CN1167737C - Rubber containing nano zinc oxide and mixing method thereof - Google Patents
Rubber containing nano zinc oxide and mixing method thereof Download PDFInfo
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- CN1167737C CN1167737C CNB021120447A CN02112044A CN1167737C CN 1167737 C CN1167737 C CN 1167737C CN B021120447 A CNB021120447 A CN B021120447A CN 02112044 A CN02112044 A CN 02112044A CN 1167737 C CN1167737 C CN 1167737C
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- rubber
- zinc oxide
- nano zine
- zine oxide
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 57
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000002156 mixing Methods 0.000 title claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 235000021355 Stearic acid Nutrition 0.000 claims description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000008117 stearic acid Substances 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 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 8
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002632 lipids Chemical class 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 3
- -1 diaryl secondary amine Chemical class 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001206 natural gum Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 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 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000013585 weight reducing agent Substances 0.000 abstract 1
- 235000014692 zinc oxide Nutrition 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 239000000779 smoke Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006235 reinforcing carbon black Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- LTSHBNVFPQOLEX-UHFFFAOYSA-N butylbenzene Chemical compound CC[CH]CC1=CC=CC=C1 LTSHBNVFPQOLEX-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses rubber containing nano zinc oxide and a mixing method thereof. The rubber comprises a rubber matrix, a vulcanizing agent and zinc oxide serving as a vulcanizing active agent, wherein the particle size of the zinc oxide is 10-80nm, and the content of the zinc oxide is 1-3 parts by weight based on 100 parts by weight of the rubber matrix. The rubber matrix and the nano zinc oxide treated by the silane coupling agent are placed in an open mill to prepare nano zinc oxide master batch, and then the rubber matrix, the nano zinc oxide master batch, the accelerator, the anti-aging agent and the sulfur are sequentially put into the open mill according to the proportion to be mixed, so that the rubber is obtained. The invention has the same effect as 5 parts of common zinc oxide under the condition that the nano zinc oxide has 60 percent of weight reduction. The rubber material added with the nano zinc oxide has longer scorching time and can provide greater processing safety. The mechanical properties of the product, such as 300% elongation at break, tensile strength, elongation at break, permanent deformation, Shore hardness and the like, are all traditionally close to or equal to each other.
Description
Technical field
The present invention relates to a kind of rubber and compounding process thereof that contains zinc oxide.
Background technology
Zinc oxide is used T﹠B as vulcanization leveller in rubber, it can be accelerated vulcanization rate and can improve sulphidity again as promoting agent.Because zinc oxide is big to the affinity of electronics, big to the effect of promotor surface adsorption, so be the strongest a kind of of active function in the metal oxide.At present, generally more than 100nm, the conventional amount of zinc oxide (rubber is in 100 parts) is 5 parts for the zinc oxide of industrial use, its particle diameter, and at country variant, in the variant production, the past all is considered as classics, indubitable to this consumption.When the consumption of zinc oxide is lower than 5 parts, will the situation of mechanical properties decrease appear.This be since the particle diameter of common zinc oxide big, active relatively poor due to.Now adopt the nano zine oxide of particle diameter below 100nm as vulcanization leveller, just can overcome above-mentioned defective.But practice result shows that too small when the particle diameter of material, its dissemination is just poor.Will cause dispersion inhomogeneous so process nano zine oxide, the unsettled phenomenon of material property occur with the compounding process that disperses common zinc oxide.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of rubber that contains nano zine oxide, and the compounding process that cooperates with described rubber phase, are used for overcoming the defective of prior art.
Technical scheme of the present invention:
The present invention is the rubber that contains nano zine oxide, the rubber phase of its component and routine together, comprise rubber matrix, vulcanizing agent, promotor, anti-aging agent and as the stearic acid and the zinc oxide of vulcanization leveller, wherein, the particle diameter of the zinc oxide of being addressed is 10-80nm, and content is counted 1～3 part with the weight of 100 parts of rubber matrixs.
In optimized technical scheme of the present invention, the rubber matrix of being addressed comprises natural rubber or natural gum/butylbenzene blended rubber, the vulcanizing agent of being addressed is a sulphur, the promotor of being addressed is thiazole accelerator, as 2-benzothiazolyl mercaptan (captax), dibenzothiazyl disulfide (altax) and sulfenamide type accelerators, as N cyclohexyl 2 benzothiazole sulfenamide (accelerant CZ), the vulcanization leveller of being addressed is nano zine oxide and stearic acid, the anti-aging agent of being addressed is a diaryl secondary amine antioxidant, as N-phenyl-a-naphthylamine (antioxidant A), the parts by weight of each component are as follows:
Rubber matrix: 100; Sulphur: 1.5～4; Captax: 0.5～1.5;
Altax: 0.3～1.0; Accelerant CZ: 0.5～1.5; Stearic acid: 0.8～2.0;
Nano zine oxide (particle diameter 10～80nm): 1～3; Antioxidant A: 0.5～1.5;
Light calcium carbonate: 20～60.
The compounding process of the above-mentioned rubber that contains nano zine oxide comprises the steps:
1. nano zine oxide is infiltrated on the silane coupling agent aqueous solution or C
5～C
20In the water miscible liquid of lipid acid and salt thereof 5～15 minutes, the nano zine oxide that takes out after soaking into carried out drying;
Said silane coupling agent is the compound with following general structure:
RSiX
3。Wherein: the alkoxyl group that X representative can hydrolysis, as methoxyl group, second cyano group or chlorine etc., it can with the mineral filler on possess hydrophilic property surface, chemical reaction takes place as silicon-dioxide, silicate etc., generate the Si-O-Si chemical bond; R is the organic radical with reactive behavior, as vinyl, amino, thiol group etc.
Preferred C
5～C
20Lipid acid and salt thereof are stearic acid and salt thereof.
The concentration of preferred water miscible liquid is 5%～20wt%;
2. rubber matrix and above-mentioned treated nano zine oxide being placed mill, is to carry out mixingly under 30～85 ℃ the condition in temperature, makes the nano zine oxide master batch.The weight ratio of rubber matrix and treated nano zine oxide is: rubber matrix: nano zine oxide=90～95: 10～5;
3. successively rubber matrix, zinc oxide master batch, promotor, anti-aging agent, sulphur are dropped into according to aforementioned proportion and carry out mixingly in the mill, promptly obtain rubber of the present invention.
Owing to adopt nano zine oxide, show excellent performance such as small-size effect, interfacial effect and quantum tunneling effect, this just increases the contact surface and the activity of its chemical reaction greatly.Using under the situation of 2 parts of nano zine oxides, mechanical properties such as 300% tensile modulus of product, tensile strength, tensile yield, tension set, Shao Er hardness are all with the approaching of 5 parts of use common zinc oxides or equate.And the sizing material that adds nano zine oxide has long time of scorch, and bigger processing safety can be provided.
Embodiment
Rubber preparing device:
Mill: rubber machinery plant, XK-160 type φ 160 * 320mm Shanghai;
Vulcanizing press QLB-350mm * 350mm * first rubber machinery plant, 2 Shanghai
The testing standard that adopts:
Rheological: GB 1683-87, GB 686-85;
300% tensile modulus, tensile strength, tensile yield, tensile set: GB528-83;
Hardness: GB 531-83.
Embodiment 1
The nano zine oxide that with an amount of particle diameter is 60～80nm is to soak into 5 minutes in the silane coupling agent aqueous solution (above-mentioned silane coupling agent adopts the commercially available prod, down with) of 20wt% in concentration, filters the back and be dried to constant weight under 100 ℃;
With 95 part 3
#Smoke sheet rubber and above-mentioned treated nano zine oxide place mill for 5 parts, in temperature are to carry out mixingly under 50 ℃ the condition, make the nano zine oxide master batch;
With rubber: 81 parts; Sulphur: 4 parts; Captax: 0.5 part; Altax: 1 part; Stearic acid: 0.8 part; Nano zine oxide master batch: 20 parts; Antioxidant A: 0.5 part; Light calcium carbonate: 60 parts.Place mill, mixing under 55 ℃ temperature (mixing take traditional method, down with) promptly obtains rubber of the present invention.
Carry out rheometer test according to GB 1683-87, GB 686-85, Heating temperature is 155 ℃, and the result is as follows: T
10=1 ' 48 "; T
90=3 ' 24 ".T
10Be time of scorch.Incipient scorch is a sizing material in mixing, calendering or the scorching that extrudes in the operation and occur during parking before the sulfuration.T
90Be the technology sulfurizing time, the sulfided state when at this moment the over-all properties of cross-linked rubber reaches optimum value claims the most suitable sulfuration again.
Carry out the physical and mechanical properties test according to GB 528-83 standard, the result is as follows:
| Performance project | ||||
| 300% stretches MPa surely | Tensile strength MPa | Tensile yield % | Tension set % | Hardness Shao Er A |
| 2.051 | 20.881 | 650 | 18 | 48 |
Embodiment 2
The nano zine oxide that with an amount of particle diameter is 10～40nm soaked into 10 minutes in concentration is the silane coupling agent aqueous solution of 5wt%, filters the back and is dried to constant weight under 100 ℃;
With 90 part 3
#Smoke sheet rubber and above-mentioned treated nano zine oxide place mill for 10 parts, in temperature are to carry out mixingly under 50 ℃ the condition, make the nano zine oxide master batch;
With 3
#Smoke sheet rubber: 82 parts; Sulphur: 2.5 parts; Captax: 0.7 part; Altax: 0.8 part; Stearic acid: 1.5 parts; Nano zine oxide master batch: 20 parts; Antioxidant A: 1 part; Light calcium carbonate: 50 parts.Place mill, mixing under 55 ℃ temperature, promptly obtain rubber of the present invention.
Carry out rheometer test according to GB 1683-87, GB 686-85, Heating temperature is 155 ℃, and the result is as follows: T
10=2 ' 6 "; T
90=4 ' 24 ".
Carry out the physical and mechanical properties test according to GB 528-83 standard, the result is as follows:
| Performance project | ||||
| 300% stretches MPa surely | Tensile strength MPa | Tensile yield % | Tension set % | Hardness Shao Er A |
| 3.424 | 20.875 | 625 | 20 | 51 |
Embodiment 3
The nano zine oxide that with an amount of particle diameter is 40～60nm soaked into 10 minutes in concentration is the lipid acid water miscible liquid of 10wt%, filters the back and is dried to constant weight under 80 ℃;
With 90 part 3
#Smoke sheet rubber and above-mentioned treated nano zine oxide place mill for 10 parts, in temperature are to carry out mixingly under 60 ℃ the condition, make the nano zine oxide master batch;
With butadiene-styrene rubber 1502:60 part of Jilin chemical company production, 3
#Smoke sheet rubber: 13 parts; Sulphur: 1.5 parts; Captax: 1.5 parts; Altax: 0.5 part; Accelerant CZ: 1.5 parts; Stearic acid: 2 parts; Nano zine oxide master batch: 30 parts; Antioxidant A: 1.5 parts; Antioxidant 4010NA: 0.8 part; High abrasion carbon black N330:20 part; Semi-reinforcing carbon black: 15 parts; Machinery oil: 8.0; Light calcium carbonate: 20 parts.Place mill, mixing under 60 ℃ temperature, promptly obtain rubber of the present invention.
Carry out rheometer test according to GB 1683-87, GB 686-85, Heating temperature is 155 ℃, and the result is as follows: T
10=3 ' 30 "; T
90=6 ' 18 ".
Carry out the physical and mechanical properties test according to GB 528-83 standard, the result is as follows:
| Performance project | ||||
| 300% stretches MPa surely | Tensile strength MPa | Tensile yield % | Tension set % | Hardness Shao Er A |
| 8.869 | 13.879 | 403 | 10 | 65 |
Embodiment 4
The nano zine oxide that with an amount of particle diameter is 10～40nm soaked into 15 minutes in concentration is the lipid acid water miscible liquid of 15wt%, filters the back and is dried to constant weight under 80 ℃;
With 95 part 3
#Smoke sheet rubber and above-mentioned treated nano zine oxide place mill for 5 parts, in temperature are to carry out mixingly under 60 ℃ the condition, make the nano zine oxide master batch;
Butadiene-styrene rubber 1502:62 part with the production of Jilin chemical company; Sulphur: 2.0 parts; Altax: 0.3 part; Accelerant CZ: 1.0 parts; Stearic acid: 1.5 parts; Nano zine oxide master batch: 40 parts; Antioxidant A: 1.0 parts; Antioxidant 4010NA: 0.6 part; High abrasion carbon black N330:24.0 part; Semi-reinforcing carbon black: 10.0 parts; Machinery oil: 5.0; Light calcium carbonate: 25 parts.Place mill, mixing under 60 ℃ temperature, promptly obtain rubber of the present invention.
Carry out rheometer test according to GB 1683-87, GB 686-85, Heating temperature is 155 ℃, and the result is as follows: T
10=3 ' 18 "; T
90=5 ' 51 ".
Carry out the physical and mechanical properties test according to GB 528-83 standard, the result is as follows:
| Performance project | ||||
| 300% stretches MPa surely | Tensile strength MPa | Tensile yield % | Tension set % | Hardness Shao Er A |
| 8.453 | 16.548 | 442 | 15 | 63 |
Claims (7)
1. the rubber that contains nano zine oxide, comprise rubber matrix, vulcanizing agent, promotor, anti-aging agent and as the zinc oxide of vulcanization leveller, it is characterized in that the particle diameter of the zinc oxide of being addressed is 10-80nm, content is counted 1～3 part with the weight of 100 parts of rubber matrixs.
2. rubber as claimed in claim 1, it is characterized in that, the rubber matrix of being addressed comprises natural rubber or natural gum/butylbenzene blended rubber, the vulcanizing agent of being addressed is a sulphur, the promotor of being addressed is that thiazole accelerator is or/and sulfenamide type accelerators, the vulcanization leveller of being addressed is a nano zine oxide or/and stearic acid, and the anti-aging agent of being addressed is a diaryl secondary amine antioxidant.
3. rubber as claimed in claim 2 is characterized in that, the parts by weight of each component are as follows:
Rubber matrix: 100; Sulphur: 1.5～4; Promotor 2-benzothiazolyl mercaptan: 0.5～1.5;
Accelerator dibenzothiazyl disulfide: 0.3～1.0; Accelerant N-cyclohexyl-2-[4-morpholinodithio sulphenamide: 0.5～1.5; Stearic acid: 0.8～2.0;
Nano zine oxide: 1～3; Anti-aging agent N-phenyl-a-naphthylamine: 0.5～1.5; Light calcium carbonate: 20～60.
4. as the preparation method of claim 1,2 or 3 described rubber, it is characterized in that this method comprises the steps:
(1) nano zine oxide is infiltrated on the silane coupling agent aqueous solution or C
5～C
20In the water miscible liquid of lipid acid and salt thereof 5～15 minutes, the nano zine oxide that takes out after soaking into carried out drying;
Said silane coupling agent is the compound with following general structure: RSiX
3, wherein: the alkoxyl group that X representative can hydrolysis, R represents vinyl, amino or thiol group;
(2) rubber matrix and above-mentioned treated nano zine oxide are placed mill, in temperature be carry out under 30～85 ℃ the condition mixing, make the nano zine oxide master batch, the weight ratio of rubber matrix and treated nano zine oxide is: rubber matrix: nano zine oxide=90～95: 10～5;
(3) successively rubber matrix, zinc oxide master batch, promotor, anti-aging agent, sulphur are dropped into according to aforementioned proportion and carry out mixingly in the mill, promptly obtain rubber of the present invention.
5. method as claimed in claim 4 is characterized in that, X representation methoxy, second cyano group or chlorine.
6. method as claimed in claim 4 is characterized in that lipid acid of being addressed and salt thereof are stearic acid and salt thereof.
7. method as claimed in claim 4 is characterized in that, the concentration of water miscible liquid is 5%～20wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021120447A CN1167737C (en) | 2002-06-12 | 2002-06-12 | Rubber containing nano zinc oxide and mixing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021120447A CN1167737C (en) | 2002-06-12 | 2002-06-12 | Rubber containing nano zinc oxide and mixing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1386788A CN1386788A (en) | 2002-12-25 |
| CN1167737C true CN1167737C (en) | 2004-09-22 |
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|---|---|---|---|
| CNB021120447A Expired - Fee Related CN1167737C (en) | 2002-06-12 | 2002-06-12 | Rubber containing nano zinc oxide and mixing method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2460744C2 (en) * | 2006-05-23 | 2012-09-10 | Раббер Нано Продактс (Пропрайетери) Лимитед | Rubber compositions |
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| US6972307B2 (en) * | 2003-07-29 | 2005-12-06 | The Goodyear Tire & Rubber Company | Rubber composition containing nanoscaled zinc oxide particles |
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-
2002
- 2002-06-12 CN CNB021120447A patent/CN1167737C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2460744C2 (en) * | 2006-05-23 | 2012-09-10 | Раббер Нано Продактс (Пропрайетери) Лимитед | Rubber compositions |
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| Publication number | Publication date |
|---|---|
| CN1386788A (en) | 2002-12-25 |
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