CN103254511A - Ethylene-propylene-diene monomer - Google Patents
Ethylene-propylene-diene monomer Download PDFInfo
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- CN103254511A CN103254511A CN2012100389824A CN201210038982A CN103254511A CN 103254511 A CN103254511 A CN 103254511A CN 2012100389824 A CN2012100389824 A CN 2012100389824A CN 201210038982 A CN201210038982 A CN 201210038982A CN 103254511 A CN103254511 A CN 103254511A
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Abstract
The invention discloses an ethylene-propylene-diene monomer. The ethylene-propylene-diene monomer is a product formed through mixing and vulcanizing a composition, wherein the composition includes 100 parts of an ethylene-propylene-diene monomer material, 0.5-4.5 parts by weight of a vulcanizing agent, 4-13 parts by weight of a vulcanizing activator system, 3-10 parts by weight of a promoter, 40-90 parts by weight of a reinforcing agent, and 5-60 parts of a softening plasticizer; the vulcanizing agent is insoluble sulfur and/or pre-dispersed sulfur; the vulcanizing activator system contains a component A and stearic acid; the component A is selected from zinc oxide and/or pre-dispersed zinc oxide; and the weight ratio of the component A to the stearic acid is 1-10:1. The optimal ethylene-propylene-diene monomer has the advantages of no blooming, no generation of nitrosamine, and good mechanical properties.
Description
Technical field
The present invention relates to a kind of terpolymer EP rubber.
Background technology
The degree of unsaturation of terpolymer EP rubber (EPDM) and other high unsaturated alkadiene rubber phase are than much lower, when vulcanizing with sulfur sulfide system, the activity of sulfuration is lower, for vulcanization rate and the state of vulcanization that improves sizing material, adopts the accelerator combination system of high consumption usually in prescription.Terpolymer EP rubber is owing to lack active group in the molecular structure, and internal cohesive energy is low, and autohension and mutual viscosity are very poor, and sizing material is when the accelerator content that adds is high, and sizing material is easy to bloom.And in order to obtain the good mechanical performance, the application of high reactivity ultra fast accelerator (as dithiocarbamate(s) and thiurams) in terpolymer EP rubber is very general.These promotor often have the secondary amine structure, can generate the N-nitrosamine with nitrosation agent (amino-oxide Nox) reaction.Definite, the N-nitrosamine has carinogenicity.Germany rules TRGS 552 has stipulated to forbid 12 kinds of carcinogenic N-nitrosamine, relates to the rubber ingredients of multiple present domestic widespread use." following chemical policy strategy white paper " that particularly October calendar year 2001, European Union delivered listed vulcanizing agent DTDM and some thiuram type accelerator (as TMTD etc.) in chemical that time limit is eliminated.
Disclosing a kind of light sealed strip that nitrosamine discharges that do not have among the CN102140206A, is that the one-tenth by following weight part is grouped into: as 100 parts of terpolymer EP rubbers, nano kaoline 10-30 part, coarse whiting 10-30 part, white carbon black 5-20 part, titanium dioxide 5-30 part, paraffin oil 30-50 part, Vaseline 2-8 part, anti-aging agent 0.5-5 part, peroxide vulcanizing agent 0.5-5 part, poly-dihydric alcohol 0.5-3 part and zinc acrylate resin 5-10 part of basic recipe.Although this invention can solve the problem that nitrosamine discharges, the terpolymer EP rubber that this invention prepares when obtaining preferably mechanical property, tends to produce bloom.To sum up, need a kind of vulcanization rate at present badly comparatively fast and have no blooming concurrently and the terpolymer EP rubber of better mechanical property.Preferably, this terpolymer EP rubber not generate nitrosamines.
Summary of the invention
Purpose of the present invention is in order to overcome existing terpolymer EP rubber in order to obtain the good mechanical performance, thereby often need to add the shortcoming that a large amount of promotor is caused the easy bloom of terpolymer EP rubber, provide a kind of vulcanization rate comparatively fast and have no blooming concurrently and the terpolymer EP rubber of better mechanical property.
To achieve these goals, the invention provides a kind of terpolymer EP rubber, this rubber is for containing the terpolymer EP rubber sizing material, vulcanizing agent, the vulcanization leveller system, promotor, mixing and the sulfuration of the composition of toughener and softening softening agent and the product that forms, wherein, described vulcanizing agent is insoluble sulfuy and/or pre-dispersed Sulfur, described vulcanization leveller system contains component A and stearic acid, described component A is selected from active zinc flower and/or pre-dispersed zinc oxide, in described composition, with respect to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is the 0.5-4.5 weight part, the content of described vulcanization leveller system is the 4-13 weight part, the content of described promotor is the 3-10 weight part, the content of described toughener is the 40-90 weight part, the content of described softening softening agent is the 5-60 weight part, and described component A and stearic weight ratio are 1-10: 1.
Compare with existing ethylene-propylene rubber(EPR), terpolymer EP rubber no blooming provided by the invention and mechanical property are good.Under the preferable case, terpolymer EP rubber provided by the invention has no blooming concurrently, mechanical property is good and the advantage of not generate nitrosamines.For example, the sulfurizing time T of the terpolymer EP rubber that provides of the embodiment of the invention 1
90It is 34 minutes 23 seconds; Tensile strength at normal temperatures is 15.1MPa, and 100% stress at definite elongation is 2.0MPa, and 300% stress at definite elongation is 9.0MPa, and tensile yield is 476%, and tear strength is 27KN/m; Tensile strength after 120 ℃ * 24h is aging is 16.4MPa, and 100% stress at definite elongation is 5.8MPa, and tensile yield is 239%; Tensile strength after 120 ℃ * 72h is aging is 18.3MPa, and tensile yield is 193%.The bloom experimental result is no blooming, because promotor is ZDBP, can not produce nitrosamine.And the sulfurizing time T of the terpolymer EP rubber that Comparative Examples 1 provides
90It is 11 minutes 37 seconds; Tensile strength under the normal temperature is 13.3MPa, and 100% stress at definite elongation is 3.7MPa, and 300% stress at definite elongation is 11.3MPa, and tensile yield is 350%, and tear strength is 30KN/m; Tensile strength after 120 ℃ * 24h is aging is 14.2MPa, and 100% stress at definite elongation is 4.9MPa, and tensile yield is 252%; Tensile strength after 120 ℃ * 72h is aging is 12.7MPa, and 100% stress at definite elongation is 5.6MPa, and tensile yield is 189%.The bloom experimental result is bloom.Owing to contain TM monex TD, produce nitrosamine.
Description of drawings
Accompanying drawing is to be used to provide further understanding of the present invention, and constitutes the part of specification sheets, is used from explanation the present invention with following embodiment one, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the bloom experimental result photo of the terpolymer EP rubber that makes of Comparative Examples 1;
Fig. 2 is the EPDM bloom experimental result photo that embodiment 1 makes;
Fig. 3 is the bloom experimental result photo of the terpolymer EP rubber that makes of embodiment 2;
Fig. 4 is the bloom experimental result photo of the terpolymer EP rubber that makes of embodiment 3;
Fig. 5 is the bloom experimental result photo of the terpolymer EP rubber that makes of embodiment 4;
Fig. 6 is the bloom experimental result photo of the terpolymer EP rubber that makes of embodiment 5;
Fig. 7 is the bloom experimental result photo of the terpolymer EP rubber that makes of embodiment 6;
Fig. 8 is the bloom experimental result photo of the terpolymer EP rubber that makes of embodiment 7;
Fig. 9 is the bloom experimental result photo of the terpolymer EP rubber that makes of embodiment 8.
Embodiment
According to terpolymer EP rubber of the present invention, this rubber is for containing the terpolymer EP rubber sizing material, vulcanizing agent, the vulcanization leveller system, promotor, mixing and the sulfuration of the composition of toughener and softening softening agent and the product that forms, wherein, described vulcanizing agent is insoluble sulfuy and/or pre-dispersed Sulfur, described vulcanization leveller system contains component A and stearic acid, described component A is selected from active zinc flower and/or pre-dispersed zinc oxide, in described composition, with respect to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is the 0.5-4.5 weight part, the content of described vulcanization leveller system is the 4-13 weight part, the content of described promotor is the 3-10 weight part, the content of described toughener is the 40-90 weight part, the content of described softening softening agent is the 5-60 weight part, and described component A and stearic weight ratio are 1-10: 1.
According to terpolymer EP rubber of the present invention, preferably, in described composition, with respect to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is that the content of 1-3 weight part, described vulcanization leveller system is that the content of 5-7 weight part, described promotor is the 4-9 weight part, the content of described toughener is that the content of 75-85 weight part, described softening softening agent is the 45-55 weight part, and described component A and stearic weight ratio are 4-6: 1.When the preparation terpolymer EP rubber, in described composition, the terpolymer EP rubber sizing material accounts for 36.04 weight % to 65.57 weight %.
According to terpolymer EP rubber of the present invention, preferably, described promotor is contained first promotor and second promotor, and described first promotor is promotor ZDBP, and described second promotor is not for generating the promotor of nitrosamine except ZDBP.When adopting aforementioned promotor, the terpolymer EP rubber of acquisition can be when having good mechanical system energy and no blooming concurrently, not generate nitrosamines.
According to terpolymer EP rubber of the present invention, the present invention does not have particular requirement to the kind of described second promotor, variously in the prior art do not generate the promotor of nitrosamine except ZDBP and all can realize purpose of the present invention, preferably, described second promotor is selected from one or more in vulkacit D TDC, captax, the accelerator CBS, is preferably captax.Aforesaid promotor all can be commercially available.
According to terpolymer EP rubber of the present invention, although first promotor of various weight ratios and second promotor all can be realized purpose of the present invention, preferably, the weight ratio of described first promotor and second promotor is 10-18: 1, be preferably 12-16: 1.Adopt the weight ratio of aforementioned first promotor and second promotor, can improve the mechanical property of terpolymer EP rubber further.
As those skilled in the known, insoluble sulfuy is gained the name because being insoluble to dithiocarbonic anhydride.According to terpolymer EP rubber of the present invention, the present invention does not have particular restriction to the kind of described insoluble sulfuy, various conventional insoluble sulfuy of the prior art all can be used for the present invention, preferably, the insoluble sulphur content of described insoluble sulfuy is 30-90 weight %, and being preferably insoluble sulphur content is the insoluble sulfuy IS60 of 60 weight %.
As those skilled in the known, pre-dispersed Sulfur refers to can discharge under the normal cure conditions Sulfur of free sulphur, different with common Sulfur, pre-dispersed Sulfur mainly forms monosulfidic bond and cystine linkage, and according to terpolymer EP rubber of the present invention, the present invention does not have particular restriction to the kind of described pre-dispersed Sulfur, the pre-dispersed Sulfur of various routines of the prior art all can be used for the present invention, preferably, described pre-dispersed Sulfur is pre-dispersed S-80, and Sulfur amount wherein is 80 weight %; As those skilled in the known, described pre-dispersed zinc oxide is the indirect process zinc oxide through pre-dispersed processing.The present invention does not have particular restriction to the kind of described pre-dispersed zinc oxide, the pre-dispersed zinc oxide of various routines of the prior art all can be used for the present invention, preferably, described pre-dispersed zinc oxide is pre-dispersed zinc oxide master batch ZnO-80, and wherein zinc oxide content is 80 weight %.
As those skilled in the known, described active zinc flower is a kind of zinc oxide of the activated processing of particle surface.According to terpolymer EP rubber of the present invention, the present invention does not have particular restriction to the kind of described active zinc flower, and various conventional active zinc flowers of the prior art all can be used for the present invention, preferably, the median size of described active zinc flower is 1-100nm, is preferably 1-50nm.
According to terpolymer EP rubber of the present invention, the present invention does not have particular requirement to the kind of described toughener, various tougheners all can be realized purpose of the present invention in the prior art, preferably, described toughener is selected from one or more in carbon black, white carbon black, staple fibre, calcium carbonate and the aluminium carbonate, is preferably carbon black.
According to terpolymer EP rubber of the present invention, the present invention does not have particular requirement to the kind of softening softening agent, various softening softening agent all can be realized purpose of the present invention in the prior art, wherein, softening softening agent is selected from one or more in paraffin oil, aromatic hydrocarbon oil, the naphthenic oil, is preferably ASTM103# oil.
According to terpolymer EP rubber of the present invention, the present invention does not have particular requirement to the kind of terpolymer EP rubber, and various terpolymer EP rubbers of the prior art all can be realized purpose of the present invention.
According to terpolymer EP rubber of the present invention, the present invention does not have particular requirement to described condition mixing and sulfuration, and prior art condition mixing to terpolymer EP rubber and sulfuration all can realize purpose of the present invention, preferably, described mixing temperature is 30-40 ℃, is preferably 32-38 ℃; Time is 15-30 minute, is preferably 18-24 minute; The temperature of described sulfuration is 140-180 ℃, is preferably 150-170 ℃; Pressure is 5-10MPa, is preferably 6.5-8.5MPa; Time is 5-55 minute, is preferably 10-50 minute.
Below will describe the present invention by embodiment.In following examples, unless stated otherwise, part expression weight part, the method that performance test relates to is as follows:
1, adopts the vulcanization characteristics of vulkameter test analysis terpolymer EP rubber.
2, adopt the ambient temperature mechanical properties of puller system test analysis terpolymer EP rubber, the aging back of 120 ℃ * 24h mechanical property, the aging back of 120 ℃ * 72h mechanical property.
3, adopt ageing oven to the bloom performance test analysis of terpolymer EP rubber.Setting oven temperature is 70 ℃, gets the water (guaranteeing not dried in the 72h) that container at a gulp holds capacity, with fine rule the cross-linked rubber sample is hung on apart from the about 20mm of water surface place, takes out behind the insulation 72h and observes.
Comparative Examples 1
Terpolymer EP rubber sizing material (Jiization J4045) is added 5 parts in zinc oxide in 35 ± 5 ℃ of priorities of temperature for 100 parts on two roll rubber mixing mill, 1 part of stearic acid, 80 parts of carbon blacks, 50 parts of ASTM103# oil (evolution worker company limited of Ningbo association), 1 part of TM monex TD, 0.5 part of captax, 1.5 parts of Sulfurs are mixing even, the mixing time is 21 minutes, obtains blend.Again with blend 160 ℃ of temperature, sulfuration is 20 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtains terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90It is 11 minutes 37 seconds; Tensile strength under the normal temperature is 13.3MPa, and 100% stress at definite elongation is 3.7MPa, and 300% stress at definite elongation is 11.3MPa, and tensile yield is 350%, and tear strength is 30kN/m.Tensile strength after 120 ℃ * 24h is aging is 14.2MPa, and 100% stress at definite elongation is 4.9MPa, and tensile yield is 252%.Tensile strength after 120 ℃ * 72h is aging is 12.7MPa, and 100% stress at definite elongation is 5.6MPa, and tensile yield is 189%.The bloom experimental result is bloom, and photo is seen Fig. 1.Promotor is TMTD, can produce nitrosamine.
Embodiment 1
Terpolymer EP rubber sizing material (Jiization J4045) is added 5 parts of active zinc flowers in 35 ± 5 ℃ of priorities of temperature for 100 parts on two roll rubber mixing mill, 1 part of stearic acid, 80 parts of carbon blacks, 50 parts of ASTM103# oil, 4 parts of promotor ZDBP, 1.5 part insoluble sulfuy IS60-10 is mixing evenly, the mixing time is 21 minutes, obtains blend.Again with blend 160 ℃ of temperature, sulfuration is 40 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtains terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90It is 34 minutes 23 seconds; Tensile strength under the normal temperature is 15.1MPa, and 100% stress at definite elongation is 2.0MPa, and 300% stress at definite elongation is 9.0MPa, and tensile yield is 476%, and tear strength is 27KN/m.Tensile strength after 120 ℃ * 24h is aging is 16.4MPa, and 100% stress at definite elongation is 5.8MPa, and tensile yield is 239%.Tensile strength after 120 ℃ * 72h is aging is 18.3MPa, and tensile yield is 193%.The bloom experimental result is no blooming, and photo is seen Fig. 2.Promotor is ZDBP, can not produce nitrosamine.
By embodiment 1 and Comparative Examples 1 more as can be seen, according to the terpolymer EP rubber that the invention provides formulation, can be when having the good mechanical performance concurrently no blooming and not generate nitrosamines.
Embodiment 2
Terpolymer EP rubber sizing material (Jiization J4045) is added 6 parts of active zinc flowers in 35 ± 5 ℃ of priorities of temperature for 100 parts on two roll rubber mixing mill, 1 part of stearic acid, 75 parts of carbon blacks, 45 parts of ASTM103# oil (evolution worker company limited of Ningbo association), 8 parts of promotor ZDBP, 3 parts of insoluble sulfuy are mixing even, and the mixing time is 21 minutes, obtains blend.Again with blend 160 ℃ of temperature, sulfuration is 40 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtains terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90It is 32 minutes 55 seconds; Tensile strength under the normal temperature is 14.9MPa, and 100% stress at definite elongation is 3.7MPa, and 300% stress at definite elongation is 13.8MPa, and tensile yield is 325%, and tear strength is 30KN/m.Tensile strength after 120 ℃ * 24h is aging is 13.2MPa, and 100% stress at definite elongation is 6.0MPa, and tensile yield is 184%.Tensile strength after 120 ℃ * 72h is aging is 11.9MPa, and 100% stress at definite elongation is 7.5MPa, and tensile yield is 144%.The bloom experimental result is no blooming, and photo is seen Fig. 3.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 3
Terpolymer EP rubber sizing material (Jiization J4045) is added 4 parts of active zinc flowers in 35 ± 5 ℃ of priorities of temperature for 100 parts on two roll rubber mixing mill, 1 part of stearic acid, 85 parts of carbon blacks, 55 parts of ASTM103# oil (evolution worker company limited of Ningbo association), 6 parts of promotor ZDBP, 0.5 part of captax, 1 part of insoluble sulfuy is mixing even, the mixing time is 21 minutes, obtains blend.Again with blend 160 ℃ of temperature, sulfuration is 30 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtains terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90It is 25 minutes 57 seconds; Tensile strength under the normal temperature is 13.2MPa, and 100% stress at definite elongation is 2.7MPa, and 300% stress at definite elongation is 11.0MPa, and tensile yield is 355%, and tear strength is 32KN/m.Tensile strength after 120 ℃ * 24h is aging is 12.5MPa, and 100% stress at definite elongation is 3.7MPa, and tensile yield is 264%.Tensile strength after 120 ℃ * 72h is aging is 12.9MPa, and 100% stress at definite elongation is 4.8MPa, and tensile yield is 224%.The bloom experimental result is no blooming, and photo is seen Fig. 4.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 4
Terpolymer EP rubber sizing material (Jiization J4045) is added 5 parts of active zinc flowers in 35 ± 5 ℃ of priorities of temperature for 100 parts on two roll rubber mixing mill, 1 part of stearic acid, 80 parts of carbon blacks, 50 parts of ASTM103# oil (evolution worker company limited of Ningbo association), 8 parts of promotor ZDBP, 0.5 part of captax, 2 parts of insoluble sulfuy are mixing even, the mixing time is 21 minutes, obtains blend.Again with blend 160 ℃ of temperature, sulfuration is 25 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtains terpolymer EP rubber..
The sulfurizing time T of this terpolymer EP rubber
90It is 18 minutes 45 seconds; Tensile strength under the normal temperature is 12.4MPa, and 100% stress at definite elongation is 3.3MPa, and tensile yield is 291%, and tear strength is 29KN/m.Tensile strength after 120 ℃ * 24h is aging is 11.3MPa, and 100% stress at definite elongation is 4.9MPa, and tensile yield is 189%.Tensile strength after 120 ℃ * 72h is aging is 11.0MPa, and 100% stress at definite elongation is 6.5MPa, and tensile yield is 184%.The bloom experimental result is no blooming, and photo is seen Fig. 5.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 5
Terpolymer EP rubber sizing material (Jiization J4045) is added 5 parts of active zinc flowers in 35 ± 5 ℃ of priorities of temperature for 100 parts on two roll rubber mixing mill, 1 part of stearic acid, 80 parts of carbon blacks, 50 parts of ASTM103# oil (evolution worker company limited of Ningbo association), 8 parts of promotor ZDBP, 0.5 part of captax, 1.5 parts of insoluble sulfuy are mixing even, the mixing time is 21 minutes, obtains blend.Again with blend 160 ℃ of temperature, sulfuration is 25 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtains terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90It is 18 minutes 04 second; Tensile strength under the normal temperature is 13.3MPa, and 100% stress at definite elongation is 2.4MPa, and 300% stress at definite elongation is 9.2MPa, and tensile yield is 415%, and tear strength is 31KN/m.Tensile strength after 120 ℃ * 24h is aging is 11.7MPa, and 100% stress at definite elongation is 3.9MPa, and tensile yield is 249%.Tensile strength after 120 ℃ * 72h is aging is 11.2MPa, and 100% stress at definite elongation is 5.3MPa, and tensile yield is 184%.The bloom experimental result is no blooming, and photo is seen Fig. 6.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 6
Terpolymer EP rubber sizing material (Jiization J4045) is added 5 parts of active zinc flowers in 35 ± 5 ℃ of priorities of temperature for 100 parts on two roll rubber mixing mill, 1 part of stearic acid, 80 parts of carbon blacks, 50 parts of ASTM103# oil (evolution worker company limited of Ningbo association), 8 parts of promotor ZDBP, 0.5 part of captax, 1.5 parts of pre-dispersed Sulfurs are mixing even, the mixing time is 21 minutes, obtains blend.Again with blend 160 ℃ of temperature, sulfuration is 15 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtains terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90It is 9 minutes 57 seconds; Tensile strength under the normal temperature is 13.6MPa, and 100% stress at definite elongation is 2.0MPa, and 300% stress at definite elongation is 7.5MPa, and tensile yield is 481%, and tear strength is 35KN/m.Tensile strength after 120 ℃ * 24h is aging is 11.9MPa, and 100% stress at definite elongation is 4.9MPa, and tensile yield is 209%.Tensile strength after 120 ℃ * 72h is aging is 11.1MPa, and 100% stress at definite elongation is 5.9MPa, and tensile yield is 165%.The bloom experimental result is no blooming, and photo is seen Fig. 7.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 7
Terpolymer EP rubber sizing material (Jiization J4045) is added 5 parts in pre-dispersed zinc oxide in 35 ± 5 ℃ of priorities of temperature for 100 parts on two roll rubber mixing mill, 1 part of stearic acid, 80 parts of carbon blacks, 50 parts of ASTM103# oil (evolution worker company limited of Ningbo association), 8 parts of promotor ZDBP, 0.5 part of captax, 1.5 parts of insoluble sulfuy are mixing even, the mixing time is 21 minutes, obtains blend.Again with blend 160 ℃ of temperature, sulfuration is 20 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtains terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90It is 15 minutes 08 second; Tensile strength under the normal temperature is 13.4MPa, and 100% stress at definite elongation is 2.1MPa, and 300% stress at definite elongation is 8.4MPa, and tensile yield is 444%, and tear strength is 35KN/m.Tensile strength after 120 ℃ * 24h is aging is 11.5MPa, and 100% stress at definite elongation is 4.3MPa, and tensile yield is 225%.Tensile strength after 120 ℃ * 72h is aging is 11.2MPa, and 100% stress at definite elongation is 5.4MPa, and tensile yield is 183%.The bloom experimental result is no blooming, and photo is seen Fig. 8.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 8
Terpolymer EP rubber sizing material (Jiization J4045) is added 5 parts in pre-dispersed zinc oxide in 35 ± 5 ℃ of priorities of temperature for 100 parts on two roll rubber mixing mill, 1 part of stearic acid, 80 parts of carbon blacks, 50 parts of ASTM103# oil (evolution worker company limited of Ningbo association), 8 parts of promotor ZDBP, 0.5 part of captax, 1.5 parts of pre-dispersed Sulfurs are mixing even, the mixing time is 21 minutes, obtains blend.Again with blend 160 ℃ of temperature, sulfuration is 20 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtains terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90It is 15 minutes 04 second; Tensile strength under the normal temperature is 12.5MPa, and 100% stress at definite elongation is 2.5MPa, and 300% stress at definite elongation is 9.7MPa, and tensile yield is 376%, and tear strength is 32KN/m.Tensile strength after 120 ℃ * 24h is aging is 11.6MPa, and 100% stress at definite elongation is 4.6MPa, and tensile yield is 216%.Tensile strength after 120 ℃ * 72h is aging is 11.0MPa, and 100% stress at definite elongation is 5.7MPa, and tensile yield is 170%.The bloom experimental result is no blooming, and photo is seen Fig. 9.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 9
Terpolymer EP rubber sizing material (Jiization J4045) is added 5 parts in pre-dispersed zinc oxide in 35 ± 5 ℃ of priorities of temperature for 100 parts on two roll rubber mixing mill, 1 part of stearic acid, 80 parts of carbon blacks, 50 parts of ASTM103# oil (evolution worker company limited of Ningbo association), 1.5 parts of TM monex TD, 0.5 part of captax, 1.5 parts of pre-dispersed Sulfurs are mixing even, the mixing time is 21 minutes, obtains blend.Again with blend 160 ℃ of temperature, sulfuration is 20 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtains terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90It is 13 minutes 04 second; Tensile strength under the normal temperature is 13.5MPa, and 100% stress at definite elongation is 3.5MPa, and 300% stress at definite elongation is 10.7MPa, and tensile yield is 426%, and tear strength is 33KN/m.Tensile strength after 120 ℃ * 24h is aging is 14.6MPa, and 100% stress at definite elongation is 4.9MPa, and tensile yield is 206%.Tensile strength after 120 ℃ * 72h is aging is 12.0MPa, and 100% stress at definite elongation is 5.9MPa, and tensile yield is 180%.The bloom experimental result is no blooming, and photo is seen Fig. 9.
From the result of embodiment 1-9 as can be seen, according to the terpolymer EP rubber that the invention provides formulation, all can be implemented in no blooming and not generate nitrosamines when having the good mechanical performance concurrently.
Claims (10)
1. terpolymer EP rubber, this rubber is for containing the terpolymer EP rubber sizing material, vulcanizing agent, the vulcanization leveller system, promotor, mixing and the sulfuration of the composition of toughener and softening softening agent and the product that forms, it is characterized in that, described vulcanizing agent is insoluble sulfuy and/or pre-dispersed Sulfur, described vulcanization leveller system contains component A and stearic acid, described component A is selected from active zinc flower and/or pre-dispersed zinc oxide, in described composition, with respect to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is the 0.5-4.5 weight part, the content of described vulcanization leveller system is the 4-13 weight part, the content of described promotor is the 3-10 weight part, the content of described toughener is the 40-90 weight part, the content of described softening softening agent is the 5-60 weight part, and described component A and stearic weight ratio are 1-10: 1.
2. terpolymer EP rubber according to claim 1, wherein, in described composition, with respect to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is that the content of 1-3 weight part, described vulcanization leveller system is that the content of 5-7 weight part, described promotor is the 4-9 weight part, the content of described toughener is that the content of 75-85 weight part, described softening softening agent is the 45-55 weight part, and described component A and stearic weight ratio are 4-6: 1.
3. terpolymer EP rubber according to claim 1 and 2, wherein, described promotor is contained first promotor and second promotor, and described first promotor is promotor ZDBP, and described second promotor is not for generating the promotor except ZDBP of nitrosamine.
4. terpolymer EP rubber according to claim 3, wherein, described second promotor is selected from one or more in vulkacit D TDC, captax, the accelerator CBS, is preferably captax.
5. according to claim 3 or 4 described terpolymer EP rubbers, wherein, the weight ratio of described first promotor and second promotor is 10-18: 1, be preferably 12-16: 1.
6. terpolymer EP rubber according to claim 1 and 2, wherein, the insoluble sulphur content of described insoluble sulfuy is 30-90 weight %, being preferably insoluble sulphur content is the insoluble sulfuy IS60 of 60 weight %.
7. terpolymer EP rubber according to claim 1 and 2, wherein, described pre-dispersed Sulfur is pre-dispersed S-80; Described pre-dispersed zinc oxide is pre-dispersed zinc oxide master batch ZnO-80.
8. terpolymer EP rubber according to claim 1 and 2, wherein, the median size of described active zinc flower is 1-100nm, is preferably 1-50nm.
9. terpolymer EP rubber according to claim 1 and 2, wherein, described toughener is selected from one or more in carbon black, white carbon black, staple fibre, calcium carbonate and the aluminium carbonate, is preferably carbon black; Described softening softening agent is selected from one or more in paraffin oil, aromatic hydrocarbon oil, the naphthenic oil, is preferably ASTM103# oil.
10. terpolymer EP rubber according to claim 1, wherein, described mixing temperature is 30-40 ℃, is preferably 32-38 ℃; Time is 15-30 minute, is preferably 18-24 minute; The temperature of described sulfuration is 140-180 ℃, is preferably 150-170 ℃; Pressure is 10-20MPa, is preferably 12-18MPa; Time is 5-55 minute, is preferably 10-50 minute.
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| CN104387677A (en) * | 2014-11-05 | 2015-03-04 | 安徽龙川橡塑科技有限公司 | Anti-aging rubber |
| CN104389949A (en) * | 2014-11-25 | 2015-03-04 | 阮益谊 | Triangle belt |
| CN105566775A (en) * | 2015-11-24 | 2016-05-11 | 南京利德东方橡塑科技有限公司 | Environment-friendly low-odor ethylene-propylene-diene monomer rubber formulation |
| CN105694108A (en) * | 2016-01-22 | 2016-06-22 | 上海京海（安徽）化工有限公司 | Low-static-electricity explosion-proof insoluble sulfur and production process thereof |
| CN106700281A (en) * | 2016-11-29 | 2017-05-24 | 芜湖集拓橡胶技术有限公司 | Superconductor thermal ethylene propylene diene methylene rubber |
| CN107216661A (en) * | 2017-07-13 | 2017-09-29 | 无锡朴业橡塑有限公司 | A kind of ageing-resistant EPT rubber composition and preparation method thereof |
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| CN107216661A (en) * | 2017-07-13 | 2017-09-29 | 无锡朴业橡塑有限公司 | A kind of ageing-resistant EPT rubber composition and preparation method thereof |
| CN107216661B (en) * | 2017-07-13 | 2020-03-24 | 无锡朴业橡塑有限公司 | Aging-resistant ethylene propylene diene monomer composition and preparation method thereof |
| CN109049748A (en) * | 2018-06-22 | 2018-12-21 | 太仓市开源橡胶有限公司 | Battery truck foot pad and its preparation process |
| CN109354779A (en) * | 2018-09-29 | 2019-02-19 | 芜湖集拓橡胶技术有限公司 | A kind of high-performance rubber spring |
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