CN104558791A - Rubber composition and vulcanized rubber and application of rubber composition and vulcanized rubber - Google Patents
Rubber composition and vulcanized rubber and application of rubber composition and vulcanized rubber Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The invention discloses a rubber composition, vulcanized rubber which is obtained by vulcanizing the rubber composition, and application of the rubber composition and/or the vulcanized rubber in preparation of a rubber sealing gasket for a shield material. The rubber composition contains a terpolymer of ethylene and propylene and ethylidene norbornene, a vulcanizing agent, a vulcanization accelerator, an activating agent and a reinforcing agent, wherein on the basis of the total weight of the terpolymer, the content of an ethylene structure unit is not lower than 58wt%, and the content of an ethylidene norbornene structure unit is not lower than 4.5wt%. The vulcanized rubber obtained by vulcanizing the rubber composition disclosed by the invention has the advantages of relatively high mechanical property and heat resistance and relatively low compressed permanent deformation value, and is suitable for preparation of the rubber sealing gasket for the shield material.
Description
Technical field
The present invention relates to a kind of rubber combination, obtained vulcanized rubber and described rubber combination and/or the application of vulcanized rubber in the rubber gasket for the preparation of shield structure material by described rubber combination sulfuration.
Background technology
Terpolymer EP rubber (be called for short EPDM) is with ethene and propylene for main raw material, and with a kind of general purpose synthetic rubber with low-unsaturation-degree that a small amount of non-conjugated diene hydrocarbon Third monomer (as Norbornene derivative, dicyclopentadiene class monomer, hexadiene class monomer) is polymerized under Ziegler-Natta catalyst effect.Because the add-on of Third monomer is less, the degree of unsaturation in the side chain of EPDM is made to be generally only 1-2%.Relative to ethylene propylene rubber, except peroxide cure, EPDM can also pass through insoluble sulfur sulfuration, and the rubber item obtained has the advantages such as good weathering resistance, heat-resistant aging, resistance to ozone, can be applied in the field such as automotive sealant, heat resistance conveyor belt by wide model.
Rubber gasket in shield structure material is the mainstay material of the current Western European countries for piecing assembly tunnel duct piece hermetic seal, and shield pipe-plate is composited by single multi-hole type terpolymer EP rubber or multi-hole type terpolymer EP rubber and expanded rubber.Seal washer mainly serves the effects such as damping, sealing, sealing in shield structure material.Subway engineering application terpolymer EP rubber is used as pipe-plate lining seam waterproof material, but the EPDM elastic waterstop bar in report is mainly provided by American-European countries, also seldom has report at home by the sealing-ring of terpolymer EP rubber for the preparation of shield structure material.In addition, in terpolymer EP rubber conventional at present, the content of ethylene unit unit is not usually higher than 55 % by weight, all lower by the mechanical property of the vulcanized rubber obtained containing the sulfuration of this terpolymer EP rubber rubber combination, thermotolerance and Compression Set value, and be not suitable for the rubber gasket for the preparation of shield structure material.
Summary of the invention
The object of this invention is to provide a kind of new rubber combination, obtained vulcanized rubber and described rubber combination and/or the application of vulcanized rubber in the rubber gasket for the preparation of shield structure material by described rubber combination sulfuration.
The invention provides a kind of rubber combination, wherein, described rubber combination contains the terpolymer of ethene and propylene and ethylidene norbornene, vulcanizing agent, vulcanization accelerator, activator and toughener, and with the gross weight of described terpolymer for benchmark, the content of ethylene unit unit is not less than 58 % by weight, and the content of ethylidene norbornene structural unit is not less than 4.5 % by weight.
Present invention also offers and obtain vulcanized rubber by described rubber combination sulfuration.
In addition, present invention also offers described rubber combination and/or the application of vulcanized rubber in the rubber gasket for the preparation of shield structure material.
The present inventor is by finding after further investigation, ethylidene norbornene is adopted to control as Third monomer and by the content of ethylene unit unit in described terpolymer be not less than 58 % by weight, controlled by the content of ethylidene norbornene structural unit be not less than 4.5 % by weight, the vulcanized rubber obtained by described rubber combination sulfuration can be made to have higher mechanical property and thermotolerance and lower compression set value, be highly suitable for the application in the rubber gasket for the preparation of shield structure material.
According to another kind of preferred implementation of the present invention, when described activator be average particulate diameter is the nano zine oxide of 1-100nm, more be conducive to the dispersion of described promoting agent in rubber combination, thus improve the mechanical property of described vulcanized rubber more significantly.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Rubber combination provided by the invention contains the terpolymer of ethene and propylene and ethylidene norbornene, vulcanizing agent, vulcanization accelerator, activator and toughener, and with the gross weight of described terpolymer for benchmark, the content of ethylene unit unit is not less than 58 % by weight, and the content of ethylidene norbornene structural unit is not less than 4.5 % by weight.
According to the present invention, as long as although adopt ethylidene norbornene as Third monomer and the content of ethylene unit unit in described terpolymer controlled be not less than 58 % by weight, the content of ethylidene norbornene structural unit is controlled be not less than 4.5 % by weight, the vulcanized rubber obtained by described rubber combination sulfuration just can be made to have very excellent mechanical property, resistance toheat and compression set performance, but in order to make the vulcanized rubber obtained, there is more excellent over-all properties, preferably, with the gross weight of described terpolymer for benchmark, the content of ethylene unit unit is 60-70 % by weight, the content of propylene structural unit is 25-35 % by weight, the content of ethylidene norbornene structural unit is 5-10 % by weight.
The mooney viscosity of the present invention to described terpolymer is not particularly limited, preferably, the mooney viscosity of described terpolymer is 70-90, can make up because higher the brought green strength of ethylene unit unit content is lower like this, problem that tensile strength and wear resistance loss and mixing cycle extend, make the vulcanized rubber obtained have higher tensile strength and shorten mixing cycle.In the present invention, described mooney viscosity can measure according to method disclosed in GB/T1232.1-2000 and obtain, and wherein, warm up time is 1min, and rotation time is 4min, and test temperature is 125 DEG C.
On described rubber combination and vulcanized rubber, the application in the rubber gasket for the preparation of shield structure material has larger impact to the molecular weight distribution of described terpolymer.As a rule, the terpolymer of described narrow molecular weight distribution can make the rubber combination obtained have higher curing efficiency and lower compression set value, but the intensity of rubber is lower; The wide terpolymer of molecular weight distribution has good mobility, but can reduce vulcanization rate and final state of vulcanization, and therefore, combined factors is from every side considered, the molecular weight distribution of described terpolymer is preferably 3-5.
According to the present invention, described terpolymer can pass through commercially available, also can according to well known to a person skilled in the art that various method prepares, and all can know these those skilled in the art, therefore not to repeat here.
According to the present invention, in described rubber combination, the consumption of each component can be all the routine selection of this area, such as, with the described terpolymer of 100 weight parts for benchmark, the content of described vulcanizing agent can be 1-3 weight part, the content of described vulcanization accelerator can be 2-10 weight part, and the content of described activator can be 2-10 weight part, and the content of described toughener can be 100-200 weight part; Preferably, with the described terpolymer of 100 weight parts for benchmark, the content of described vulcanizing agent is 1.5-2 weight part, and the content of described vulcanization accelerator is 5-7 weight part, the content of described activator is 5-9 weight part, and the content of described toughener is 120-160 weight part.
According to the present invention, described vulcanizing agent can be the vulcanizing agent of various routine, such as, can be insoluble sulfur and/or four sulfuration two morpholines, be particularly preferably insoluble sulfur.Described insoluble sulfur is the allotropic substance of sulphur, and it is insoluble to sulfurous gas and other solvent, is also insoluble to rubber, exists in rubber with dispersion state; After reaching curing temperature, these insoluble sulfurs be dispersed in rubber have one " activation stage ", i.e. chain type unzipping makes vulcanization rate accelerate, and reduce insoluble sulfur consumption, are conducive to the aging resistance improving rubber.
According to the present invention, described vulcanization accelerator can be the existing various curing time that can shorten, reduce curing temperature, reduce vulcanizing agent consumption and improve the material of the mechanical property of rubber, such as, can be that (commodity are called zinc dibutyl dithiocaarbamate: accelerant B Z), thiazole accelerator (such as, the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide (commodity are called TBBS or NS), 2, 2 '-dibenzothiazyl disulfide (commodity are called: altax), curing mercaptobenzothiazole (commodity are called: accelerant MBT S) etc.), N, the two thiamide (trade(brand)name: Vulcanization accelerator TMTD) of N-tetramethyl-two sulphur, 4, 4 '-dithio morpholine (trade(brand)name: vulkacit D TDM), one or more in the N-tertiary butyl-bis-(2-[4-morpholinodithio) sulfenamide (commodity be called: accelerator TBSI) and vulkacit D (commodity are by name: vulkacit D).
According to the present invention, described activator refers to the activity that can increase vulcanization accelerator, and then reduces the consumption of described vulcanization accelerator or shorten the material of curing time.Add sulphidity and thermotolerance that a small amount of promoting agent can significantly improve described rubber.Vulcanizing agent of the present invention can be existing various vulcanizing agent, such as, can be one or more in zinc oxide, stearic acid and polyoxyethylene glycol.Wherein, the nano zine oxide of described zinc oxide to be particularly preferably average particulate diameter be 1-100nm.The equal molecule of number of described polyoxyethylene glycol can be 200-8000.
According to the present invention, described toughener can be the existing various material that can improve the intensity of described rubber combination and vulcanized rubber, such as, can be carbon black and/or white carbon black.Wherein, described carbon black and white carbon black all can be commercially available, and such as, described carbon black can be one or more in industrial reference black 7#, high abrasion furnace black(HAF) N330 and medium super abrasion furnace black N220, is preferably medium super abrasion furnace black N220.Described white carbon black can purchased from Qingdao Rhodia, and the trade mark is Z1165MP.
According to the present invention, in described rubber combination can also according to practical situation selectivity contain in anti-aging agent, dispersion agent, inorganic filler and rubber filling oil one or more.The content of described anti-aging agent, dispersion agent, inorganic filler and rubber filling oil can be the routine selection of this area, will not repeat at this.
According to the present invention, the kind of described anti-aging agent is known to the skilled person, such as, can 2 be selected from, 2,4-trimethylammonium-1,2-dihyaroquinoline polymer, N-(1,3-dimethylbutyl) one or more in-N '-diphenyl-para-phenylene diamine (commodity be called: antioxidant 4020), N-cumyl-N '-diphenyl-para-phenylene diamine (commodity are called: antioxidant 4010NA) and N-phenyl-2-naphthylamine (commodity are by name: antioxidant D).It should be noted that, 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymers of the present invention refer to the dimer of 2,2,4-trimethylammonium-1,2-dihyaroquinoline, tripolymer or the tetramer (that is, n=2,3 or 4); And due to the dimeric anti-old performance of described 2,2,4-trimethylammonium-1,2-dihyaroquinolines very excellent, therefore, described 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymers are preferably dimer or dimer and tripolymer and/or tetrameric mixture.More preferably, when described 2,2,4-trimethylammonium-1,2-dihyaroquinoline dimer be dimer and tripolymer and/or tetrameric mixture time, with the gross weight of described mixture for benchmark, described dimeric content is 25-55 % by weight, and described dimer and trimerical total content are 45-75 % by weight.
In addition, the kind of described dispersion agent, mineral filler and rubber filling oil can be all that the routine of this area is selected, and such as, described dispersion agent can be one or more in paraffin, Microcrystalline Wax, aliphatic category dispersion agent and lipid dispersion agent.Described inorganic filler can be one or more in calcium carbonate, kaolin and calcinated argil.Described rubber filling oil can be one or more in paraffin oil, machine oil and naphthenic oil.
Present invention also offers the vulcanized rubber obtained by above-mentioned rubber combination sulfuration.
According to the present invention, as a rule, method and the condition of described rubber combination being carried out sulfuration are conventionally known to one of skill in the art.Such as, described sulfuration can be carried out in vulcanization bed or vulcanizing press; Described cure conditions generally includes the temperature of sulfuration, pressure and time, and wherein, in order to more be conducive to the sulfuration of described rubber, the temperature of described sulfuration is preferably 140-160 DEG C, and the pressure of sulfuration is preferably 5-15MPa, and the time of sulfuration is preferably 0.15-1 hour.
In addition, present invention also offers above-mentioned rubber combination and/or the application of vulcanized rubber in the rubber gasket for the preparation of shield structure material.
Main improvement of the present invention mainly there are provided a kind of new rubber combination and vulcanized rubber, and can be same as the prior art for the detailed process of the rubber gasket of shield structure material described in prepared by this rubber combination and/or vulcanized rubber, therefore not to repeat here.
Below will be described the present invention by embodiment.
In following examples and comparative example:
Mooney viscosity adopts the SMV-300 type mooney's viscosimeter of Japanese Shimadzu Corporation to obtain according to GB/T1232.1-2000 standard test, and wherein, warm up time is 1min, and rotation time is 4min, and test temperature is 125 DEG C.Molecular weight distribution adopts 2000 type gel permeation chromatographs (GPC) of WATERS company of the U.S. to measure, and take trichlorobenzene as moving phase, Narrow distribution polystyrene is standard specimen, and probe temperature is 150 DEG C.In terpolymer, the content of each structural unit adopts Switzerland Bruker company AVANCE DRX400MHz nuclear magnetic resonance spectrometer to measure, and solvent is deuterochloroform.
In following examples and comparative example:
The average particulate diameter of nano zine oxide is 100nm, and purchased from Shanghai company of Yi Hui nanosecond science and technology company limited, the trade mark is YH-Zn-01;
Stearic acid: purchased from the polite Chemical Co., Ltd. in Hong Kong, the trade mark is SA1801;
Polyoxyethylene glycol: the trade mark is PEG-300;
Dispersion agent is aliphatic category dispersion agent, and purchased from company of Hua Shi rubber and plastic Science and Technology Ltd., the trade mark is FC-303;
Carbon black is medium super abrasion furnace black N220, purchased from Tianjin gold autumn real carbon black Chemical Co., Ltd.;
Insoluble sulfur: contain Science and Technology Ltd. purchased from Jinchang, Guangzhou, S-80;
Paraffin oil: purchased from Hengshui City Bi Song Chemical Co., Ltd., the trade mark is SK-300#;
Accelerant B Z: the Accelerator77 of purchased from American;
Vulcanization accelerator TMTD: purchased from northeast auxiliary agent Chemical Co., Ltd., the trade mark is promotor TT;
Vulkacit D TDM: purchased from sky Science and Technology Ltd.;
Thiophene-based promotor is MBTS, and purchased from Tianjin La Bo auxiliary agent company limited, the trade mark is altax.
Embodiment 1
This embodiment is for illustration of rubber combination provided by the invention and vulcanized rubber and preparation method thereof.
The rubber combination prepared in this embodiment and the component of vulcanized rubber as shown in table 1, wherein, terpolymer J1 used is China Petrochemical Industry Beijing Yanshan Mountain branch office pilot product, is obtained by ethene, propylene and ethylidene norbornene copolymerization; With the gross weight of described terpolymer for benchmark, the content of ethylene unit unit is 60.8 % by weight, and the content of propylene structural unit is 34.0 % by weight, and the content of ethylidene norbornene structural unit is 5.2 % by weight; Mooney viscosity is 78, and molecular weight distribution is 3.4.
Table 1
| Component | Mass fraction |
| Terpolymer J1 | 100 |
| Nano zine oxide | 5 |
| Stearic acid | 1 |
| Polyoxyethylene glycol | 2.5 |
| Dispersion agent | 2 |
| Calcium carbonate | 50 |
| Carbon black | 120 |
| Paraffin oil | 90 |
| Calcium oxide | 10 |
| Insoluble sulfur | 1.5 |
| Accelerant B Z | 2 |
| Vulcanization accelerator TMTD | 0.75 |
| Vulkacit D TDM | 0.75 |
| Thiazole accelerator MBTS | 2.5 |
Each component shown in table 1 is placed in mill, and roller temperature be 70 ± 5 DEG C, roller speed is 24 ± 1 revs/min, mix under the condition of roller speed ratio 1.0:1.4, obtains rubber combination rubber unvulcanizate H1.Then 150 DEG C, under 5MPa, rubber combination rubber unvulcanizate H1 is carried out sulfidizing 0.2 hour at vulcanizing press, obtains vulcanized rubber S1.
Embodiment 2
This embodiment is for illustration of rubber combination provided by the invention and vulcanized rubber and preparation method thereof.
The rubber combination prepared in this embodiment and the component of vulcanized rubber as shown in table 2, wherein, terpolymer J2 used, purchased from Jin Hu company of Korea S, is obtained by ethene, propylene and ethylidene norbornene copolymerization; With the gross weight of described terpolymer for benchmark, the content of ethylene unit unit is 67 % by weight, and the content of propylene structural unit is 27.3 % by weight, and the content of ethylidene norbornene structural unit is 5.7 % by weight; Mooney viscosity is 82, and molecular weight distribution is 4.5.
Table 2
| Component | Mass fraction |
| Terpolymer J2 | 100 |
| Nano zine oxide | 5 |
| Stearic acid | 1.5 |
| Polyoxyethylene glycol | 2 |
| Dispersion agent | 2 |
| Calcium carbonate | 40 |
| Carbon black | 140 |
| Paraffin oil | 90 |
| Calcium oxide | 12 |
| Insoluble sulfur | 1.4 |
| Accelerant B Z | 2 |
| Vulcanization accelerator TMTD | 0.75 |
| Vulkacit D TDM | 0.75 |
| Thiazole accelerator MBTS | 3 |
Each component shown in table 2 is placed in mill, and roller temperature be 70 ± 5 DEG C, roller speed is 24 ± 1 revs/min, mix under the condition of roller speed ratio 1.0:1.4, obtains rubber combination rubber unvulcanizate H2.Then 150 DEG C, under 5MPa, rubber combination rubber unvulcanizate H2 is carried out sulfidizing 0.2 hour at vulcanizing press, obtains vulcanized rubber S2.
Embodiment 3
This embodiment is for illustration of rubber combination provided by the invention and vulcanized rubber and preparation method thereof.
The rubber combination prepared in this embodiment and the component of vulcanized rubber as shown in table 3, wherein, terpolymer J3 used is China Petrochemical Industry Beijing Yanshan Mountain branch office pilot product, is obtained by ethene, propylene and ethylidene norbornene copolymerization; With the gross weight of described terpolymer for benchmark, the content of ethylene unit unit is 63.7 % by weight, and the content of propylene structural unit is 30.8 % by weight, and the content of ethylidene norbornene structural unit is 5.5 % by weight; Mooney viscosity is 84, and molecular weight distribution is 3.4.
Table 3
| Component | Mass fraction |
| Terpolymer J3 | 100 |
| Nano zine oxide | 4.5 |
| Stearic acid | 1 |
| Polyoxyethylene glycol | 3 |
| Dispersion agent | 2.5 |
| Calcium carbonate | 45 |
| Carbon black | 130 |
| Paraffin oil | 90 |
| Calcium oxide | 12 |
| Insoluble sulfur | 1.7 |
| Accelerant B Z | 2 |
| Vulcanization accelerator TMTD | 0.5 |
| Vulkacit D TDM | 0.5 |
| Thiazole accelerator MBTS | 2 |
Each component shown in table 3 is placed in mill, and roller temperature be 70 ± 5 DEG C, roller speed is 24 ± 1 revs/min, mix under the condition of roller speed ratio 1.0:1.4, obtains rubber combination rubber unvulcanizate H3.Then 150 DEG C, under 5MPa, rubber combination rubber unvulcanizate H3 is carried out sulfidizing 0.2 hour at vulcanizing press, obtains vulcanized rubber S3.
Embodiment 4
This embodiment is for illustration of rubber combination provided by the invention and vulcanized rubber and preparation method thereof.
Rubber combination and vulcanized rubber is prepared according to the method for embodiment 1, unlike, terpolymer J4(China Petrochemical Industry Beijing Yanshan Mountain branch office pilot product of described terpolymer J1 identical weight part) substitute, it is obtained by ethene, propylene and ethylidene norbornene copolymerization; With the gross weight of described terpolymer for benchmark, the content of ethylene unit unit is 58.3 % by weight, and the content of propylene structural unit is 37.0 % by weight, and the content of ethylidene norbornene structural unit is 4.7 % by weight; Mooney viscosity is 82, and molecular weight distribution is 3.7.Obtain vulcanized rubber S4.
Embodiment 5
This embodiment is for illustration of rubber combination provided by the invention and vulcanized rubber and preparation method thereof.
Prepare rubber combination and vulcanized rubber according to the method for embodiment 1, the average particulate diameter unlike, described nano zine oxide identical weight part is that the common zinc oxide of 1 micron substitutes.Obtain vulcanized rubber S5.
Embodiment 6
This embodiment is for illustration of rubber combination provided by the invention and vulcanized rubber and preparation method thereof.
Rubber combination and vulcanized rubber is prepared according to the method for embodiment 1, unlike, the consumption of described insoluble sulfur is 1.2 weight parts.Obtain vulcanized rubber S6.
Comparative example 1
This comparative example is for illustration of the rubber combination and vulcanized rubber and preparation method thereof of reference.
Rubber combination and vulcanized rubber is prepared according to the method for embodiment 1, unlike, described terpolymer-1 reference terpolymer DJ1(China Petrochemical Industry Beijing Yanshan Mountain branch office pilot product of identical weight part) substitute, it is obtained by ethene, propylene and ethylidene norbornene copolymerization; With the gross weight of described terpolymer for benchmark, the content of ethylene unit unit is 55.1 % by weight, and the content of propylene structural unit is 40.4 % by weight, and the content of ethylidene norbornene structural unit is 4.5 % by weight; Mooney viscosity is 98, and molecular weight distribution is 3.8.Obtain reference vulcanized rubber DS1.
Test case 1-6
Test case 1-6 is for illustration of the test of vulcanized rubber performance provided by the invention.
(1) minimum torque (ML), the highest moment of torsion (MH), Ts2 and Tc90:
Test the minimum torque of vulcanized rubber S1-S6, the highest moment of torsion, Ts2 and Tc90 respectively according to GB/T16584-1996 standard, test condition comprises: temperature is 160 DEG C, and the test duration is 0.2h.Acquired results is as shown in table 4.Wherein, time when Ts2 represents that sizing material moment of torsion reaches (minimal torque+2), the now sulfuration of sizing material reaches given pace, indirectly can think the time that sizing material finalizes the design almost; T90 represents and refers to that sizing material reaches the time of 90% sulfuration.
(2) tensile strength and elongation at break:
Test the tensile strength of vulcanized rubber S1-S6 and elongation at break respectively according to GB/T528-2009 standard, acquired results is as shown in table 4.
(3) shore hardness:
Test the shore hardness of vulcanized rubber S1-S6 respectively according to GB/T531.1-2008 standard, acquired results is as shown in table 4.
(4) angle tear strength:
Test the angle tear strength of vulcanized rubber S1-S6 respectively according to GB/T529-2008 standard, acquired results is as shown in table 4.
(5) 24h permanent compression set:
Test the 24h permanent compression set of vulcanized rubber S1-S6 respectively according to GB/T7759-1996 standard, acquired results is as shown in table 4.
(6) hardness:
Test the aging front hardness of vulcanized rubber S1-S6 respectively according to the method specified in GB/T531.1-2008, acquired results is as shown in table 4;
Carry out thermal ageing 24h to vulcanized rubber S1-S6 respectively according to the method specified in GB/T3512-2001, then test the hardness after the aging 24h of vulcanized rubber S1-S6 respectively according to the method specified in GB/T531.1-2008, acquired results is as shown in table 4.
Contrast test example 1
Contrast test example 1 is for illustration of the test of reference vulcanized rubber performance.
Test according to the performance of method to the reference vulcanized rubber DS1 obtained by comparative example 1 of test case 1-6, acquired results is as shown in table 4.
Table 4
| Project | S1 | S2 | S3 | S4 | S5 | S6 | DS1 |
| ML | 4.1 | 4.2 | 4.4 | 4.2 | 4.1 | 4.0 | 5.3 |
| MH | 14.6 | 15.3 | 14.9 | 14.2 | 14.5 | 14.5 | 14.2 |
| Ts2 | 0:52 | 0:55 | 0:50 | 1:10 | 0:56 | 0:53 | 1:08 |
| Tc90 | 1:30 | 1:58 | 1:40 | 1:44 | 1:45 | 1:35 | 3:11 |
| Tensile strength, MPa | 11.2 | 11.8 | 10.8 | 10.4 | 11.1 | 11.0 | 10.1 |
| Elongation at break, % | 349 | 354 | 375 | 331 | 340 | 344 | 329 |
| Shore hardness, A | 70 | 72 | 69 | 70 | 71 | 68 | 74 |
| Angle tear strength, KN/m | 27 | 30 | 27 | 26 | 26 | 24 | 25 |
| 24h permanent compression set value, % | 18.1 | 17.5 | 18.9 | 19.1 | 18.5 | 19.4 | 29.2 |
| Aging front hardness | 68 | 71 | 68 | 69 | 70 | 67 | 72 |
| Hardness after aging 24h | 71 | 73 | 70 | 72 | 72 | 72 | 78 |
From the results shown in Table 4, the vulcanized rubber obtained by rubber combination sulfuration provided by the invention has higher mechanical property and thermotolerance (is reacted by the changing value of aging front and back hardness, changing value large explanation resistance toheat is poor, changing value little explanation resistance toheat is good) and lower compression set value, be highly suitable for the application in the rubber gasket for the preparation of shield structure material.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a rubber combination, it is characterized in that, described rubber combination contains the terpolymer of ethene and propylene and ethylidene norbornene, vulcanizing agent, vulcanization accelerator, activator and toughener, and with the gross weight of described terpolymer for benchmark, the content of ethylene unit unit is not less than 58 % by weight, and the content of ethylidene norbornene structural unit is not less than 4.5 % by weight.
2. rubber combination according to claim 1, wherein, with the gross weight of described terpolymer for benchmark, the content of ethylene unit unit is 60-70 % by weight, the content of propylene structural unit is 25-35 % by weight, and the content of ethylidene norbornene structural unit is 5-10 % by weight.
3. rubber combination according to claim 1 and 2, wherein, the mooney viscosity of described terpolymer is 70-90.
4. rubber combination according to claim 1 and 2, wherein, the molecular weight distribution of described terpolymer is 3-5.
5. rubber combination according to claim 1, wherein, with the described terpolymer of 100 weight parts for benchmark, the content of described vulcanizing agent is 1-3 weight part, the content of described vulcanization accelerator is 2-10 weight part, the content of described activator is 2-10 weight part, and the content of described toughener is 100-200 weight part.
6. rubber combination according to claim 1 or 5, wherein, described vulcanizing agent is insoluble sulfur and/or four sulfuration two morpholines; Preferably, described vulcanization accelerator is zinc dibutyl dithiocaarbamate, the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide, 2,2 '-dibenzothiazyl disulfide, curing mercaptobenzothiazole, N, the two thiamide, 4 of N-tetramethyl-two sulphur, one or more in 4 '-dithio morpholine, the N-tertiary butyl-bis-(2-[4-morpholinodithio) sulfenamide and vulkacit D; Preferably, described activator is one or more in zinc oxide, stearic acid and polyoxyethylene glycol; Preferably, described toughener is carbon black and/or white carbon black.
7. rubber combination according to claim 6, wherein, described vulcanizing agent is insoluble sulfur; The nano zine oxide of described activator to be average particulate diameter be 1-100nm.
8. rubber combination according to claim 1, wherein, described rubber combination is also containing one or more in anti-aging agent, dispersion agent, inorganic filler and rubber filling oil.
9. obtain vulcanized rubber by the rubber combination sulfuration in claim 1-8 described in any one.
10. the rubber combination in claim 1-8 described in any one and/or the application of vulcanized rubber according to claim 9 in the rubber gasket for the preparation of shield structure material.
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| CN113881148A (en) * | 2021-09-24 | 2022-01-04 | 安徽京鸿密封件技术有限公司 | Low-compression permanent-deformation sulfur-vulcanized sealing ring ethylene propylene diene monomer rubber material |
| CN114426263A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing insoluble sulfur by low-temperature melting process |
| CN115490966A (en) * | 2021-12-14 | 2022-12-20 | 江苏锐巴新材料科技有限公司 | High-performance continuous vulcanized rubber material and application thereof |
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| CN114426263B (en) * | 2020-10-13 | 2023-07-04 | 中国石油化工股份有限公司 | Method for preparing insoluble sulfur by low-temperature melting process |
| CN113881148A (en) * | 2021-09-24 | 2022-01-04 | 安徽京鸿密封件技术有限公司 | Low-compression permanent-deformation sulfur-vulcanized sealing ring ethylene propylene diene monomer rubber material |
| CN115490966A (en) * | 2021-12-14 | 2022-12-20 | 江苏锐巴新材料科技有限公司 | High-performance continuous vulcanized rubber material and application thereof |
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