CN104448435A - 120-DEG C aging-resistant nitrile/polyvinyl chloride rubber composition - Google Patents
120-DEG C aging-resistant nitrile/polyvinyl chloride rubber composition Download PDFInfo
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- CN104448435A CN104448435A CN201410699115.4A CN201410699115A CN104448435A CN 104448435 A CN104448435 A CN 104448435A CN 201410699115 A CN201410699115 A CN 201410699115A CN 104448435 A CN104448435 A CN 104448435A
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- polyvinyl chloride
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
The invention develops a 120-DEG C aging-resistant nitrile/polyvinyl chloride rubber composition which mainly comprises nitrile/polyvinyl chloride rubber, ester ether ADB-30, polyester adipate and fast extruding carbon black; through the development of a formula and the preparation of a rubber tube, the fuel B and 93# gasoline resistance, the excellent elongation at break resisting a high temperature of 120 DEG C for above 500 hours and heat aging performance of a surplus and the performance of no crack at a low temperature of below 30 DEG C below zero required in product standards are better solved; the 120-DEG C aging-resistant nitrile/polyvinyl chloride rubber composition has greater advantages in aspects of cost and performance in comparison with imported sizing material; meanwhile, the high-temperature long-time aging resistance, the low-temperature performance and the user value of the rubber are also improved; the 120-DEG C aging-resistant nitrile/polyvinyl chloride rubber composition has important significance in better playing roles of a nitrile/polyvinyl chloride rubber material and a product thereof in the auto industry and other fields, the safety guarantee of the product is improved, and the service life of the product is prolonged.
Description
Technical field
The present invention relates to field of rubber technology, particularly relate to the rubber hose of oil resistance, butyronitrile/polyvinyl chloride rubber combination that a kind of resistance to 120 DEG C of aging life cycles are long.
Background technology
In automobile industry, machinofacture, oil production, oil refining and other industrial production, need all to need to use rubber hose in gasoline, fuel oil, lubricating oil, hydraulic pressure wet goods oils transmitting procedure, but all there is the deficiency of oil resistant aspect by the rubber hose that standard technology is produced.If rubber hose in use steeps in oil based media for a long time, oils can penetrate into sebific duct inside, and to make it produce swelling, causes the intensity of rubber and other mechanical properties to reduce, cause sebific duct to roll over flat obstruction pipeline.
Butyronitrile/polyvinyl chloride rubber is obtained macromolecular elastomer by paracril and polyvinyl chloride mechanical blending.Because having polarity containing vinyl cyanide, therefore have excellent resistance to nonpolar and low-pole oils and solvent, the existence of polyvinyl chloride content can improve resistance to ozone and the weathering resistance of sizing material.Acrylonitrile content is higher, and better, thermotolerance is better, and lower temperature resistance is poorer for oil-proofness.Be widely used in as a kind of oil resisting rubber and manufacture in oil resisting rubber hose goods.But along with the fast development of automotive industry and the continuous enhancing of people's environmental consciousness, require more and more higher to product performance, the standard formulated is also more and more higher, with regard to current vehicle oil filler flexible pipe except needing the superior B of resistance to fuel oil and 93# gasoline performance, also need superior high temperature resistant 120 DEG C of heat aging performances also having residual content more than 500h elongation rate of tensile failure, low temperature is-30 DEG C, the performance of 5min fragility flawless and fracture.With regard to current butyronitrile/polyvinyl chloride rubber and prepare sebific duct and also there is very large shortcoming at this in four.
Summary of the invention
Object of the present invention mainly develops a kind of new butyronitrile/polyvinyl chloride rubber combination, and for the preparation of sebific duct, this material has the superior B of resistance to fuel oil, 93# gasoline; Resistance to 120 DEG C of heat aging performances also having residual content more than 500h elongation rate of tensile failure, what still have after these severe condition deflects and sealing property; Also low temperature resistant-30 DEG C, the performance of 5min fragility flawless and fracture can be met.The preparation of this formula materials, refueling hose and ventpipe has the lifting significantly to the B/93# of resistance to fuel oil gasoline, low temperature resistant fragility and high temperature resistance and long time aging resistance, and in cost and performance comparatively import sizing material have great advantage.
Be facts have proved by research and lot of experiments, the acrylonitrile content improving butyronitrile/polyvinyl chloride rubber is significantly improved for the B/93# of the resistance to fuel oil gasoline performance improving butyronitrile/polyvinyl chloride rubber; For improving the over-all properties of rubber and sebific duct, promotor, sulfur-donor in rubber combination of the present invention, will be adopted as vulcanization system; The blended softening agent of ether-ether ADB-30 and the polyester adipate softening agent that add novelty are arranged in pairs or groups and use, this point is last word point, the high temperature resistance and long time performance of what the former was very large enhance rubber and sebific duct, the low temperature resistant fragility energy of what the latter was very large improve rubber and sebific duct; The dithiodimorpholine sulfur-donor and the promotor that add uniqueness in preventing aging system coordinate the very large anti-warm air that improve sizing material and sebific duct, anti-ozone, weather protection performance; And the sulfuration of rubber is not affected, the performance of sizing material and sebific duct can be made to have the lifting of good lifting and outward appearance and physical and mechanical properties.
Technical scheme of the present invention is as follows:
Resistance to 120 DEG C of aging butyronitrile/polyvinyl chloride rubber combinations, its component and mass fraction are:
| Component | Mass fraction |
| Butyronitrile/polyvinyl chloride rubber | 100 |
| Fast extrusion carbon black | 50～60 |
| Ether-ether ADB-30 | 8～14 |
| Polyester adipate | 6～10 |
| Zinc oxide | 5 |
| Anti-aging agent B | 1.0 |
| Antioxidant D | 0.7 |
| Anti-aging agent E | 2.0 |
| Antioxidant H | 2.0 |
| Dithiodimorpholine | 2.5～3.5 |
| Dibenzothiazyl disulfide | 1.5～2.0 |
By adopting the butyronitrile/polyvinyl chloride rubber of high acrylonitrile content in 41% ~ 43%; The blended softening agent of ether-ether ADB-30 of resistance to 120 DEG C of high temperature and resistance to-30 DEG C of low temperature plasticizer polyester adipates; Under the preventing aging system cooperatively interacted; Under the acting in conjunction of the vulcanization system of sulfur-donor, the B/93# of the resistance to fuel oil gasoline performance of butyronitrile/polyvinyl chloride rubber has had further raising, volume change clearly very stable in standard range after the experience 72h oil resistant test; High temperature resistant 120 DEG C also have the heat aging performance result of residual content more than 500h elongation rate of tensile failure after still have certain elongation,-32 DEG C can be reached and there is no crackle in low temperature brittleness, and other performances of rubber obviously do not change, sebific duct entrucking oil-resistant effect does not well roll over flat problem.
The raising of the butyronitrile/polyvinyl chloride rubber B/93# of resistance to fuel oil gasoline performance also improves the high temperature resistance and long time aging resistance of rubber simultaneously, low-temperature performance and use value, can better to play a role in fields such as automobile industries important in inhibiting for butyronitrile/polyvinyl chloride elastomeric material and goods thereof, improve safety control and the work-ing life of goods.
The exploitation of this formula and the preparation of sebific duct well solve the B of resistance to fuel oil that product standard requires and 93# gasoline performance, superior high temperature resistant 120 DEG C also have the heat aging performance of residual content, low temperature below-30 DEG C, there is no the performance of crackle more than 500h elongation rate of tensile failure.
Embodiment
The sizing material embodiment of high temperature resistance and long time aging oil resistance:
In mass fraction
| Component | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Butyronitrile/polyvinyl chloride rubber | 100 | 100 | 100 | 100 | 100 |
| Fast extrusion carbon black | 50 | 55 | 56 | 60 | 58 |
| Ether-ether ADB-30 | 8 | 10 | 10 | 14 | 8 |
| Polyester adipate | 8 | 8 | 10 | 6 | 10 |
| Zinc oxide | 5 | 5 | 5 | 5 | 5 |
| Anti-aging agent B | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Antioxidant D | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| Anti-aging agent E | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Antioxidant H | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Dithiodimorpholine | 2.5 | 3.0 | 3.5 | 3.0 | 3.0 |
| Dibenzothiazyl disulfide | 1.5 | 2.0 | 1.5 | 2.0 | 2.0 |
| Add up to | 180.7 | 188.7 | 191.7 | 195.7 | 191.7 |
Butyronitrile/polyvinyl chloride rubber is the butyronitrile/polyvinyl chloride rubber of high acrylonitrile content in domestic 41% ~ 43%.
Common mixed refining process is carried out by starting material in listed formula and consumption:
1, rubber, starting material weigh spot check
2, refining-one section of second-bottom sheet of beginning to pratise is opened in one section of banburying-a section first
3, the storage period
4, two sections of banburyings-two section first are opened refining-two section second and are opened refining-bottom sheet
5, sulfide film (160 DEG C of * 20min)
6, style is cut by standard
7, testing inspection is carried out
Here is the test-results of the properties of rubber using high temperature resistance and long time aging oil resistance:
By the summary to above-mentioned test, domestic butyronitrile/good rubber of polyvinyl chloride entrucking is selected to carry out rubber unvulcanizate Formula Development, the performance B/93# of resistance to fuel oil gasoline more excellent performance compared with traditional butyronitrile/polyvinyl chloride rubber compounding of example 1-5 formulated rubber material, resistance to elevated temperatures is aging more outstanding for a long time, resistance to low temperature is also very excellent, and production oil port flexible pipe is significantly improved in technique and performance, it is flat to there is folding in entrucking, and respond well.Film obtained for six kinds of formulas is carried out the test of fuel oil B/93# gasoline, places it in medium solution, observe after parking 72 hours at 40 DEG C and test the volume change of the film of each formula, all excellent than conventional formulation as apparent from test-results example 1-5; The film that six kinds of formulas obtain is carried out high temperature limit temperature 120 DEG C also has the heat aging performance of residual content to test more than 500h elongation rate of tensile failure, its dumbbell shape test piece is placed in thermal aging oven and carries out, at 120 DEG C, aging 72h, 120h, 240h, 500h, 650h survey its elongation rate of tensile failure respectively, according to being that 120 DEG C of aging lower elongations also have residue and two that did not lose efficacy formulas to the test observation of exemplar and test case 1 ~ 5, illustrate its long-time relative to conventional formulation aging best one group; Film obtained for six kinds of formulas is carried out low-temperature brittleness test, and by it in flakes and carry out in low-temperature brittleness test equipment, from-30 DEG C, every 5min carries out one group, compares the difference had clearly as apparent from test-results conventional formulation with the result of example 1-5; From salient features systematic analysis technique, the example formulations after improvement and product can solve material limits performance and product can not meet entrucking situation.
The B/93# of the resistance to fuel oil gasoline that the present invention proposes, resistance to superelevation ultimate temperature 120 DEG C of performances also have the butyronitrile/polyvinyl chloride rubber of the heat aging performance of residual content more than 500h elongation rate of tensile failure, by being described in detail above, test proof and practical situation confirm, person skilled obviously can realize the technology of the present invention with combination not departing from content of the present invention, spirit and scope to change formula as herein described and preparation method or suitably change.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (1)
1. resistance to 120 DEG C of aging butyronitrile/polyvinyl chloride rubber combinations, it is characterized in that component and mass fraction as follows:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410699115.4A CN104448435B (en) | 2014-11-27 | 2014-11-27 | A kind of resistance to butyronitrile 120 DEG C aging/polrvinyl chloride rubber composition |
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| CN201410699115.4A CN104448435B (en) | 2014-11-27 | 2014-11-27 | A kind of resistance to butyronitrile 120 DEG C aging/polrvinyl chloride rubber composition |
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| CN104448435A true CN104448435A (en) | 2015-03-25 |
| CN104448435B CN104448435B (en) | 2016-06-08 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674821A (en) * | 2017-01-12 | 2017-05-17 | 芜湖航天特种电缆厂股份有限公司 | High-temperature resistant cable sheathing compound and preparation method thereof |
| CN106700345A (en) * | 2017-01-12 | 2017-05-24 | 芜湖航天特种电缆厂股份有限公司 | Cold-resistant cable sheath material and preparation method thereof |
| CN106700346A (en) * | 2017-01-12 | 2017-05-24 | 芜湖航天特种电缆厂股份有限公司 | High temperature resistant sheathing material for cables and preparation method of high temperature resistant sheathing material |
| CN106751225A (en) * | 2017-01-12 | 2017-05-31 | 芜湖航天特种电缆厂股份有限公司 | Wear-resistant cable sheath material and preparation method thereof |
| CN106751224A (en) * | 2017-01-12 | 2017-05-31 | 芜湖航天特种电缆厂股份有限公司 | Wear-resistant cable sheath material and preparation method thereof |
| CN109762218A (en) * | 2019-01-28 | 2019-05-17 | 常州山水橡胶科技有限公司 | Ageing-resistant rubber of resistance to fuel oil and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674821A (en) * | 2017-01-12 | 2017-05-17 | 芜湖航天特种电缆厂股份有限公司 | High-temperature resistant cable sheathing compound and preparation method thereof |
| CN106700345A (en) * | 2017-01-12 | 2017-05-24 | 芜湖航天特种电缆厂股份有限公司 | Cold-resistant cable sheath material and preparation method thereof |
| CN106700346A (en) * | 2017-01-12 | 2017-05-24 | 芜湖航天特种电缆厂股份有限公司 | High temperature resistant sheathing material for cables and preparation method of high temperature resistant sheathing material |
| CN106751225A (en) * | 2017-01-12 | 2017-05-31 | 芜湖航天特种电缆厂股份有限公司 | Wear-resistant cable sheath material and preparation method thereof |
| CN106751224A (en) * | 2017-01-12 | 2017-05-31 | 芜湖航天特种电缆厂股份有限公司 | Wear-resistant cable sheath material and preparation method thereof |
| CN109762218A (en) * | 2019-01-28 | 2019-05-17 | 常州山水橡胶科技有限公司 | Ageing-resistant rubber of resistance to fuel oil and preparation method thereof |
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| Publication number | Publication date |
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| CN104448435B (en) | 2016-06-08 |
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Address after: 300270 No. 1703, Ge Wan Road, Zhong Tang Industrial Zone, Binhai New Area, Tianjin Patentee after: Tianjin Peng Ling group Limited by Share Ltd Address before: 300384 No. 1703, Ge Wan Road, Grand Port, Tianjin Patentee before: Tianjin Pengling Rubber Tube Co., Ltd. |