CN102050967A - Method for improving thermo-oxidative aging resistant performance of conventional sulfur vulcanizing system of natural rubber - Google Patents
Method for improving thermo-oxidative aging resistant performance of conventional sulfur vulcanizing system of natural rubber Download PDFInfo
- Publication number
- CN102050967A CN102050967A CN 201010540984 CN201010540984A CN102050967A CN 102050967 A CN102050967 A CN 102050967A CN 201010540984 CN201010540984 CN 201010540984 CN 201010540984 A CN201010540984 A CN 201010540984A CN 102050967 A CN102050967 A CN 102050967A
- Authority
- CN
- China
- Prior art keywords
- natural rubber
- parts
- situ
- surface modifying
- stearic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
- C09C1/043—Zinc oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供了一种提高天然橡胶传统硫黄硫化体系耐热氧老化性能的方法，包括如下步骤：将原位表面改性纳米氧化锌加入到天然橡胶传统硫黄硫化体系中，硫化后，获得天然橡胶制品；所述原位表面改性纳米氧化锌是以硝酸锌和失水山梨醇油酸脂为原料，以硬脂酸为分散剂制备的。本发明在保证纳米颗粒高活性的同时减弱了其由于高的比表面能而带来的团聚现象，将其应用于天然橡胶传统硫黄硫化体系，使其纳米效应得到了充分地发挥。本发明工艺简单，硫化胶的物理机械性能优良，耐热氧老化性能显著提高。本发明也可应用于其它的硫黄硫化的二烯类橡胶传统硫化体系，因此应用前景非常广阔。The invention provides a method for improving the heat and oxygen aging resistance of a traditional sulfur vulcanization system of natural rubber, comprising the following steps: adding in-situ surface-modified nano zinc oxide to the traditional sulfur vulcanization system of natural rubber, and obtaining natural rubber after vulcanization A product; the in-situ surface-modified nano-zinc oxide is prepared from zinc nitrate and sorbitan oleate as raw materials and stearic acid as a dispersant. The invention ensures the high activity of the nanoparticles and at the same time weakens the agglomeration phenomenon caused by the high specific surface energy. It is applied to the traditional sulfur vulcanization system of natural rubber, so that the nanometer effect is fully exerted. The process of the invention is simple, the vulcanized rubber has excellent physical and mechanical properties, and the heat and oxygen aging resistance performance is significantly improved. The present invention can also be applied to other sulfur vulcanized diene rubber traditional vulcanization systems, so the application prospect is very broad.
Description
Technical field
The present invention relates to a kind of method that improves natural rubber tradition sulfur sulfide system heatproof air aging performance.
Background technology
The sulfur sulfide system that polydiene is complete is made up of vulcanizing agent, promotor and promoting agent three parts.Wherein zinc oxide and stearic acid are the classics combinations of vulcanization leveller, consumption keep always 5 parts constant.Therefore, different with the relative proportion of promotor according to the vulcanizing agent Sulfur, vulcanization system can be divided into: traditional vulcanization system, efficient vulcanization system and semi effcient vulcanization system.
Yang Qingzhi chief editor's " practical rubber technology " narrated in the 6th joint " various sulfur sulfide system " chapters and sections: polydiene tradition sulfur sulfide system is meant the vulcanization system of common sulphur dosage scope.For natural rubber, the sulfury consumption is commonly used 2.5 parts, and the consumption of promotor is 0.5 part.It in the cross-linked rubber network polysulfidic bond.Cross-linked rubber has good initial fatigue property, has good dynamic and static state performance under the room temperature condition, and maximum shortcoming is thermo-labile oxygen aging, and cross-linked rubber can not be at life-time service under the comparatively high temps.
Designed the heatproof air aging performance that efficient vulcanization system and semi effcient vulcanization system improve natural rubber for this reason, but with this diplobiont is the defective that remedies natural rubber tradition sulfur sulfide system heatproof air aging performance difference, all is to be cost with the comprehensive physical and mechanical properties of sacrificing traditional sulfur sulfide system without exception.
Zinc oxide is the most frequently used activator of natural rubber, and it and stearic acid generate Zinic stearas, with crosslinked precursor chelating, increase new cross-link bond, improve the cross-linking density of natural rubber, and forms complex compound with promotor, makes promotor more active.Therefore, zinc oxide can be accelerated vulcanization rate, improve the cross-linking density and the heatproof air aging performance of cross-linked rubber, but the particle diameter of common zinc oxide is big, and is active low and limit the performance of its activation.Nanosecond science and technology have changed the activity of zinc oxide, and the nano effect that nano zine oxide brings make its sulfurate activity that the raising of matter arranged, but the particle diameter of material is more little, and its tendency of assembling conglomeration is big more, the also difficult more embodiment of nano effect.
Summary of the invention
The objective of the invention is to disclose a kind of method that improves natural rubber tradition sulfur sulfide system heatproof air aging performance, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps: the in-situ-surface modifying nano zine oxide is joined in the natural rubber tradition sulfur sulfide system, after the sulfuration
Obtain the natural rubber goods.
The in-situ-surface modifying nano zine oxide with the mass parts ratio of natural rubber is: the in-situ-surface modifying nano zine oxide: natural rubber=1～5 part: 100 parts;
Described in-situ-surface modifying nano zine oxide is to be raw material with zinc nitrate and anhydrous sorbitol olein, is the dispersion agent preparation with the stearic acid;
The preparation method comprises the steps:
(1) the dispersion agent stearic acid is heated to 80 ℃ of fusions, adds zinc nitrate and anhydrous sorbitol olein then, stir and obtain colloidal sol after 1～3 hour, cooling obtains gel;
(2) with the gel of step (1) 550～650 ℃ temperature lower calcination 4～6 hours, obtain the nano zine oxide of in-situ-surface modifying;
Mass parts is: 120 parts of stearic acid, 15.68～41.83 parts of zinc nitrates, 1.13～3.01 parts of anhydrous sorbitol oleins;
Described natural rubber tradition sulfur sulfide system is conventional, as adopting the component and the mass parts of 94 pages of reports of " rubber industry handbook " the third volume of a work;
The component and the mass parts of natural rubber tradition sulfur sulfide system of the present invention are as follows:
100 parts of natural rubbers
2～3 parts of Sulfurs
0.5～0.7 part of accelerant N OBS
1～2 part of stearic acid
Preferably, the component and the mass parts of natural rubber tradition sulfur sulfide system are as follows:
100 parts of natural rubbers
2.5 parts of Sulfurs
0.7 part of accelerant N OBS
1.2 parts of stearic acid
The chemical name of described accelerant N OBS is N-oxydiethylene-2-[4-morpholinodithio base sulphenamide.
The present invention adopts sol-gel method that nano zine oxide is carried out in-situ-surface modifying, nano zine oxide after the modification has improved the dispersiveness in rubber substrate, can give full play to its nano effect, be applied to natural rubber tradition sulfur sulfide system, the heatproof air aging performance of warm air accelerated deterioration postcure glue has raising significantly.
The in-situ-surface modifying nano zine oxide of the present invention's preparation, guaranteeing highly active its agglomeration that brings owing to high specific surface energy that weakened simultaneously of nano particle, be applied to natural rubber tradition sulfur sulfide system, make its nano effect obtain performance fully.Technology of the present invention is simple, and the physical and mechanical properties of cross-linked rubber is good, and heatproof air aging performance significantly improves.The present invention also can be applicable to the polydiene tradition vulcanization system of other sulfur vulcanization, so application prospect is boundless.
Embodiment
Among the embodiment, press the tensile strength and the elongation rate of tensile failure of GB/T 528-1998 national standard test cross-linked rubber.
The warm air accelerated deterioration of cross-linked rubber is carried out in 401A type heat aging test chamber, and aging condition is 100 ℃ * 72h, carries out according to GB/T 3512-2001 national standard.
Below in conjunction with embodiment the present invention is further described in detail, but is not limited thereto.
Comparative Examples 1
The component and the mass parts of described natural rubber tradition sulfur sulfide system are as follows:
100 parts of natural rubbers
2.5 parts of Sulfurs
0.7 part of accelerant N OBS
1.2 parts of stearic acid
5 parts of common zinc oxides.
Tensile strength, elongation rate of tensile failure and stretching strength retentivity, the elongation rate of tensile failure conservation rate of cross-linked rubber see Table 1 before and after the natural rubber warm air accelerated deterioration that records.
Embodiment 1
(1) the dispersion agent stearic acid is heated to 80 ℃ of fusions, adds zinc nitrate and anhydrous sorbitol olein then, stir and obtain colloidal sol after 1 hour, cooling obtains gel;
(2) with the gel of step (1) 550 ℃ temperature lower calcination 6 hours, obtain the nano zine oxide of in-situ-surface modifying;
Stearic acid 120 grams
Zinc nitrate 41.83 grams
Anhydrous sorbitol olein 3.01 grams
The component and the mass parts of described natural rubber tradition sulfur sulfide system are as follows:
100 parts of natural rubbers
2.5 parts of Sulfurs
0.7 part of accelerant N OBS
1.2 parts of stearic acid
1 part of in-situ-surface modifying nano zine oxide.
Tensile strength, elongation rate of tensile failure and stretching strength retentivity, the elongation rate of tensile failure conservation rate of cross-linked rubber see Table 1 before and after the natural rubber warm air accelerated deterioration that records.
Embodiment 2
(1) the dispersion agent stearic acid is heated to 80 ℃ of fusions, adds zinc nitrate and anhydrous sorbitol olein then, stir and obtain colloidal sol after 3 hours, cooling obtains gel;
(2) with the gel of step (1) 650 ℃ temperature lower calcination 4 hours, obtain the nano zine oxide of in-situ-surface modifying;
Stearic acid 120 grams
Zinc nitrate 15.68 grams
Anhydrous sorbitol olein 1.13 grams
The component and the mass parts of described natural rubber tradition sulfur sulfide system are as follows:
100 parts of natural rubbers
2.5 parts of Sulfurs
0.7 part of accelerant N OBS
1.2 parts of stearic acid
2 parts of in-situ-surface modifying nano zine oxides.
Tensile strength, elongation rate of tensile failure and stretching strength retentivity, the elongation rate of tensile failure conservation rate of cross-linked rubber see Table 1 before and after the natural rubber warm air accelerated deterioration that records.
Embodiment 3
(1) the dispersion agent stearic acid is heated to 80 ℃ of fusions, adds zinc nitrate and anhydrous sorbitol olein then, stir and obtain colloidal sol after 2 hours, cooling obtains gel;
(2) with the gel of step (1) 600 ℃ temperature lower calcination 5 hours, obtain the nano zine oxide of in-situ-surface modifying;
Stearic acid 120 grams
Zinc nitrate 20.91 grams
Anhydrous sorbitol olein 2.01 grams
The component and the mass parts of described natural rubber tradition sulfur sulfide system are as follows:
100 parts of natural rubbers
2.5 parts of Sulfurs
0.7 part of accelerant N OBS
1.2 parts of stearic acid
3 parts of in-situ-surface modifying nano zine oxides.
Tensile strength, elongation rate of tensile failure and stretching strength retentivity, the elongation rate of tensile failure conservation rate of cross-linked rubber see Table 1 before and after the natural rubber warm air accelerated deterioration that records.
Embodiment 4
Adopt the in-situ-surface modifying nano zine oxide of embodiment 3.
The component and the mass parts of described natural rubber tradition sulfur sulfide system are as follows:
100 parts of natural rubbers
2.5 parts of Sulfurs
0.7 part of accelerant N OBS
1.2 parts of stearic acid
4 parts of in-situ-surface modifying nano zine oxides.
Tensile strength, elongation rate of tensile failure and stretching strength retentivity, the elongation rate of tensile failure conservation rate of cross-linked rubber see Table 1 before and after the natural rubber warm air accelerated deterioration that records.
Embodiment 5
Adopt the in-situ-surface modifying nano zine oxide of embodiment 3.
The component and the mass parts of described natural rubber tradition sulfur sulfide system are as follows:
100 parts of natural rubbers
2.5 parts of Sulfurs
0.7 part of accelerant N OBS
1.2 parts of stearic acid
5 parts of in-situ-surface modifying nano zine oxides.
Tensile strength, elongation rate of tensile failure and stretching strength retentivity, the elongation rate of tensile failure conservation rate of cross-linked rubber see Table 1 before and after the natural rubber warm air accelerated deterioration that records.
Table 1
Compare with adding 5 parts of common zinc oxides (Comparative Examples), behind the in-situ-surface modifying nano zine oxide that adds with amount, the tensile strength before natural rubber tradition sulfur sulfide system cross-linked rubber is aging has improved 17.58%, and elongation rate of tensile failure has improved 3.72%; Stretching strength retentivity and elongation rate of tensile failure conservation rate after aging have then improved 34.27% and 19.17% respectively.
Claims (5)
1. improve the method for natural rubber tradition sulfur sulfide system heatproof air aging performance, it is characterized in that, comprise the steps: the in-situ-surface modifying nano zine oxide is joined in the natural rubber tradition sulfur sulfide system, after the sulfuration, obtain the natural rubber goods;
Described in-situ-surface modifying nano zine oxide is to be raw material with zinc nitrate and anhydrous sorbitol olein, is the dispersion agent preparation with the stearic acid.
2. method according to claim 1 is characterized in that, described in-situ-surface modifying nano-ZnO preparation comprises the steps:
(1) the dispersion agent stearic acid is heated to 80 ℃ of fusions, adds zinc nitrate and anhydrous sorbitol olein then, stir and obtain colloidal sol, cooling obtains gel;
(2) with the gel of step (1) 550～650 ℃ temperature lower calcination 4～6 hours, obtain the nano zine oxide of in-situ-surface modifying.
3. method according to claim 2 is characterized in that, mass parts is: 120 parts of stearic acid, 15.68～41.83 parts of zinc nitrates, 1.13～3.01 parts of anhydrous sorbitol oleins.
4. according to claim 1,2 or 3 described methods, it is characterized in that the in-situ-surface modifying nano zine oxide with the mass parts ratio of natural rubber is: the in-situ-surface modifying nano zine oxide: natural rubber=1～5 part: 100 parts.
5. method according to claim 4 is characterized in that, the component and the mass parts of described natural rubber tradition sulfur sulfide system are as follows: 100 parts of natural rubbers, 2～3 parts of Sulfurs, accelerant N OBS0.5～0.7 part, 1～2 part of stearic acid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010540984 CN102050967A (en) | 2010-11-11 | 2010-11-11 | Method for improving thermo-oxidative aging resistant performance of conventional sulfur vulcanizing system of natural rubber |
| PCT/CN2011/070840 WO2012062057A1 (en) | 2010-11-11 | 2011-01-31 | Method for improving anti-aging performance due to heat or oxygen of natural rubber traditional sulfur vulcanization system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010540984 CN102050967A (en) | 2010-11-11 | 2010-11-11 | Method for improving thermo-oxidative aging resistant performance of conventional sulfur vulcanizing system of natural rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102050967A true CN102050967A (en) | 2011-05-11 |
Family
ID=43955802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010540984 Pending CN102050967A (en) | 2010-11-11 | 2010-11-11 | Method for improving thermo-oxidative aging resistant performance of conventional sulfur vulcanizing system of natural rubber |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102050967A (en) |
| WO (1) | WO2012062057A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072819A (en) * | 2014-06-27 | 2014-10-01 | 江西耐普矿机新材料股份有限公司 | Highly wear-resistant and tear-resistant rubber formula for vibrating screen |
| CN109233002A (en) * | 2018-07-26 | 2019-01-18 | 安徽锦华氧化锌有限公司 | A kind of preparation method for the rubber material that mechanical property is good |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525441A (en) * | 2009-01-19 | 2009-09-09 | 中国热带农业科学院农产品加工研究所 | Method for preparing nanometer zinc oxide/caoutchouc antibacterial composite material |
| CN101555035A (en) * | 2009-05-19 | 2009-10-14 | 上海工程技术大学 | Preparation and application of local surface-modified nanometre zinc oxide by sol-gel method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003118032A (en) * | 2001-10-12 | 2003-04-23 | Tokai Rubber Ind Ltd | Vibrationproof rubber laminate |
| KR100542274B1 (en) * | 2003-04-07 | 2006-01-11 | 금호타이어 주식회사 | Tire Rubber Composition with Nano Zinc |
| US7560510B2 (en) * | 2005-12-20 | 2009-07-14 | Bridgestone Corporation | Nano-sized inorganic metal particles, preparation thereof, and application thereof in improving rubber properties |
| CN101544788A (en) * | 2009-04-30 | 2009-09-30 | 上海大学 | High performance nano powder body-based tread rubber of engineering tire and preparation process thereof |
-
2010
- 2010-11-11 CN CN 201010540984 patent/CN102050967A/en active Pending
-
2011
- 2011-01-31 WO PCT/CN2011/070840 patent/WO2012062057A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525441A (en) * | 2009-01-19 | 2009-09-09 | 中国热带农业科学院农产品加工研究所 | Method for preparing nanometer zinc oxide/caoutchouc antibacterial composite material |
| CN101555035A (en) * | 2009-05-19 | 2009-10-14 | 上海工程技术大学 | Preparation and application of local surface-modified nanometre zinc oxide by sol-gel method |
Non-Patent Citations (2)
| Title |
|---|
| 《弹性体》 20071225 孙霞容等 不同氧化锌对天然橡胶疲劳性能影响的研究 第46-49页 1-5 第17卷, 第6期 2 * |
| 《特种橡胶制品》 20091031 孙霞容等 纳米氧化锌对天然橡胶疲劳性能的影响 第15-18页 1-5 第30卷, 第5期 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072819A (en) * | 2014-06-27 | 2014-10-01 | 江西耐普矿机新材料股份有限公司 | Highly wear-resistant and tear-resistant rubber formula for vibrating screen |
| CN109233002A (en) * | 2018-07-26 | 2019-01-18 | 安徽锦华氧化锌有限公司 | A kind of preparation method for the rubber material that mechanical property is good |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012062057A1 (en) | 2012-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102382489B (en) | Method for preparing low-zinc vulcanized active agents by active carrier method | |
| CN107955224B (en) | Carbon material reinforced rubber and preparation method thereof | |
| WO2015154492A1 (en) | Organic-inorganic composite vulcanized nitrile rubber for sealing element and preparation method therefor | |
| CN101649074A (en) | Compression and fatigue resisting rubber composition | |
| CN103113682A (en) | Wide-temperature-domain high-damping environment-friendly damping material for electronic product and preparation method thereof | |
| CN103059362B (en) | Nitrile rubber vulcanized rubber and preparation method thereof | |
| CN105175821B (en) | High-strength low-pressure variable oil-resistant valve seal ring | |
| CN108641150A (en) | A kind of repeatable processing rubber material and preparation method thereof | |
| CN101955600B (en) | Rubber sealing composite with excellent comprehensive performance and preparation method thereof | |
| CN114957818A (en) | Nitrile rubber-phenolic resin composite material and preparation method and application thereof | |
| CN109096624A (en) | A kind of rubber composition and preparation method thereof for automotive hose rubber core | |
| CN102977532A (en) | Acrylate rubber composition | |
| CN102050967A (en) | Method for improving thermo-oxidative aging resistant performance of conventional sulfur vulcanizing system of natural rubber | |
| CN109912968A (en) | Nano-alumina synergistic glass fiber composite reinforced nylon material and preparation method thereof | |
| CN109021342A (en) | A kind of high performance hydrogenated butyronitrile base rubber composite and preparation method thereof | |
| TW201905091A (en) | Formulations for producing elastomeric composite materials and methods for producing the same | |
| CN106674624B (en) | A kind of rubber material and preparation method thereof | |
| CN102942650A (en) | Core-shell type double-active acrylate elastic body and preparation method thereof | |
| CN106987058A (en) | A kind of compressor air-breathing bellows and its processing method | |
| CN107189131B (en) | Rubber composition for inner layer of railway general air hose with steel wire braided structure, preparation method and product thereof | |
| CN105694134A (en) | A kind of high thermal conductivity tire apex composition | |
| CN106589504A (en) | High-temperature-resistant heat-conducting stator rubber material and preparation method thereof | |
| CN110003536A (en) | A kind of preparation method of heat-dissipation type wear-resistant rubber material | |
| CN103804733A (en) | Vibration-isolation rubber material for steam turbine water pump set and preparation method thereof | |
| CN104087030B (en) | A kind of fluorubber special magnesium oxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110511 |