CN105524312A - Cold-resistant and light-resistant NBR (nitrile-butadiene rubber) sole material and preparation method thereof - Google Patents
Cold-resistant and light-resistant NBR (nitrile-butadiene rubber) sole material and preparation method thereof Download PDFInfo
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- CN105524312A CN105524312A CN201610038948.5A CN201610038948A CN105524312A CN 105524312 A CN105524312 A CN 105524312A CN 201610038948 A CN201610038948 A CN 201610038948A CN 105524312 A CN105524312 A CN 105524312A
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000459 Nitrile rubber Polymers 0.000 title abstract description 45
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 17
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 17
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008117 stearic acid Substances 0.000 claims abstract description 17
- 239000011787 zinc oxide Substances 0.000 claims abstract description 17
- 238000005728 strengthening Methods 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims description 29
- 239000005060 rubber Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 24
- 230000003712 anti-aging effect Effects 0.000 claims description 20
- 239000003381 stabilizer Substances 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 235000014692 zinc oxide Nutrition 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 15
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical group [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical group C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 claims description 14
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 10
- 238000005987 sulfurization reaction Methods 0.000 claims description 9
- 239000005995 Aluminium silicate Substances 0.000 claims description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 8
- 229910001887 tin oxide Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004902 Softening Agent Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 abstract description 8
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 239000003017 thermal stabilizer Substances 0.000 abstract 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 15
- 229920006380 polyphenylene oxide Polymers 0.000 description 15
- 239000003921 oil Substances 0.000 description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920013649 Paracril Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 210000003953 foreskin Anatomy 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- 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
- C08L2201/08—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
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (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 provides a cold-resistant and light-resistant NBR (nitrile-butadiene rubber) sole material, which is prepared from the following ingredients in parts by weight: 100 parts of NBR, 5 to 7 parts of plasticizing agents, 10 to 14 parts of filling materials, 3 to 4 parts of thermal stabilizers, 3 to 4 parts of strengthening agents, 2 to 3 parts of age inhibitors, 1 to 2 parts of vulcanizing agents, 1 to 2 parts of accelerating agents, 5 to 6 parts of compatilizers, 7 to 9 parts of nanometer tin dioxide, 9 to 12 parts of PPO/PS, 1 to 2 parts of stearic acid and 4 to 5 parts of zinc oxide. The invention also provides a preparation method of the sole material. The sole material provided by the invention has the advantages of good cold resistance, good light aging-resistant performance and long service life.
Description
Technical field:
The present invention relates to a kind of material for sole of shoe, particularly relate to a kind of cold-resistant fast light NBR material for sole of shoe and preparation method thereof.
Background technology:
Paracril, English NitrileButadieneRubber by name, referred to as NBR, is obtained through emulsion polymerization by divinyl and vinyl cyanide.Butadiene monomers copolymerizable becomes cis, the trans chain structure different with three kinds, 1,2-alkyl.Transly in typical NBR structure account for about 78%.Due in NBR molecular chain structure containing cyano group, so its oil-proofness (as resistance to mineral oil, liquid fuel, vegetable and animals oils and solvent) is better than natural rubber, chloroprene rubber and styrene-butadiene rubber(SBR), to have the use temperature of more wide area than NBR with other rubber phases.NBR chemical-resistant stability is good, and processing characteristics is good, and along with its relative density of increase of the acrylonitrile content in its structure increases, vulcanization rate is accelerated, and tensile strength performance improves, but rebound performance declines, and winter hardiness is deteriorated.Due to the easy electric field polarization of the cyano group in NBR, thus dielectric properties decline, and belong to semi-conducting rubber.NBR can by the height of ACN content, be divided into superelevation, height, middle height, neutralize low third rare nitrile 5 class, the mode of production is divided continuously and batchwise polymerization method two kinds, continuous polymerization is generally used for few kind and large turnout is produced, and consume low, batchwise polymerization method is applicable to multi items and small serial production, before polymerization, usage quantity is few, engineering construction consumes high, so far, does not also see the trend of phase trans-substitution.The oil-proofness of NBR and physical and mechanical properties excellence; therefore be widely used in manufacturing various oil resistant as glue goods, as at the bottom of O type circle, packing ring, flexible pipe and fuel container line with rubber, printing cylinder, tank linning, insulation ground private school plate, oil-resistant shoe, the field such as impeller and electric wire foreskin, tackiness agent, food packing film, rubber gloves of vulcanite part, fabric coating, gas thread protective layer, pump.
Such as, the Chinese patent that publication number is CN102796292A, publication date is 2012.11.28, application people is Jihua 3537 Shoe-making Co., Ltd. discloses " High-elongation wear-resistant oil-resistant rubber sole and preparation method thereof ", according to listed as parts by weight, it comprises paracril 65 ~ 75 parts, natural rubber 15 ~ 25 parts, cis-1,4-polybutadiene rubber 8 ~ 12 parts, 1.8 ~ 2.0 parts, sulphur, vulcanization accelerator 1.5 ~ 2.1 parts, vulcanization leveller 6 ~ 7 parts, Rubber Softener 15 ~ 21 parts, N330 carbon black 50 ~ 58 parts and silicon-dioxide 8 ~ 12 parts.This invention is by the sizing compound formula of design rubber overshoes sole, the processing conditions of sole rubber and the sulfuration process of sole, enhance the external force resistance ability of rubber self and improve the elongation of rubber, substantially increase outer bottom resilience, fundamentally realize the requirement of wear-resistant type oil-resistant characteristic, solve existing rubber overshoes sole oil resistant ability, the problem that not wear-resisting, elongation is low, improve the wear resisting property of rubber overshoes sole, oil-resistant characteristic and work-ing life.But, still there is certain defect in this material: winter hardiness, light aging resisting property are poor, easily brittle time in for cold environment, is easily subject to ultraviolet photochemical degradation when outdoor application, degradation is relatively more serious, and work-ing life receives impact.
Summary of the invention:
The technical problem to be solved in the present invention is to provide a kind of cold-resistant fast light NBR material for sole of shoe, and have good winter hardiness and light aging resisting property, work-ing life is longer.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of cold-resistant fast light NBR material for sole of shoe, by weight, is made up of following component: NBR100 part, 5 ~ 7 parts, softening agent, filler 10 ~ 14 parts, thermo-stabilizer 3 ~ 4 parts, strengthening agent 3 ~ 4 parts, 2 ~ 3 parts, anti-aging agent, vulcanizing agent 1 ~ 2 part, promotor 1 ~ 2 part, compatilizer 5 ~ 6 parts, nano tin dioxide 7 ~ 9 parts, PPO/PS9 ~ 12 part, stearic acid 1 ~ 2 part, zinc white 4 ~ 5 parts.
Preferably, softening agent of the present invention is DOP.
Preferably, filler of the present invention is calcium carbonate or kaolin.
Preferably, thermo-stabilizer of the present invention is calcium-zinc composite stabilizing agent.
Preferably, strengthening agent of the present invention is carbon black.
Preferably, anti-aging agent of the present invention is anti-aging agent RD.
Preferably, vulcanizing agent of the present invention is sulphur.
Preferably, promotor of the present invention is accelerator DZ.
Preferably, compatilizer of the present invention is SEBS.
Another technical problem that the present invention will solve is to provide the preparation method of above-mentioned cold-resistant fast light NBR material for sole of shoe.
For solving the problems of the technologies described above, technical scheme is:
A preparation method for cold-resistant fast light NBR material for sole of shoe, its step is as follows:
(1) nano tin-oxide powder is added in deionized water, ultrasonic disperse 12 minutes obtained massfractions are the slurries of 15%, ultrasonic disperse is continued 15 minutes after adding PEG20000, move in reflux vessel and reflux 3 hours at 80 DEG C, be cooled to discharging after room temperature, be dried to constant weight after filtration, after grinding, obtain modified Nano stannic oxide;
(2) NBR being added mill mixer roller temperature is plasticate at 80 DEG C, it is mixing at 100 DEG C for after 12 minutes, compatilizer, PPO/PS being added mill mixer roller temperature, adding the modified Nano stannic oxide that step (1) obtains after 10 minutes continues mixing, after 9 minutes, roller temperature is adjusted to 80 DEG C, roll spacing is adjusted to 2mm, then add softening agent, filler, thermo-stabilizer, strengthening agent, anti-aging agent, zinc white, stearic acid, promotor, mixing 40 minutes of vulcanizing agent successively, obtain rubber unvulcanizate;
(3) rubber unvulcanizate that step (2) obtains is placed on rolling press is rolled into film, film to be put at 110 DEG C, mould sulfuration 1 hour, take out rear microtome, obtain cold-resistant fast light NBR material for sole of shoe.
Therefore compared with prior art, the present invention has following beneficial effect:
(1) PPO is that the English name of polyphenylene oxide is write a Chinese character in simplified form, its embrittlement temperature is low to moderate-170 DEG C, there is fabulous winter hardiness, but its machine-shaping is more difficult, and therefore the present invention chooses PPO/PS alloy replacement PPO, with the addition of compatilizer in addition, under the compatible role of compatilizer and the synergy of PS, form stronger blended in interface between PPO/PS and NBR, thus greatly reduce the embrittlement temperature of material for sole of shoe, improve the winter hardiness of material for sole of shoe.
(2) nano tin dioxide has good ultraviolet absorption ability, can be used as UV light absorber, but its surfaces hydrophilic, and the consistency between the NBR matrix of surfaces hydrophobic is poor, therefore the present invention carries out modification by PEG20000 to it, PEG20000 is coated on the surface of nano tin dioxide, the wetting ability on its surface is changed into hydrophobicity, consistency between nano tin dioxide and NBR matrix is greatly improved, modified nano tin dioxide can be scattered in NBR matrix well, when material for sole of shoe is subject to illumination, nano tin dioxide effectively can absorb ultraviolet, greatly reduce the photodegradation that NBR is subject to, thus greatly improve the light aging resisting property of material for sole of shoe.
Embodiment:
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1
A kind of cold-resistant fast light NBR material for sole of shoe, by weight, is made up of following component: NBR100 part, DOP5 part, 14 parts, calcium carbonate, calcium-zinc composite stabilizing agent 3.6 parts, carbon black 3.4 parts, anti-aging agent RD 2.5 parts, 1.8 parts, sulphur, accelerator DZ 1.6 parts, compatilizer SEBS5 part, nano tin dioxide 7.5 parts, PPO/PS10 part, stearic acid 1.5 parts, zinc white 4.8 parts.
The step of its preparation method is as follows:
(1) nano tin-oxide powder is added in deionized water, ultrasonic disperse 12 minutes obtained massfractions are the slurries of 15%, ultrasonic disperse is continued 15 minutes after adding PEG20000, move in reflux vessel and reflux 3 hours at 80 DEG C, be cooled to discharging after room temperature, be dried to constant weight after filtration, after grinding, obtain modified Nano stannic oxide;
(2) NBR being added mill mixer roller temperature is plasticate at 80 DEG C, it is mixing at 100 DEG C for after 12 minutes, SEBS, PPO/PS being added mill mixer roller temperature, adding the modified Nano stannic oxide that step (1) obtains after 10 minutes continues mixing, after 9 minutes, roller temperature is adjusted to 80 DEG C, roll spacing is adjusted to 2mm, then add DOP, calcium carbonate, calcium-zinc composite stabilizing agent, carbon black, anti-aging agent RD, zinc white, stearic acid, accelerator DZ, mixing 40 minutes of sulphur successively, obtain rubber unvulcanizate;
(3) rubber unvulcanizate that step (2) obtains is placed on rolling press is rolled into film, film to be put at 110 DEG C, mould sulfuration 1 hour, take out rear microtome, obtain cold-resistant fast light NBR material for sole of shoe.
Embodiment 2
A kind of cold-resistant fast light NBR material for sole of shoe, by weight, is made up of following component: NBR100 part, DOP7 part, 12 parts, calcium carbonate, calcium-zinc composite stabilizing agent 3.2 parts, carbon black 4 parts, anti-aging agent RD 2.4 parts, 1.2 parts, sulphur, accelerator DZ 1.5 parts, compatilizer SEBS6 part, nano tin dioxide 8.5 parts, PPO/PS9 part, stearic acid 1.2 parts, zinc white 5 parts.
The step of its preparation method is as follows:
(1) nano tin-oxide powder is added in deionized water, ultrasonic disperse 12 minutes obtained massfractions are the slurries of 15%, ultrasonic disperse is continued 15 minutes after adding PEG20000, move in reflux vessel and reflux 3 hours at 80 DEG C, be cooled to discharging after room temperature, be dried to constant weight after filtration, after grinding, obtain modified Nano stannic oxide;
(2) NBR being added mill mixer roller temperature is plasticate at 80 DEG C, it is mixing at 100 DEG C for after 12 minutes, SEBS, PPO/PS being added mill mixer roller temperature, adding the modified Nano stannic oxide that step (1) obtains after 10 minutes continues mixing, after 9 minutes, roller temperature is adjusted to 80 DEG C, roll spacing is adjusted to 2mm, then add DOP, calcium carbonate, calcium-zinc composite stabilizing agent, carbon black, anti-aging agent RD, zinc white, stearic acid, accelerator DZ, mixing 40 minutes of sulphur successively, obtain rubber unvulcanizate;
(3) rubber unvulcanizate that step (2) obtains is placed on rolling press is rolled into film, film to be put at 110 DEG C, mould sulfuration 1 hour, take out rear microtome, obtain cold-resistant fast light NBR material for sole of shoe.
Embodiment 3
A kind of cold-resistant fast light NBR material for sole of shoe, by weight, is made up of following component: NBR100 part, DOP6.5 part, kaolin 11 parts, calcium-zinc composite stabilizing agent 4 parts, carbon black 3 parts, anti-aging agent RD 1.5 parts, 1.4 parts, sulphur, accelerator DZ 1.4 parts, compatilizer SEBS5.5 part, nano tin dioxide 8 parts, PPO/PS11 part, stearic acid 1 part, zinc white 4.2 parts.
The step of its preparation method is as follows:
(1) nano tin-oxide powder is added in deionized water, ultrasonic disperse 12 minutes obtained massfractions are the slurries of 15%, ultrasonic disperse is continued 15 minutes after adding PEG20000, move in reflux vessel and reflux 3 hours at 80 DEG C, be cooled to discharging after room temperature, be dried to constant weight after filtration, after grinding, obtain modified Nano stannic oxide;
(2) NBR being added mill mixer roller temperature is plasticate at 80 DEG C, it is mixing at 100 DEG C for after 12 minutes, SEBS, PPO/PS being added mill mixer roller temperature, adding the modified Nano stannic oxide that step (1) obtains after 10 minutes continues mixing, after 9 minutes, roller temperature is adjusted to 80 DEG C, roll spacing is adjusted to 2mm, then add DOP, kaolin, calcium-zinc composite stabilizing agent, carbon black, anti-aging agent RD, zinc oxide, stearic acid, accelerator DZ, mixing 40 minutes of sulphur successively, obtain rubber unvulcanizate;
(3) rubber unvulcanizate that step (2) obtains is placed on rolling press is rolled into film, film to be put at 110 DEG C, mould sulfuration 1 hour, take out rear microtome, obtain cold-resistant fast light NBR material for sole of shoe.
Embodiment 4
A kind of cold-resistant fast light NBR material for sole of shoe, by weight, is made up of following component: NBR100 part, DOP5.5 part, kaolin 12.5 parts, calcium-zinc composite stabilizing agent 3.3 parts, carbon black 3.2 parts, anti-aging agent RD 2.7 parts, 2 parts, sulphur, accelerator DZ 1 part, compatilizer SEBS5.4 part, nano tin dioxide 7 parts, PPO/PS12 part, stearic acid 1.8 parts, zinc white 4.5 parts.
The step of its preparation method is as follows:
(1) nano tin-oxide powder is added in deionized water, ultrasonic disperse 12 minutes obtained massfractions are the slurries of 15%, ultrasonic disperse is continued 15 minutes after adding PEG20000, move in reflux vessel and reflux 3 hours at 80 DEG C, be cooled to discharging after room temperature, be dried to constant weight after filtration, after grinding, obtain modified Nano stannic oxide;
(2) NBR being added mill mixer roller temperature is plasticate at 80 DEG C, it is mixing at 100 DEG C for after 12 minutes, SEBS, PPO/PS being added mill mixer roller temperature, adding the modified Nano stannic oxide that step (1) obtains after 10 minutes continues mixing, after 9 minutes, roller temperature is adjusted to 80 DEG C, roll spacing is adjusted to 2mm, then add DOP, kaolin, calcium-zinc composite stabilizing agent, carbon black, anti-aging agent RD, zinc oxide, stearic acid, accelerator DZ, mixing 40 minutes of sulphur successively, obtain rubber unvulcanizate;
(3) rubber unvulcanizate that step (2) obtains is placed on rolling press is rolled into film, film to be put at 110 DEG C, mould sulfuration 1 hour, take out rear microtome, obtain cold-resistant fast light NBR material for sole of shoe.
Embodiment 5
A kind of cold-resistant fast light NBR material for sole of shoe, by weight, is made up of following component: NBR100 part, DOP6 part, kaolin 10 parts, calcium-zinc composite stabilizing agent 3.5 parts, carbon black 3.6 parts, anti-aging agent RD 2 parts, 1.4 parts, sulphur, accelerator DZ 1.8 parts, compatilizer SEBS5.7 part, nano tin dioxide 8.8 parts, PPO/PS10.5 part, stearic acid 2 parts, zinc white 4 parts.
The step of its preparation method is as follows:
(1) nano tin-oxide powder is added in deionized water, ultrasonic disperse 12 minutes obtained massfractions are the slurries of 15%, ultrasonic disperse is continued 15 minutes after adding PEG20000, move in reflux vessel and reflux 3 hours at 80 DEG C, be cooled to discharging after room temperature, be dried to constant weight after filtration, after grinding, obtain modified Nano stannic oxide;
(2) NBR being added mill mixer roller temperature is plasticate at 80 DEG C, it is mixing at 100 DEG C for after 12 minutes, SEBS, PPO/PS being added mill mixer roller temperature, adding the modified Nano stannic oxide that step (1) obtains after 10 minutes continues mixing, after 9 minutes, roller temperature is adjusted to 80 DEG C, roll spacing is adjusted to 2mm, then add DOP, kaolin, calcium-zinc composite stabilizing agent, carbon black, anti-aging agent RD, zinc oxide, stearic acid, accelerator DZ, mixing 40 minutes of sulphur successively, obtain rubber unvulcanizate;
(3) rubber unvulcanizate that step (2) obtains is placed on rolling press is rolled into film, film to be put at 110 DEG C, mould sulfuration 1 hour, take out rear microtome, obtain cold-resistant fast light NBR material for sole of shoe.
Embodiment 6
A kind of cold-resistant fast light NBR material for sole of shoe, by weight, is made up of following component: NBR100 part, DOP6.6 part, 13 parts, calcium carbonate, calcium-zinc composite stabilizing agent 3 parts, carbon black 3.9 parts, anti-aging agent RD 2.1 parts, 1 part, sulphur, accelerator DZ 1.2 parts, compatilizer SEBS5.2 part, nano tin dioxide 9 parts, PPO/PS11.5 part, stearic acid 1.4 parts, zinc white 4.9 parts.
The step of its preparation method is as follows:
(1) nano tin-oxide powder is added in deionized water, ultrasonic disperse 12 minutes obtained massfractions are the slurries of 15%, ultrasonic disperse is continued 15 minutes after adding PEG20000, move in reflux vessel and reflux 3 hours at 80 DEG C, be cooled to discharging after room temperature, be dried to constant weight after filtration, after grinding, obtain modified Nano stannic oxide;
(2) NBR being added mill mixer roller temperature is plasticate at 80 DEG C, it is mixing at 100 DEG C for after 12 minutes, SEBS, PPO/PS being added mill mixer roller temperature, adding the modified Nano stannic oxide that step (1) obtains after 10 minutes continues mixing, after 9 minutes, roller temperature is adjusted to 80 DEG C, roll spacing is adjusted to 2mm, then add DOP, calcium carbonate, calcium-zinc composite stabilizing agent, carbon black, anti-aging agent RD, zinc oxide, stearic acid, accelerator DZ, mixing 40 minutes of sulphur successively, obtain rubber unvulcanizate;
(3) rubber unvulcanizate that step (2) obtains is placed on rolling press is rolled into film, film to be put at 110 DEG C, mould sulfuration 1 hour, take out rear microtome, obtain cold-resistant fast light NBR material for sole of shoe.
After tested, winter hardiness and the ageing-resistant performance of embodiment 1-6 and comparative example are as shown in the table, wherein,
The Chinese patent of comparative example to be publication number be CN102796292A;
Winter hardiness is according to the embrittlement temperature of GB/T5470-2008 test material, and the lower winter hardiness of embrittlement temperature is better;
Ageing-resistant performance test process is: material is placed in 4cm place under ultraviolet lamp, under room temperature, exposure intensity is 33.3 μ W/cm
2ultraviolet, the rate of weight loss of test material after 1000 hours, the less light aging resisting property of rate of weight loss is better.
As seen from the above table, embrittlement temperature of the present invention and rate of weight loss are all starkly lower than comparative example, winter hardiness and ageing-resistant performance better.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. a cold-resistant fast light NBR material for sole of shoe, is characterized in that: by weight, is made up of following component: NBR100 part, 5 ~ 7 parts, softening agent, filler 10 ~ 14 parts, thermo-stabilizer 3 ~ 4 parts, strengthening agent 3 ~ 4 parts, 2 ~ 3 parts, anti-aging agent, vulcanizing agent 1 ~ 2 part, promotor 1 ~ 2 part, compatilizer 5 ~ 6 parts, nano tin dioxide 7 ~ 9 parts, PPO/PS9 ~ 12 part, stearic acid 1 ~ 2 part, zinc white 4 ~ 5 parts.
2. one according to claim 1 resists cold fast light NBR material for sole of shoe, it is characterized in that: described softening agent is DOP.
3. one according to claim 1 resists cold fast light NBR material for sole of shoe, it is characterized in that: described filler is calcium carbonate or kaolin.
4. one according to claim 1 resists cold fast light NBR material for sole of shoe, it is characterized in that: described thermo-stabilizer is calcium-zinc composite stabilizing agent.
5. one according to claim 1 resists cold fast light NBR material for sole of shoe, it is characterized in that: described strengthening agent is carbon black.
6. one according to claim 1 resists cold fast light NBR material for sole of shoe, it is characterized in that: described anti-aging agent is anti-aging agent RD.
7. one according to claim 1 resists cold fast light NBR material for sole of shoe, it is characterized in that: described vulcanizing agent is sulphur.
8. one according to claim 1 resists cold fast light NBR material for sole of shoe, it is characterized in that: described promotor is accelerator DZ.
9. one according to claim 1 resists cold fast light NBR material for sole of shoe, it is characterized in that: described compatilizer is SEBS.
10. the preparation method of a kind of cold-resistant fast light NBR material for sole of shoe according to claim 1 ~ 9 any one, is characterized in that: its step is as follows:
(1) nano tin-oxide powder is added in deionized water, ultrasonic disperse 12 minutes obtained massfractions are the slurries of 15%, ultrasonic disperse is continued 15 minutes after adding PEG20000, move in reflux vessel and reflux 3 hours at 80 DEG C, be cooled to discharging after room temperature, be dried to constant weight after filtration, after grinding, obtain modified Nano stannic oxide;
(2) NBR being added mill mixer roller temperature is plasticate at 80 DEG C, it is mixing at 100 DEG C for after 12 minutes, compatilizer, PPO/PS being added mill mixer roller temperature, adding the modified Nano stannic oxide that step (1) obtains after 10 minutes continues mixing, after 9 minutes, roller temperature is adjusted to 80 DEG C, roll spacing is adjusted to 2mm, then add softening agent, filler, thermo-stabilizer, strengthening agent, anti-aging agent, zinc white, stearic acid, promotor, mixing 40 minutes of vulcanizing agent successively, obtain rubber unvulcanizate;
(3) rubber unvulcanizate that step (2) obtains is placed on rolling press is rolled into film, film to be put at 110 DEG C, mould sulfuration 1 hour, take out rear microtome, obtain cold-resistant fast light NBR material for sole of shoe.
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