CN103073872A - Chlorohydrin rubber composition and fuel oil rubber tube - Google Patents
Chlorohydrin rubber composition and fuel oil rubber tube Download PDFInfo
- Publication number
- CN103073872A CN103073872A CN2011103273346A CN201110327334A CN103073872A CN 103073872 A CN103073872 A CN 103073872A CN 2011103273346 A CN2011103273346 A CN 2011103273346A CN 201110327334 A CN201110327334 A CN 201110327334A CN 103073872 A CN103073872 A CN 103073872A
- Authority
- CN
- China
- Prior art keywords
- chlorohydrin rubber
- rubber composition
- chlorohydrin
- rubber
- parts
- 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
Landscapes
- Rigid Pipes And Flexible Pipes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a novel chlorohydrin rubber composition which comprises, by weight, 100 parts of chlorhydrin rubber, 2 to 30 parts of modified polybutadiene and 0.5 to 20 parts of a vulcanizing agent. The invention further provides a fuel oil rubber tube which comprises a fluorubber layer, an aramid fiber layer and a chlorhydrin rubber layer from interior to exterior. The chlorhydrin rubber composition provided by the invention has improved bonding performance during co-extrusion with fluorubber.
Description
Technical Field
The invention relates to a chlorohydrin rubber composition and a fuel hose.
Background
The fuel hose generally adopts a double-layer structure of inner layer rubber and outer layer rubber or a composite structure of the inner layer rubber/the enhancement layer/the outer layer rubber. The inner layer rubber is required to be high temperature resistant and fuel oil resistant, the fuel oil transmittance is low, the reinforcing layer is made of polyester fiber or aramid fiber, and the outer layer rubber is required to be ozone resistant and oil resistant. With the stricter standards of automobile emission and the like, the commonly used materials of the fuel rubber hose are changed from a nitrile rubber/chloroprene rubber composite structure into a composite structure of fluororubber and chlorohydrin rubber from inside to outside or a composite structure of fluororubber, aramid fiber and chlorohydrin rubber from inside to outside. The fluororubber has excellent oil resistance and high temperature resistance, the chlorohydrin rubber has ozone resistance and oil resistance, and the composite structure can meet higher standard requirements.
Co-extrusion of fluororubbers with epichlorohydrin rubbers requires good adhesion of the vulcanized rubber. In the actual production process, the composite fuel rubber pipe has the defects of layering or poor bonding strength and the like, and hidden troubles are brought to the safe use of vehicles. The traditional solution is not only poor in processability, but also high in material cost.
Disclosure of Invention
The invention provides a novel chlorohydrin rubber composition for solving the problem of poor adhesive property in the co-extrusion of fluororubber and chlorohydrin rubber, and the adhesive property in the co-extrusion of the fluororubber and the chlorohydrin rubber is improved.
The chlorohydrin rubber composition provided by the invention comprises 100 parts by weight of chlorohydrin rubber, 2-30 parts by weight of modified polybutadiene and 0.5-20 parts by weight of vulcanizing agent.
The invention also provides a fuel rubber hose which sequentially comprises a fluororubber layer, a chlorohydrin rubber layer, an aramid fiber layer and a chlorohydrin rubber layer from inside to outside, wherein the chlorohydrin rubber is the chlorohydrin rubber provided by the invention.
The chlorohydrin rubber composition provided by the invention is added with modified polybutadiene, such as hydroxyl-terminated polybutadiene or maleated polybutadiene, wherein both hydroxyl and maleic acid groups are polar groups, and the hydroxyl and maleic acid groups exist at the combined interface of the chlorohydrin rubber and the fluororubber and can participate in the vulcanization process of the fluororubber. The polybutadiene molecular chain contains double bonds and can participate in the crosslinking reaction of the chlorohydrin rubber.
Therefore, the chlorohydrin rubber and the fluororubber provided by the invention are extruded together to prepare the fuel hose, and the chlorohydrin rubber and the fluororubber have better adhesiveness; in addition, the prepared fuel rubber hose also has better oil resistance and heat resistance.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a chlorohydrin rubber composition which comprises 100 parts by weight of chlorohydrin rubber, 2-30 parts by weight of modified polybutadiene and 0.5-20 parts by weight of vulcanizing agent.
Wherein,
the chlorohydrin rubber is a common chlorohydrin rubber known to those skilled in the art, and a chlorohydrin rubber with a Mooney viscosity of 30-120 is generally adopted; the chlorohydrin rubber required is commercially available, and the chlorohydrin rubber C2000L from Raynaud corporation is used in the examples.
The modified polybutadiene may be hydroxyl-terminated polybutadiene or maleated polybutadiene, and has a viscosity (cps, 25 ℃) of 500-500000 and an average molecular weight of 1000-15000; the desired modified polybutadiene is commercially available, and examples below employ modified polybutadiene Ricobond1756 (maleated modified polybutadiene), modified polybutadiene Ricon134 (hydroxyl-terminated modified polybutadiene) available from sartomer specialty chemicals.
The above-mentioned vulcanizing agents may be various conventional vulcanizing agents, for example: one or more of sulfur, lead tetraoxide or ethylene thiourea; the following examples used the vulcanizing agent ethylene thiourea (NA-22) from Zhejiang Huang Dong rubber Co.
30-150 parts by weight of carbon black is also doped in the chlorohydrin rubber, the surface of a carbon black aggregate can be physically and chemically crosslinked with a rubber matrix, and a plurality of molecular chains can be connected to a single aggregate, so that loose high-molecular chain segments become a whole, the mechanical property of the rubber is greatly improved, the lubrication degree of the chlorohydrin rubber is increased, the friction force is reduced, and the wear resistance is improved; the method of adding rubber to rubber is a common method in the art and is not described herein. The specific surface area of the carbon black is 20-120 square meters per gram; the above carbon black is commercially available, and carbon black N550 manufactured by Tianjin Kabo chemical Co., Ltd is used in the following examples.
The chlorohydrin rubber can also be mixed with one or more of an anti-aging agent, a plasticizer and an accelerator.
The antioxidant can be various conventional antioxidants, and can be one or more of 2, 2, 4-trimethyl-1, 2-dihydroquinoline, nickel dibutyldithiocarbamate and 4, 4' -di (phenylisopropyl) diphenylamine; the anti-aging agent can be obtained commercially, and NBC (N-bromosuccinimide) produced by Nippon rubber Co., Ltd in Huangjiang Huang and Zhe Dong is used in the following examples.
The plasticizer can be various conventional plasticizers, and can be one or more of dioctyl sebacate, dioctyl phthalate and dibutoxyethyl adipate; the plasticizer is commercially available And used in the examples below is plasticizer TP-759 from Rohm And Haas Company (Rohm And Haas Company).
The accelerator can be various conventional accelerators, and can be one or more of tetramethylthiuram disulfide, tetraethylthiuram disulfide, N-cyclohexyl-2-benzothiazole sulfonamide, dibenzothiazyl disulfide and zinc dimethyldithiocarbamate; the accelerator is also commercially available, and the following examples use the accelerator N-cyclohexyl-2-benzothiazolesulfenamide available from Zhejiang yellow rock, Zhendong rubber Chemicals, Inc.
In the present invention, the method for preparing the chlorohydrin rubber composition comprises the following steps:
100 parts by weight of chlorohydrin rubber, 2-30 parts by weight of modified polybutadiene, 30-150 parts by weight of carbon black, 0-3 parts by weight of an anti-aging agent, 0-25 parts by weight of a plasticizer, 0.5-20 parts by weight of a vulcanizing agent and 0-10 parts by weight of an accelerator are added into a mixing device and mixed for 2-40 minutes at the temperature of 30-150 ℃ to obtain the chlorohydrin rubber composition.
The invention also provides a fuel hose, wherein the fluororubber in the fuel hose is fluororubber commonly used in the field, the fluororubber mixture DCC57005 is adopted in the following embodiment, then a reticular aramid layer is woven outside the fluororubber layer, and finally the epichlorohydrin rubber composition provided by the invention is coated on the aramid layer to form the hose.
Examples 1 to 3:
according to the weight ratio of each component in Table 1, epichlorohydrin rubber C2000L, modified polybutadiene Ricobond1756, modified polybutadiene Ricobond 134 or the mixture of modified polybutadiene Ricobond1756 and modified polybutadiene Ricobond 134, carbon black N550, antioxidant NBC, plasticizer TP-759, ethylene thiourea (NA-22) and N-cyclohexyl-2-benzothiazole sulfenamide were added in turn to an internal mixer and mixed at 100 ℃ for 8 minutes to obtain the epichlorohydrin rubber composition.
Comparative example:
the chlorohydrin rubber C2000L, carbon black N550, antioxidant NBC, plasticizer TP-759, ethylene thiourea (NA-22) and N-cyclohexyl-2-benzothiazole sulfonamide were added to the mixer in the following order according to the weight ratio of the components in Table 1, and mixed for 8 minutes at 100 ℃ to obtain a chlorohydrin rubber composition.
The formula of each component is shown in table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Chlorohydrin rubber C2000L | 100g | 100g | 100g | 100g | 100g | 100g |
| Modified polybutadiene Ricobond1756 | 5g | -- | 6g | -- | -- | -- |
| Modified polybutadiene Ricon134 | -- | 8g | 5g | -- | -- | -- |
| Carbon Black N550 | 60g | 80g | 100g | 60g | 80g | 100g |
| Antiager NBC | 2g | 0.5g | 1g | 2g | 0.5g | 1g |
| Plasticizer TP-759 | 5g | 10g | 16g | 5g | 10g | 16g |
| Ethylene thiourea (NA-22) | 2g | 2.5g | 1.5g | 2g | 2.5g | 1.5g |
| N-cyclohexyl-2-benzothiazolesulfenamides | 0.5g | 0 | 1.5g | 0.5g | 0 | 1.5g |
And (3) testing:
the inner layer fluororubber is extruded by using a fluororubber mixture DCC57005 on an extruder, then a reinforcing layer aramid fiber with a net structure is woven on an inner rubber pipe by using a weaving machine, then the chlorohydrin rubber composition prepared in the above example 1 or comparative example is coated on the reinforcing layer by using the extruder, and the extruded rubber pipe is molded after first-stage vulcanization in a vulcanizing tank (the temperature is 160 ℃ and the time is 50 minutes) and second-stage vulcanization in an oven (the temperature is 165 ℃ and the time is 1 hour).
The results of the product tests on the formed hose are as shown in table 2:
TABLE 2
As can be seen from the test results shown in table 2, the hose co-extruded with the chlorohydrin rubber composition and the fluororubber composition proposed in the present invention is slightly better in burst pressure than the hose co-extruded with the chlorohydrin rubber composition and the fluororubber composition prepared according to the formulation of the comparative example; on the other hand, the adhesive strength of the chlorohydrin rubber composition and the fluororubber composition proposed in the present invention is significantly higher than that of the chlorohydrin rubber composition and the fluororubber composition in the comparative examples.
The above-mentioned adhesive strength test was carried out according to GB/T14905-; the burst pressure is tested according to the GB/T5563-2006 standard.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (11)
1. A chlorohydrin rubber composition comprises 100 parts by weight of chlorohydrin rubber, 2-30 parts by weight of modified polybutadiene and 0.5-20 parts by weight of a vulcanizing agent.
2. The chlorohydrin rubber composition of claim 1, wherein: the modified polybutadiene is hydroxyl terminated polybutadiene and/or maleated polybutadiene.
3. The chlorohydrin rubber composition of claim 1 or 2 wherein: the number average molecular weight of the modified polybutadiene is 1000-15000.
4. The chlorohydrin rubber composition of claim 1, wherein: the vulcanizing agent is one or more of sulfur, lead tetraoxide and ethylene thiourea.
5. The chlorohydrin rubber composition of claim 1, wherein: also comprises 30-150 parts by weight of carbon black.
6. The chlorohydrin rubber composition of claim 5, wherein: the specific surface area of the carbon black is 20-120 square meters per gram.
7. The chlorohydrin rubber composition of claim 1 or 5 wherein: the chlorohydrin rubber composition also comprises one or more of an anti-aging agent, a plasticizer and an accelerator.
8. The chlorohydrin rubber composition of claim 7, wherein: the anti-aging agent is one or more of 2, 2, 4-trimethyl-1, 2-dihydroquinoline, nickel dibutyl dithiocarbamate and 4, 4' -bis (phenyl isopropyl) diphenylamine.
9. The chlorohydrin rubber composition of claim 7, wherein: the plasticizer is one or more of dioctyl sebacate, dioctyl phthalate and dibutoxyethyl adipate.
10. The chlorohydrin rubber composition of claim 7, wherein: the accelerator is one or more of tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, N-cyclohexyl-2-benzothiazole sulfonamide, dibenzothiazyl disulfide and zinc dimethyldithiocarbamate.
11. A fuel rubber pipe comprises a fluororubber layer, an aramid fiber layer and a chlorohydrin rubber layer from inside to outside in sequence; the method is characterized in that: the chlorohydrin rubber layer is prepared from the chlorohydrin rubber composition of any one of claims 1-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103273346A CN103073872A (en) | 2011-10-25 | 2011-10-25 | Chlorohydrin rubber composition and fuel oil rubber tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103273346A CN103073872A (en) | 2011-10-25 | 2011-10-25 | Chlorohydrin rubber composition and fuel oil rubber tube |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103073872A true CN103073872A (en) | 2013-05-01 |
Family
ID=48150578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103273346A Pending CN103073872A (en) | 2011-10-25 | 2011-10-25 | Chlorohydrin rubber composition and fuel oil rubber tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103073872A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408916A (en) * | 2013-08-07 | 2013-11-27 | 安徽中鼎泰克汽车密封件有限公司 | Sealing gasket material for automobile braking pressure increasing valve and manufacturing method of sealing gasket |
| CN103627160A (en) * | 2013-11-20 | 2014-03-12 | 济南开发区星火科学技术研究院 | A kind of chlorohydrin rubber |
| CN105813841A (en) * | 2013-12-24 | 2016-07-27 | 株式会社日轮 | Vulcanization-bonded laminate, and rubber composition for use in same |
| CN106543683A (en) * | 2016-11-25 | 2017-03-29 | 安徽美翔塑业有限公司 | A kind of automobile engine fuel rubber pipe and preparation method thereof |
| CN108799646A (en) * | 2017-04-26 | 2018-11-13 | 通用汽车环球科技运作有限责任公司 | Wear-resistant hose |
| CN112143205A (en) * | 2020-10-13 | 2020-12-29 | 安徽威能电源科技有限公司 | Preparation method of lead-acid storage battery pole plate supporting plastic spring material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5662975A (en) * | 1993-01-13 | 1997-09-02 | Elf Atochem S.A. | Composite tubular article consisting of a . . . petrol pipe and process for the preparation of such an article |
| CN1415472A (en) * | 2002-11-12 | 2003-05-07 | 天津大港鹏翎胶管股份有限公司 | Method for producing fuel line hose made from fluoro-resin |
| CN101307178A (en) * | 2007-05-18 | 2008-11-19 | 上海道氟化工科技有限公司 | Epichlorohydrin rubber composition sulfidization molding products thereof |
| CN101608039A (en) * | 2009-07-16 | 2009-12-23 | 蒋亨雷 | Material for rubber tube of automobile fuel oil |
| CN101654063A (en) * | 2009-09-23 | 2010-02-24 | 安徽中鼎密封件股份有限公司 | Low-permeability rubber tube of oil filling port of vehicle oil tank and manufacturing process thereof |
| WO2011118569A1 (en) * | 2010-03-24 | 2011-09-29 | 株式会社ニチリン | Vulcanization-adhered laminate of fluororubber and synthetic rubber |
-
2011
- 2011-10-25 CN CN2011103273346A patent/CN103073872A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5662975A (en) * | 1993-01-13 | 1997-09-02 | Elf Atochem S.A. | Composite tubular article consisting of a . . . petrol pipe and process for the preparation of such an article |
| CN1415472A (en) * | 2002-11-12 | 2003-05-07 | 天津大港鹏翎胶管股份有限公司 | Method for producing fuel line hose made from fluoro-resin |
| CN101307178A (en) * | 2007-05-18 | 2008-11-19 | 上海道氟化工科技有限公司 | Epichlorohydrin rubber composition sulfidization molding products thereof |
| CN101608039A (en) * | 2009-07-16 | 2009-12-23 | 蒋亨雷 | Material for rubber tube of automobile fuel oil |
| CN101654063A (en) * | 2009-09-23 | 2010-02-24 | 安徽中鼎密封件股份有限公司 | Low-permeability rubber tube of oil filling port of vehicle oil tank and manufacturing process thereof |
| WO2011118569A1 (en) * | 2010-03-24 | 2011-09-29 | 株式会社ニチリン | Vulcanization-adhered laminate of fluororubber and synthetic rubber |
Non-Patent Citations (2)
| Title |
|---|
| 孙晓民等: ""MLPB在橡胶改性中的应用初探"", 《特种橡胶制品》 * |
| 朱闰平等: ""马来酸酐化聚丁二烯对NR硫化胶抗撕裂性能的影响"", 《特种橡胶制品》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408916A (en) * | 2013-08-07 | 2013-11-27 | 安徽中鼎泰克汽车密封件有限公司 | Sealing gasket material for automobile braking pressure increasing valve and manufacturing method of sealing gasket |
| CN103627160A (en) * | 2013-11-20 | 2014-03-12 | 济南开发区星火科学技术研究院 | A kind of chlorohydrin rubber |
| CN103627160B (en) * | 2013-11-20 | 2016-04-27 | 济南开发区星火科学技术研究院 | A kind of chlorohydrin rubber |
| CN105813841A (en) * | 2013-12-24 | 2016-07-27 | 株式会社日轮 | Vulcanization-bonded laminate, and rubber composition for use in same |
| CN105813841B (en) * | 2013-12-24 | 2018-08-03 | 株式会社日轮 | Bonding by Vulcanization layered product and its used rubber composition |
| US10377885B2 (en) | 2013-12-24 | 2019-08-13 | Nichirin Co., Ltd. | Vulcanization-bonded laminate, and rubber composition used therefor |
| CN106543683A (en) * | 2016-11-25 | 2017-03-29 | 安徽美翔塑业有限公司 | A kind of automobile engine fuel rubber pipe and preparation method thereof |
| CN108799646A (en) * | 2017-04-26 | 2018-11-13 | 通用汽车环球科技运作有限责任公司 | Wear-resistant hose |
| CN112143205A (en) * | 2020-10-13 | 2020-12-29 | 安徽威能电源科技有限公司 | Preparation method of lead-acid storage battery pole plate supporting plastic spring material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073872A (en) | Chlorohydrin rubber composition and fuel oil rubber tube | |
| CN101407602B (en) | Rubber composition for non-aqueous pipe for automobile and non-aqueous pipe using same | |
| EP3001084B1 (en) | Rubber composition for hoses, and hose | |
| CN102719024B (en) | Heat resistance sealing ring and manufacturing process thereof | |
| CN102563237B (en) | Hydraulic-controlled clutch pipe and production process thereof | |
| EP1995275A1 (en) | Elastomer composition, method for producing same, and pneumatic tire using same | |
| EP3553120B1 (en) | Rubber composition for marine hose and marine hose | |
| CN108570168A (en) | Nitrile rubber vulcanising composition and sulfurized nitrile rubber and the preparation method and application thereof | |
| KR101914355B1 (en) | Rubber composition for tire innerliner, manufacturing method thereof and tire manufactured by using the same | |
| CN105585748A (en) | Ozone aging resistance rubber and preparation method thereof | |
| CN107683304A (en) | Fire-retardant flexible pipe rubber composition and fire-retardant flexible pipe | |
| CN105237894A (en) | Formula of ethylene propylene diene monomer rubber for rubber layer in rubber tube of air conditioner | |
| CN101654063A (en) | Low-permeability rubber tube of oil filling port of vehicle oil tank and manufacturing process thereof | |
| US10221306B2 (en) | Rubber composition for hose, and hose | |
| CN105199164B (en) | Automobile vacuum booster rubbery membrana dermalis | |
| US20220162433A1 (en) | Fire resistant rubber compositions and hose | |
| CN118238474A (en) | High-toughness aging-resistant EPDM rubber tube | |
| CN107400270B (en) | Low temperature resistant minus 60 DEG C of rubber hydralic hose outer layer glue | |
| US10962149B2 (en) | Fuel hose with rubber cover layer | |
| DE102015203877A1 (en) | Hose, in particular for the transport of a coolant, its use and method for its production | |
| CN111303803A (en) | Environment-friendly ultralow-specific-gravity weld joint sealant and preparation method thereof | |
| JP3683372B2 (en) | Pneumatic tire | |
| CN114181470B (en) | Acid-resistant rubber composition and application thereof, vulcanized rubber and preparation method and application thereof | |
| DE102011050882A1 (en) | Hose that transports an acidic medium, in particular a diesel particulate filter tube or differential pressure hose, as well as a bisphenolic cross-linked and acid-resistant fluorinated rubber mixture | |
| JP5205936B2 (en) | Rubber composition and composite material and hose using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130501 |