CN104448435B - A kind of resistance to butyronitrile 120 DEG C aging/polrvinyl chloride rubber composition - Google Patents
A kind of resistance to butyronitrile 120 DEG C aging/polrvinyl chloride rubber composition Download PDFInfo
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- CN104448435B CN104448435B CN201410699115.4A CN201410699115A CN104448435B CN 104448435 B CN104448435 B CN 104448435B CN 201410699115 A CN201410699115 A CN 201410699115A CN 104448435 B CN104448435 B CN 104448435B
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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 Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
The present invention develops a kind of resistance to butyronitrile 120 DEG C aging/polrvinyl chloride rubber composition, mainly includes butyronitrile/polrvinyl chloride rubber, ether-ether ADB 30, polyester adipate and extrudes white carbon black soon; The exploitation of this formula and the preparation of sebific duct well solve product standard require the B of resistance to fuel oil and 93# gasoline performance, superior high temperature resistant 120 DEG C also have the heat aging performance of surplus, low temperature there is no the performance of crackle below 30 DEG C more than 500h elongation rate of tensile failure. And relatively import sizing material has great advantage in cost and performance. Also improve the high temperature resistance and long time ageing properties of rubber simultaneously, cryogenic property and use value, can better play a role in fields such as automobile industries important in inhibiting for butyronitrile/polrvinyl chloride elastomeric material and goods thereof, improve safety guarantee and the service life of goods.
Description
Technical field
The present invention relates to field of rubber technology, particularly relate to the rubber hose of oil resistance, the butyronitrile/polrvinyl chloride rubber composition of a kind of resistance to 120 DEG C of aging life cycle length.
Background technology
In automobile industry, machine-building, oil exploitation, oil refining and other commercial production, need to be required for using in gasoline, fuel oil, lubricating oil, hydraulic pressure wet goods oils transmitting procedure rubber hose, but the rubber hose produced by standard technology all exists the deficiency of oil resistant aspect. If rubber hose in use steeps in oil based media for a long time, oils can penetrate into that to make it produce inside sebific duct swelling, causes the intensity of rubber and other mechanical properties to reduce, causes that flat obstruction pipeline rolled over by sebific duct.
Butyronitrile/polrvinyl chloride rubber is prepared macromolecular elastomer by nitrile rubber and polrvinyl chloride mechanical blending. Because having polarity containing acrylonitrile, therefore nonpolar and low pole oils and solvent having the resistance of excellence, the existence of polyvinyl chloride content can improve resistance to ozone and the weatherability of sizing material. Acrylonitrile content is higher, and better, thermostability is more good, and lower temperature resistance is more poor for oil resistivity. It is widely used in manufacture oil-resisting rubber hose goods as a kind of oil resistant rubber. But it is as the fast development of auto industry and the continuous enhancing of people's environmental consciousness, properties of product are required more and more higher, 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 needing to superior high temperature resistant 120 DEG C of heat aging performances also having surplus more than 500h elongation rate of tensile failure, low temperature is in the performance of-30 DEG C, 5min fragility flawless and fracture. With regard to current butyronitrile/polrvinyl chloride rubber and prepare sebific duct and there is also very big shortcoming at this in four.
Summary of the invention
The purpose of the present invention mainly develops a kind of new butyronitrile/polrvinyl chloride rubber composition, is used for preparing sebific duct, and this material has the superior B of resistance to fuel oil, 93# gasoline; Resistance to 120 DEG C of heat aging performances also having surplus more than 500h elongation rate of tensile failure, what still have after these harsh conditions deflects and sealing property;Also the performance of low temperature resistant-30 DEG C, 5min fragility flawless and fracture can be met. The preparation of this formula materials, refueling hose and breather has a significantly lifting to the B/93# of resistance to fuel oil gasoline, low temperature resistant fragility and high temperature resistance and long time ageing properties, and relatively import sizing material has great advantage in cost and performance.
By studying with lot of experiments it was verified that the acrylonitrile content improving butyronitrile/polrvinyl chloride rubber is significantly improved for the B/93# of the resistance to fuel oil gasoline performance improving butyronitrile/polrvinyl chloride rubber; For improving the combination property of rubber and sebific duct, the rubber composition of the present invention will adopt accelerator, sulfur-donor as vulcanizing system; Add the novel blended plasticizer of ether-ether ADB-30 and polyester adipate plasticizer is arranged in pairs or groups and uses, this point is last word point, what the former was very big enhances the high temperature resistance and long time performance of rubber and sebific duct, and what the latter was very big improves the low temperature resistant fragility energy of rubber and sebific duct; Preventing aging system adds the dithiodimorpholine sulfur-donor of uniqueness and accelerator coordinates and very big improves sizing material and the anti-hot-air of 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 is as follows:
A kind of resistance to butyronitrile 120 DEG C aging/polrvinyl chloride rubber composition, its component and mass fraction be:
| Component | Mass fraction |
| Butyronitrile/polrvinyl chloride rubber | 100 |
| Extrude white carbon black soon | 50��60 |
| Ether-ether ADB-30 | 8��14 |
| Polyester adipate | 6��10 |
| Zinc oxide | 5 |
| Age resistor B | 1.0 |
| Antioxidant D | 0.7 |
| Age resistor E | 2.0 |
| Antioxidant H | 2.0 |
| Dithiodimorpholine | 2.5��3.5 |
| Dibenzothiazyl disulfide | 1.5��2.0 |
By adopting the butyronitrile/polrvinyl chloride rubber of high acrylonitrile content in 41%��43%; The blended plasticizer 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 cooperated; Under the combined effect of the vulcanizing system of sulfur-donor, the B/93# of the resistance to fuel oil gasoline performance of butyronitrile/polrvinyl chloride rubber has had further raising, experience 72h oil resistant test after change in volume clearly in critical field and very stable; Certain percentage elongation is still had after high temperature resistant 120 DEG C of heat aging performance results also having surplus more than 500h elongation rate of tensile failure,-32 DEG C can be reached in black brittleness and there is no crackle, and other performances of rubber substantially do not change, sebific duct entrucking oil-resistant effect does not well roll over flat problem.
The raising of the butyronitrile/polrvinyl chloride rubber B/93# of resistance to fuel oil gasoline performance also improves the high temperature resistance and long time ageing properties of rubber simultaneously, cryogenic property and use value, can better play a role in fields such as automobile industries important in inhibiting for butyronitrile/polrvinyl chloride elastomeric material and goods thereof, improve safety guarantee and the service life of goods.
The exploitation of this formula and the preparation of sebific duct well solve product standard require the B of resistance to fuel oil and 93# gasoline performance, superior high temperature resistant 120 DEG C also have the heat aging performance of surplus, low temperature there is no the performance of crackle below-30 DEG C more than 500h elongation rate of tensile failure.
Detailed description of the invention
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/polrvinyl chloride rubber | 100 | 100 | 100 | 100 | 100 |
| Extrude white carbon black soon | 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 |
| Age resistor B | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Antioxidant D | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
| Age resistor 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/polrvinyl chloride rubber is the butyronitrile/polrvinyl chloride rubber of high acrylonitrile content in domestic 41%��43%.
Common mixed refining process is carried out by raw material in listed formula and consumption:
1, rubber, raw material weigh spot check
2 ,-one section of second-bottom sheet of beginning to pratise of refining is opened in one section of banburying-a section first
3, the storage period
4, two-stage nitration banburying-two-stage nitration first is opened refining-two-stage nitration second and is opened refining-bottom sheet
5, sulfide film (160 DEG C of * 20min)
6, style is cut by standard
7, testing inspection is carried out
The result of the test of the properties of rubber that use high temperature resistance and long time aging oil resistance is presented herein below:
By the summary to above-mentioned test, domestic butyronitrile/good rubber of polrvinyl chloride entrucking is selected to carry out elastomeric compound Formula Development, the performance of example 1-5 formulated rubber material is the B/93# of resistance to fuel oil gasoline more excellent performance compared with tradition butyronitrile/polrvinyl chloride rubber compounding, resistance to elevated temperatures is aging more prominent for a long time, resistance to low temperature is also very excellent, and produce oil filler flexible pipe and be significantly improved in technique and performance, entrucking will not occur folding flat and respond well. The film that six kinds of formula prepare is carried out the test of fuel oil B/93# gasoline, places it in medium solution, observe and test the change in volume of the film of each formula after parking 72 hours at 40 DEG C, will become apparent from example 1-5 from result of the test all excellent than conventional formulation; The film that six kinds of formula prepare is carried out high temperature limit temperature 120 DEG C also has the heat aging performance of surplus to test more than 500h elongation rate of tensile failure, it is placed in thermal aging oven by its dumbbell shape test piece to carry 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 percentage elongations also have residue and two formula not lost efficacy to the test observation of exemplar and test case 1��5, illustrate its long-time relative to conventional formulation aging best one group; The film that six kinds of formula prepare is carried out low-temperature brittleness test, it in flakes and is carried out in low-temperature brittleness test equipment, start every 5min from-30 DEG C and carry out one group, will become apparent from conventional formulation from result of the test and compare, with the result of example 1-5, the difference having clearly; From main performance systematic analysis technique, example formulations and product after improvement can solve the problem that 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, 120 DEG C of performances of resistance to superelevation limiting temperature also have the butyronitrile/polrvinyl chloride rubber of the heat aging performance of surplus more than 500h elongation rate of tensile failure, had passed through detailed description carried out above it have been experienced that and practical situation confirm, formula as herein described and preparation method substantially can be modified or suitably change realizing the technology of the present invention with combination by person skilled in without departing from present invention, spirit and scope. Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are considered as including in present invention spirit, scope and content.
Claims (1)
1. resistance to butyronitrile 120 DEG C aging/polrvinyl chloride rubber composition, is characterized in that component and mass fraction are as follows:
Described butyronitrile/polrvinyl chloride rubber is the butyronitrile/polrvinyl chloride rubber of the high acrylonitrile content of 41%��43%.
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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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| 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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| CN104448435B true CN104448435B (en) | 2016-06-08 |
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| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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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| DE10061174A1 (en) * | 2000-12-07 | 2002-06-20 | Bayer Ag | NBR gels in butyl rubber compounds |
| JP3985547B2 (en) * | 2002-02-26 | 2007-10-03 | Ｊｓｒ株式会社 | Thermoplastic elastomer composition and molded article |
| CN101555327B (en) * | 2009-05-19 | 2011-01-26 | 天津鹏翎胶管股份有限公司 | Formulation of high-concentration ozone resistant rubber tube |
| CN103709470A (en) * | 2013-12-19 | 2014-04-09 | 天津鹏翎胶管股份有限公司 | Hot-air-ageing-resistant nitrile-butadiene rubber composition |
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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. |