1
Mass ratio, which coordinates, to be formed
10 parts of modified white carbon black
2 parts of zinc oxide
1 part of accelerator, is combined by accelerant CZ and altax according to mass ratio 1: 1
0.1 part of antioxidant, primary antioxidant are antioxidant 1010, auxiliary antioxidant TPP
2.5 parts of activating agent, it is stearic acid
20 parts of four acicular type zinc oxide crystal whisker
2 parts of sulphur
In the present embodiment, the preparation method of TDI modified white carbon blacks is：It is being passed through the reaction bar of nitrogen and condensing reflux
Under part, TDI and nano-SiO 2 is added in four-hole boiling flask according to 1: 1 mass ratio, places into acetone, magnetic agitation, heating
Reacted 4.5 hours to 82 DEG C, cooling, wash and be dried in vacuo, obtain modified white carbon black.
In the present embodiment, the surface treatment step of four acicular type zinc oxide crystal whisker is：Four acicular type zinc oxide crystal whisker is cleaned
And dry, adding KH550 makes the two blending reaction 0.5 hour, and reaction is washed to product, filters, dries successively after terminating
Processing, is obtained through coupling agent modified four acicular type zinc oxide crystal whisker.
The preparation method of composite-material abrasive sole：
(1) that natural rubber, butadiene-styrene rubber, polar rubber are positioned over into mill according to the weight proportion in embodiment is enterprising
Row is plasticated；
(2) modified white carbon black, zinc oxide, age resistor, antioxidant, activating agent are sequentially added, slice is simultaneously shredded, continuously added
Four acicular type zinc oxide crystal whisker, mixing action is carried out in banbury, uniformly rear discharge, melting temperature is 78 DEG C, mixing time 9
Minute；
(3) it is placed in after the mixed material obtained by mixing step is placed 15~20 hours in mill, adds and promote
Agent and sulphur, vulcanize simultaneously bottom sheet using vulcanizer, obtain vulcanizate sample.
Embodiment two
100 parts of natural rubber
20 parts of butadiene-styrene rubber
15 parts of polar rubber, wherein hydrogenated nitrile-butadiene rubber, ACM, CSM are according to 1: 1: 1
Mass ratio coordinate form
10 parts of modified white carbon black
2 parts of zinc oxide
1 part of accelerator, is combined by accelerant CZ and altax according to mass ratio 1: 1
0.1 part of antioxidant, primary antioxidant are antioxidant 1010, auxiliary antioxidant TPP
2.5 parts of activating agent, it is stearic acid
20 parts of four acicular type zinc oxide crystal whisker
2 parts of sulphur
In the present embodiment, the preparation method of TDI modified white carbon blacks is identical with embodiment one.
In the present embodiment, the surface treatment step of four acicular type zinc oxide crystal whisker is identical with embodiment one.
Embodiment three
100 parts of natural rubber
20 parts of butadiene-styrene rubber
15 parts of polar rubber, wherein hydrogenated nitrile-butadiene rubber, ACM, CSM are according to 1: 1: 1
Mass ratio coordinate form
30 parts of modified white carbon black
2 parts of zinc oxide
1 part of accelerator, is combined by accelerant CZ and altax according to mass ratio 1: 1
0.1 part of antioxidant, primary antioxidant are antioxidant 1010, auxiliary antioxidant TPP
2.5 parts of activating agent, it is stearic acid
10 parts of four acicular type zinc oxide crystal whisker
2 parts of sulphur
In the present embodiment, the preparation method of TDI modified white carbon blacks is identical with embodiment one.
In the present embodiment, the surface treatment step of four acicular type zinc oxide crystal whisker is identical with embodiment one.
Example IV
100 parts of natural rubber
20 parts of butadiene-styrene rubber
15 parts of polar rubber, wherein hydrogenated nitrile-butadiene rubber, ACM, CSM are according to 1: 1: 1
Mass ratio coordinate form
40 parts of modified white carbon black
4 parts of zinc oxide
2 parts of accelerator, is combined by accelerant CZ and altax according to mass ratio 1: 1
0.3 part of antioxidant, primary antioxidant are antioxidant 1010, auxiliary antioxidant TPP
3.5 parts of activating agent, it is stearic acid
15 parts of four acicular type zinc oxide crystal whisker
2 parts of sulphur
In the present embodiment, the preparation method of TDI modified white carbon blacks is identical with embodiment one.
In the present embodiment, the surface treatment step of four acicular type zinc oxide crystal whisker is identical with embodiment one.
Embodiment five
100 parts of natural rubber
20 parts of butadiene-styrene rubber
20 parts of polar rubber, wherein hydrogenated nitrile-butadiene rubber, ACM, CSM are according to 1: 1: 1
Mass ratio coordinate form
60 parts of modified white carbon black
4 parts of zinc oxide
4 parts of accelerator, is combined by accelerant CZ and altax according to mass ratio 1: 1
0.3 part of antioxidant, primary antioxidant are antioxidant 1010, auxiliary antioxidant TPP
3.5 parts of activating agent, it is stearic acid
10 parts of four acicular type zinc oxide crystal whisker
2 parts of sulphur
In the present embodiment, the preparation method of TDI modified white carbon blacks is identical with embodiment one.
In the present embodiment, the surface treatment step of four acicular type zinc oxide crystal whisker is identical with embodiment one.
Embodiment six
100 parts of natural rubber
20 parts of butadiene-styrene rubber
20 parts of polar rubber, wherein hydrogenated nitrile-butadiene rubber, ACM, CSM are according to 1: 1: 1
Mass ratio coordinate form
60 parts of modified white carbon black
4 parts of zinc oxide
4 parts of accelerator, is combined by accelerant CZ and altax according to mass ratio 1: 1
0.3 part of antioxidant, primary antioxidant are antioxidant 1010, auxiliary antioxidant TPP
3.5 parts of activating agent, it is stearic acid
5 parts of four acicular type zinc oxide crystal whisker
2 parts of sulphur
In the present embodiment, the preparation method of TDI modified white carbon blacks is identical with embodiment one.
In the present embodiment, the surface treatment step of four acicular type zinc oxide crystal whisker is identical with embodiment one.
Table 1
Performance test is carried out to above-described embodiment, test condition is as follows.
Physical and mechanical properties is tested：
The tensile property of sample is carried out according to GB/T 528-1998 standard.
The tearing strength of sample is carried out according to GB/T 529-1999 standard.
The shore hardness of sample is carried out using GB/T 531-1999 standard.
Frictional behaviour is tested：
The coefficient of friction of sample is carried out according to HG/T2729-1995 professional standard.
Test condition is as follows：
| Test event | Test condition | Unit |
| Shore hardness | Shao A | |
| Tensile strength | Specimen width 6mm, sample thickness 1mm | MPa |
| Elongation at break | Specimen width 6mm, sample thickness 1mm | % |
| Tearing strength | Right angle sample | KN/m |
Test result is as follows：
Understood with reference to above-described embodiment formula and the performance test results, in the present invention, three kinds of polar rubber HNBR,
The blending of the non-polar rubber such as ACM, CSM and natural rubber, butadiene-styrene rubber is used as rubber, and T- is also added into the system
ZnOw, with modified white carbon black fit applications, has a variety of cooperative compensating effects, the sole rub resistance of preparation as framework material
Good, tearing strength maximum can reach 67KN/m, and tensile strength maximum reaches 23.2MPa, and shore hardness maximum can reach
63 Shao A, the composite have high intensity, rub resistance characteristic, can meet the needs of user is to high-performance sole.
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
Member can make the modification of no creative contribution to the present embodiment as needed after this specification is read, but as long as at this
All protected in the right of invention by Patent Law.
Claims (6)
1. a kind of composite-material abrasive sole, it is characterised in that the sole includes following raw material according to parts by weight：
60~100 parts of natural rubber
10~50 parts of butadiene-styrene rubber
5~20 parts of polar rubber
10~60 parts of modified white carbon black
1~10 part of zinc oxide
1~4 part of accelerator
0.1~0.5 part of antioxidant
2.5~4.5 parts of activating agent
5~20 parts of filler
1~10 part of sulphur
The filler is four acicular type zinc oxide crystal whisker, and the antioxidant includes primary antioxidant and auxiliary antioxidant, and the master resists
Oxygen agent includes hindered amines and/or Hinered phenols antioxidant, including antioxidant 1010, antioxidant 1076, antioxidant 1790 and
Any one or more in antioxidant BHT, the auxiliary antioxidant are phosphite ester kind antioxidant, the auxiliary antioxidant bag
The one or more included in irgasfos 168, triphenyl phosphite are combined, and the polar rubber is hydrogenated nitrile-butadiene rubber, third
Olefin(e) acid ester rubber, CSM are according to 1：1：1~1:1.2:1.2 mass ratio, which coordinates, to be formed.
A kind of 2. composite-material abrasive sole according to claim 1, it is characterised in that the preparation of the modified white carbon black
Method is as follows：In the case where being passed through the reaction condition of nitrogen and condensing reflux, by toluene di-isocyanate(TDI) and nano silicon with
And appropriate anhydrous propanone, magnetic agitation is first carried out at room temperature and obtains more uniform dispersion, is reacted simultaneously under suitable condition
Cooling, by ethanol centrifuge washing, vacuum drying, prepare the modified white carbon black by toluene di-isocyanate(TDI) grafting.
A kind of 3. composite-material abrasive sole according to claim 2, it is characterised in that toluene in the modified white carbon black
The weight of diisocyanate and nano silicon ratio is 0.9:1~1.2:1.
A kind of 4. composite-material abrasive sole according to claim 1, it is characterised in that the four acicular type zinc oxide crystal whisker
It is surface-treated by silane coupler, detailed process is：Four acicular type zinc oxide crystal whisker is cleaned and is dried, adds coupling agent
After the two is carried out blending reaction, the time is 0.5~1 hour, and reaction is washed to product after terminating, filter, dry successively
Processing, is obtained through coupling agent modified four acicular type zinc oxide crystal whisker.
5. a kind of composite-material abrasive sole according to claim 1, it is characterised in that the activating agent is stearic acid
And/or zinc stearate.
6. a kind of composite-material abrasive sole according to claim 1, it is characterised in that the accelerator includes accelerator
N cyclohexyl 2 benzothiazole sulfenamide and accelerator 2,2 '-dithio-bis-benzothiazole, N- cyclohexyl -2-[4-morpholinodithio
Sulfenamide and 2,2'- dithio-bis-benzothiazole are 0.8 according to mass ratio:1~1.1:1 is combined.
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| CN104629100A (en) * | 2013-11-07 | 2015-05-20 | 青岛博研达工业技术研究所(普通合伙) | Wear-resistant damping flame-retardant material and manufacturing method thereof |
| CN104817731A (en) * | 2015-04-24 | 2015-08-05 | 茂泰(福建)鞋材有限公司 | Noiseless comfortable rubber heel lift and preparation method thereof |
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| CN105820383A (en) | 2016-08-03 |
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