CN103254511B - A kind of terpolymer EP rubber - Google Patents
A kind of terpolymer EP rubber Download PDFInfo
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- CN103254511B CN103254511B CN201210038982.4A CN201210038982A CN103254511B CN 103254511 B CN103254511 B CN 103254511B CN 201210038982 A CN201210038982 A CN 201210038982A CN 103254511 B CN103254511 B CN 103254511B
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Abstract
The invention discloses a kind of terpolymer EP rubber, this rubber is for containing terpolymer EP rubber sizing material, vulcanizing agent, vulcanization leveller system, promotor, mixing and the sulfuration of the composition of toughener and softening softening agent and the product formed, 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 the composition, relative to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is 0.5-4.5 weight part, the content of described vulcanization leveller system is 4-13 weight part, the content of described promotor is 3-10 weight part, the content of described toughener is 40-90 weight part, the content of described softening softening agent is 5-60 weight part, described component A and stearic weight ratio are 1-10: 1.Preferred terpolymer EP rubber no blooming provided by the invention, do not produce nitrosamine and mechanical property is good.
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) with other high unsaturated alkadiene rubber phase than much lower, when with sulfur sulfide system sulfuration, the activity of sulfuration is lower, in order to improve vulcanization rate and the state of vulcanization of sizing material, in formula, usually adopt the accelerator combination system of high consumption.Terpolymer EP rubber is owing to lacking active group in molecular structure, and internal cohesive energy is low, autohension and mutual viscosity very poor, sizing material is when the accelerator content height added, and sizing material is easy to bloom.And in order to obtain good mechanical property, high reactivity ultra fast accelerator (as dithiocarbamate(s) and the thiurams) application in terpolymer EP rubber is very general.These promotor often have secondary amine structure, can generate N-nitrosamine with nitrosation agent (amino-oxide Nox) reaction.Determine, N-nitrosamine has carinogenicity.German regulations TRGS 552 defines the carcinogenic N-nitrosamine of forbidding 12 kinds, relates to the rubber ingredients of multiple current domestic widespread use." new chemical industry product policy strategy white paper " that particularly October calendar year 2001, European Union delivered, lists the chemical that time limit is eliminated in by vulcanizing agent DTDM and some thiuram type accelerator (as TMTD etc.).
Disclosing a kind of Tint seal strip without nitrosamine release in CN102140206A, is be grouped into by the one-tenth of following weight part: as the terpolymer EP rubber 100 parts of basic recipe, 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.Although this invention can solve the problem of nitrosamine release, the terpolymer EP rubber that this invention prepares, time in order to obtain good mechanical property, often produces bloom.To sum up, a kind of vulcanization rate is needed at present badly very fast and have the terpolymer EP rubber of no blooming and better mechanical property concurrently.Preferably, this terpolymer EP rubber does not produce nitrosamine.
Summary of the invention
Object of the present invention is in order to overcome existing terpolymer EP rubber to obtain good mechanical property, often need to add a large amount of promotor thus the shortcoming causing the easy bloom of terpolymer EP rubber, provide a kind of vulcanization rate very fast and have the terpolymer EP rubber of no blooming and better mechanical property concurrently.
To achieve these goals, the invention provides a kind of terpolymer EP rubber, this rubber is for containing terpolymer EP rubber sizing material, vulcanizing agent, vulcanization leveller system, promotor, mixing and the sulfuration of the composition of toughener and softening softening agent and the product formed, 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 the composition, relative to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is 0.5-4.5 weight part, the content of described vulcanization leveller system is 4-13 weight part, the content of described promotor is 3-10 weight part, the content of described toughener is 40-90 weight part, the content of described softening softening agent is 5-60 weight part, described component A and stearic weight ratio are 1-10: 1.
Compared with existing ethylene-propylene rubber(EPR), terpolymer EP rubber no blooming provided by the invention and mechanical property is good.Under preferable case, it is good and do not produce the advantage of nitrosamine that terpolymer EP rubber provided by the invention has no blooming, mechanical property concurrently.Such as, the sulfurizing time T of terpolymer EP rubber that provides of the embodiment of the present invention 1
90it is 34 minutes 23 seconds; Tensile strength is at normal temperatures 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 DEG C × 24h is aging is 16.4MPa, and 100% stress at definite elongation is 5.8MPa, and tensile yield is 239%; Tensile strength after 120 DEG C × 72h is aging is 18.3MPa, and tensile yield is 193%.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 example 1 provides
90it is 11 minutes 37 seconds; Tensile strength under 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 DEG C × 24h is aging is 14.2MPa, and 100% stress at definite elongation is 4.9MPa, and tensile yield is 252%; Tensile strength after 120 DEG C × 72h is aging is 12.7MPa, and 100% stress at definite elongation is 5.6MPa, and tensile yield is 189%.Bloom experimental result is bloom.Due to containing Vulcanization accelerator TMTD, produce nitrosamine.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the bloom experimental result photo of the terpolymer EP rubber that comparative example 1 obtains;
Fig. 2 is the EPDM bloom experimental result photo that embodiment 1 obtains;
Fig. 3 is the bloom experimental result photo of the terpolymer EP rubber that embodiment 2 obtains;
Fig. 4 is the bloom experimental result photo of the terpolymer EP rubber that embodiment 3 obtains;
Fig. 5 is the bloom experimental result photo of the terpolymer EP rubber that embodiment 4 obtains;
Fig. 6 is the bloom experimental result photo of the terpolymer EP rubber that embodiment 5 obtains;
Fig. 7 is the bloom experimental result photo of the terpolymer EP rubber that embodiment 6 obtains;
Fig. 8 is the bloom experimental result photo of the terpolymer EP rubber that embodiment 7 obtains;
Fig. 9 is the bloom experimental result photo of the terpolymer EP rubber that embodiment 8 obtains.
Embodiment
According to terpolymer EP rubber of the present invention, this rubber is for containing terpolymer EP rubber sizing material, vulcanizing agent, vulcanization leveller system, promotor, mixing and the sulfuration of the composition of toughener and softening softening agent and the product formed, 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 the composition, relative to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is 0.5-4.5 weight part, the content of described vulcanization leveller system is 4-13 weight part, the content of described promotor is 3-10 weight part, the content of described toughener is 40-90 weight part, the content of described softening softening agent is 5-60 weight part, described component A and stearic weight ratio are 1-10: 1.
According to terpolymer EP rubber of the present invention, preferably, in the composition, relative to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is 1-3 weight part, the content of described vulcanization leveller system is 5-7 weight part, the content of described promotor is 4-9 weight part, the content of described toughener is 75-85 weight part, the content of described softening softening agent is 45-55 weight part, and described component A and stearic weight ratio are 4-6: 1.When preparing terpolymer EP rubber, in the composition, terpolymer EP rubber sizing material accounts for 36.04 % by weight to 65.57 % by weight.
According to terpolymer EP rubber of the present invention, preferably, described promotor contains the first promotor and the second promotor, and described first promotor is promotor ZDBP, and described second promotor is do not generate the promotor of nitrosamine except ZDBP.When the aforementioned promotor of employing, the terpolymer EP rubber of acquisition while having good mechanical system energy and no blooming concurrently, can not produce nitrosamine.
According to terpolymer EP rubber of the present invention, the kind of the present invention to described second promotor does not have particular requirement, variously in prior art do not generate the promotor of nitrosamine except ZDBP and all can realize object of the present invention, preferably, described second promotor be selected from vulkacit D TDC, captax, accelerator CBS one or more, be preferably captax.Aforesaid promotor all can be commercially available.
According to terpolymer EP rubber of the present invention, although the first promotor of various weight ratio and the second promotor all can realize object of the present invention, preferably, the weight ratio of described first promotor and the second promotor is 10-18: 1, is preferably 12-16: 1.Adopt the weight ratio of aforementioned first promotor and the second promotor, the mechanical property of terpolymer EP rubber can be improved 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 kind of the present invention to described insoluble sulfuy is not particularly limited, various conventional insoluble sulfuy of the prior art all may be used for the present invention, preferably, the insoluble sulphur content of described insoluble sulfuy is 30-90 % by weight, is preferably the insoluble sulfuy IS60 that insoluble sulphur content is 60 % by weight.
As those skilled in the known, pre-dispersed Sulfur can discharge the Sulfur of free sulphur under referring to normal cure conditions, different from common Sulfur, pre-dispersed Sulfur mainly forms monosulfidic bond and cystine linkage, and according to terpolymer EP rubber of the present invention, the kind of the present invention to described pre-dispersed Sulfur is not particularly limited, the pre-dispersed Sulfur of various routines of the prior art all may be used for the present invention, preferably, described pre-dispersed Sulfur is pre-dispersed S-80, and Sulfur amount is wherein 80 % by weight; As those skilled in the known, described pre-dispersed zinc oxide is through the indirect process zinc oxide of pre-dispersed process.The kind of the present invention to described pre-dispersed zinc oxide is not particularly limited, the pre-dispersed zinc oxide of various routines of the prior art all may 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 % by weight.
As those skilled in the known, described active zinc flower is a kind of zinc oxide of the activated process of particle surface.According to terpolymer EP rubber of the present invention, the kind of the present invention to described active zinc flower is not particularly limited, and various regular activated zinc oxide of the prior art all may 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 kind of the present invention to described toughener does not have particular requirement, in prior art, various toughener all can realize object of the present invention, preferably, described toughener be selected from carbon black, white carbon black, staple fibre, calcium carbonate and aluminium carbonate one or more, be preferably carbon black.
According to terpolymer EP rubber of the present invention, the kind of the present invention to softening softening agent does not have particular requirement, in prior art, various softening softening agent all can realize object of the present invention, wherein, softening softening agent be selected from paraffin oil, aromatic hydrocarbon oil, naphthenic oil one or more, be preferably ASTM103# oil.
According to terpolymer EP rubber of the present invention, the kind of the present invention to terpolymer EP rubber does not have particular requirement, and various terpolymer EP rubber of the prior art all can realize object of the present invention.
According to terpolymer EP rubber of the present invention, the present invention does not have particular requirement to described condition that is mixing and sulfuration, and prior art condition that is mixing to terpolymer EP rubber and sulfuration all can realize object of the present invention, preferably, described mixing temperature is 30-40 DEG C, is preferably 32-38 DEG C; Time is 15-30 minute, is preferably 18-24 minute; The temperature of described sulfuration is 140-180 DEG C, is preferably 150-170 DEG C; Pressure is 5-10MPa, is preferably 6.5-8.5MPa; Time is 5-55 minute, is preferably 10-50 minute.
Below will be described the present invention by embodiment.In following examples, unless stated otherwise, part represents weight part, and the method that performance test relates to is as follows:
1, the vulcanization characteristics of vulkameter test analysis terpolymer EP rubber is adopted.
2, ambient temperature mechanical properties, the aging rear mechanical property of 120 DEG C × 24h, the aging rear mechanical property of 120 DEG C × 72h of puller system test analysis terpolymer EP rubber is adopted.
3, adopt ageing oven to the bloom performance test analysis of terpolymer EP rubber.Setting oven temperature is 70 DEG C, gets container at a gulp and holds enough water (guaranteeing not dried in 72h), with fine rule, cross-linked rubber sample is hung on the distance water surface and is about 20mm place, takes out and observe after insulation 72h.
Comparative example 1
Terpolymer EP rubber sizing material (Jilin Chemical J4045) 100 parts is added 5 parts, zinc oxide in temperature 35 ± 5 DEG C of priorities on two roll rubber mixing mill, stearic acid 1 part, carbon black 80 parts, ASTM103# oil (Ningbo co evolution work company limited) 50 parts, Vulcanization accelerator TMTD 1 part, captax 0.5 part, Sulfur 1.5 parts is evenly mixing, the mixing time is 21 minutes, obtains blend.Again by blend temperature 160 DEG C, sulfuration 20 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtain terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90it is 11 minutes 37 seconds; Tensile strength under 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 DEG C × 24h is aging is 14.2MPa, and 100% stress at definite elongation is 4.9MPa, and tensile yield is 252%.Tensile strength after 120 DEG C × 72h is aging is 12.7MPa, and 100% stress at definite elongation is 5.6MPa, and tensile yield is 189%.Bloom experimental result is bloom, and Fig. 1 is shown in by photo.Promotor is TMTD, can produce nitrosamine.
Embodiment 1
Terpolymer EP rubber sizing material (Jilin Chemical J4045) 100 parts is added active zinc flower 5 parts in temperature 35 ± 5 DEG C of priorities on two roll rubber mixing mill, stearic acid 1 part, carbon black 80 parts, ASTM103# oil 50 parts, promotor ZDBP 4 parts, 1.5 parts of insoluble sulfuy IS60-10 are evenly mixing, and the mixing time is 21 minutes, obtains blend.Again by blend temperature 160 DEG C, sulfuration 40 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtain terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90it is 34 minutes 23 seconds; Tensile strength under 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 DEG C × 24h is aging is 16.4MPa, and 100% stress at definite elongation is 5.8MPa, and tensile yield is 239%.Tensile strength after 120 DEG C × 72h is aging is 18.3MPa, and tensile yield is 193%.Bloom experimental result is no blooming, and Fig. 2 is shown in by photo.Promotor is ZDBP, can not produce nitrosamine.
Compare by embodiment 1 can find out with comparative example 1, according to the terpolymer EP rubber that the invention provides formula preparation, can while having good mechanical property concurrently no blooming and do not produce nitrosamine.
Embodiment 2
Terpolymer EP rubber sizing material (Jilin Chemical J4045) 100 parts is added active zinc flower 6 parts in temperature 35 ± 5 DEG C of priorities on two roll rubber mixing mill, stearic acid 1 part, carbon black 75 parts, ASTM103# oil (Ningbo co evolution work company limited) 45 parts, promotor ZDBP 8 parts, insoluble sulfuy 3 parts is evenly mixing, and the mixing time is 21 minutes, obtains blend.Again by blend temperature 160 DEG C, sulfuration 40 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtain terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90it is 32 minutes 55 seconds; Tensile strength under 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 DEG C × 24h is aging is 13.2MPa, and 100% stress at definite elongation is 6.0MPa, and tensile yield is 184%.Tensile strength after 120 DEG C × 72h is aging is 11.9MPa, and 100% stress at definite elongation is 7.5MPa, and tensile yield is 144%.Bloom experimental result is no blooming, and Fig. 3 is shown in by photo.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 3
Terpolymer EP rubber sizing material (Jilin Chemical J4045) 100 parts is added active zinc flower 4 parts in temperature 35 ± 5 DEG C of priorities on two roll rubber mixing mill, stearic acid 1 part, carbon black 85 parts, ASTM103# oil (Ningbo co evolution work company limited) 55 parts, promotor ZDBP 6 parts, captax 0.5 part, insoluble sulfuy 1 part is evenly mixing, the mixing time is 21 minutes, obtains blend.Again by blend temperature 160 DEG C, sulfuration 30 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtain terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90it is 25 minutes 57 seconds; Tensile strength under 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 DEG C × 24h is aging is 12.5MPa, and 100% stress at definite elongation is 3.7MPa, and tensile yield is 264%.Tensile strength after 120 DEG C × 72h is aging is 12.9MPa, and 100% stress at definite elongation is 4.8MPa, and tensile yield is 224%.Bloom experimental result is no blooming, and Fig. 4 is shown in by photo.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 4
Terpolymer EP rubber sizing material (Jilin Chemical J4045) 100 parts is added active zinc flower 5 parts in temperature 35 ± 5 DEG C of priorities on two roll rubber mixing mill, stearic acid 1 part, carbon black 80 parts, ASTM103# oil 50 parts (Ningbo co evolution work company limited), promotor ZDBP 8 parts, captax 0.5 part, insoluble sulfuy 2 parts is evenly mixing, the mixing time is 21 minutes, obtains blend.Again by blend temperature 160 DEG C, sulfuration 25 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtain terpolymer EP rubber..
The sulfurizing time T of this terpolymer EP rubber
90it is 18 minutes 45 seconds; Tensile strength under 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 DEG C × 24h is aging is 11.3MPa, and 100% stress at definite elongation is 4.9MPa, and tensile yield is 189%.Tensile strength after 120 DEG C × 72h is aging is 11.0MPa, and 100% stress at definite elongation is 6.5MPa, and tensile yield is 184%.Bloom experimental result is no blooming, and Fig. 5 is shown in by photo.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 5
Terpolymer EP rubber sizing material (Jilin Chemical J4045) 100 parts is added active zinc flower 5 parts in temperature 35 ± 5 DEG C of priorities on two roll rubber mixing mill, stearic acid 1 part, carbon black 80 parts, ASTM103# oil (Ningbo co evolution work company limited) 50 parts, promotor ZDBP 8 parts, captax 0.5 part, insoluble sulfuy 1.5 parts is evenly mixing, the mixing time is 21 minutes, obtains blend.Again by blend temperature 160 DEG C, sulfuration 25 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtain terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90it is 18 minutes 04 second; Tensile strength under 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 DEG C × 24h is aging is 11.7MPa, and 100% stress at definite elongation is 3.9MPa, and tensile yield is 249%.Tensile strength after 120 DEG C × 72h is aging is 11.2MPa, and 100% stress at definite elongation is 5.3MPa, and tensile yield is 184%.Bloom experimental result is no blooming, and Fig. 6 is shown in by photo.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 6
Terpolymer EP rubber sizing material (Jilin Chemical J4045) 100 parts is added active zinc flower 5 parts in temperature 35 ± 5 DEG C of priorities on two roll rubber mixing mill, stearic acid 1 part, carbon black 80 parts, ASTM103# oil 50 parts (Ningbo co evolution work company limited), promotor ZDBP 8 parts, captax 0.5 part, pre-dispersed Sulfur 1.5 parts is evenly mixing, the mixing time is 21 minutes, obtains blend.Again by blend temperature 160 DEG C, sulfuration 15 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtain terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90it is 9 minutes 57 seconds; Tensile strength under 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 DEG C × 24h is aging is 11.9MPa, and 100% stress at definite elongation is 4.9MPa, and tensile yield is 209%.Tensile strength after 120 DEG C × 72h is aging is 11.1MPa, and 100% stress at definite elongation is 5.9MPa, and tensile yield is 165%.Bloom experimental result is no blooming, and Fig. 7 is shown in by photo.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 7
Terpolymer EP rubber sizing material (Jilin Chemical J4045) 100 parts is added 5 parts, pre-dispersed zinc oxide in temperature 35 ± 5 DEG C of priorities on two roll rubber mixing mill, stearic acid 1 part, carbon black 80 parts, ASTM103# oil (Ningbo co evolution work company limited) 50 parts, promotor ZDBP 8 parts, captax 0.5 part, insoluble sulfuy 1.5 parts is evenly mixing, the mixing time is 21 minutes, obtains blend.Again by blend temperature 160 DEG C, sulfuration 20 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtain terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90it is 15 minutes 08 second; Tensile strength under 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 DEG C × 24h is aging is 11.5MPa, and 100% stress at definite elongation is 4.3MPa, and tensile yield is 225%.Tensile strength after 120 DEG C × 72h is aging is 11.2MPa, and 100% stress at definite elongation is 5.4MPa, and tensile yield is 183%.Bloom experimental result is no blooming, and Fig. 8 is shown in by photo.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 8
Terpolymer EP rubber sizing material (Jilin Chemical J4045) 100 parts is added 5 parts, pre-dispersed zinc oxide in temperature 35 ± 5 DEG C of priorities on two roll rubber mixing mill, stearic acid 1 part, carbon black 80 parts, ASTM103# oil (Ningbo co evolution work company limited) 50 parts, promotor ZDBP 8 parts, captax 0.5 part, pre-dispersed Sulfur 1.5 parts is evenly mixing, the mixing time is 21 minutes, obtains blend.Again by blend temperature 160 DEG C, sulfuration 20 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtain terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90it is 15 minutes 04 second; Tensile strength under 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 DEG C × 24h is aging is 11.6MPa, and 100% stress at definite elongation is 4.6MPa, and tensile yield is 216%.Tensile strength after 120 DEG C × 72h is aging is 11.0MPa, and 100% stress at definite elongation is 5.7MPa, and tensile yield is 170%.Bloom experimental result is no blooming, and Fig. 9 is shown in by photo.Promotor is ZDBP, can not produce nitrosamine.
Embodiment 9
Terpolymer EP rubber sizing material (Jilin Chemical J4045) 100 parts is added 5 parts, pre-dispersed zinc oxide in temperature 35 ± 5 DEG C of priorities on two roll rubber mixing mill, stearic acid 1 part, carbon black 80 parts, ASTM103# oil (Ningbo co evolution work company limited) 50 parts, Vulcanization accelerator TMTD 1.5 parts, captax 0.5 part, pre-dispersed Sulfur 1.5 parts is evenly mixing, the mixing time is 21 minutes, obtains blend.Again by blend temperature 160 DEG C, sulfuration 20 minutes on the hydraulic flat vulcanizer of pressure 15MPa, obtain terpolymer EP rubber.
The sulfurizing time T of this terpolymer EP rubber
90it is 13 minutes 04 second; Tensile strength under 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 DEG C × 24h is aging is 14.6MPa, and 100% stress at definite elongation is 4.9MPa, and tensile yield is 206%.Tensile strength after 120 DEG C × 72h is aging is 12.0MPa, and 100% stress at definite elongation is 5.9MPa, and tensile yield is 180%.Bloom experimental result is no blooming, and Fig. 9 is shown in by photo.
As can be seen from the result of embodiment 1-9, according to the terpolymer EP rubber that the invention provides formula preparation, all can be implemented in no blooming while having good mechanical property concurrently and do not produce nitrosamine.
Claims (14)
1. a terpolymer EP rubber, this rubber is for containing terpolymer EP rubber sizing material, vulcanizing agent, vulcanization leveller system, promotor, mixing and the sulfuration of the composition of toughener and softening softening agent and the product formed, 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 the composition, relative to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is 0.5-4.5 weight part, the content of described vulcanization leveller system is 4-13 weight part, the content of described promotor is 3-10 weight part, the content of described toughener is 40-90 weight part, the content of described softening softening agent is 5-60 weight part, described component A and stearic weight ratio are 1-10:1, described promotor is the mixture of the first promotor or the first promotor and the second promotor, described first promotor is promotor ZDBP, described second promotor is the promotor except ZDBP not generating nitrosamine, when described promotor is the mixture of the first promotor and the second promotor, the weight ratio of described first promotor and the second promotor is 10-18:1.
2. terpolymer EP rubber according to claim 1, wherein, in the composition, relative to 100 weight part terpolymer EP rubber sizing materials, the content of described vulcanizing agent is 1-3 weight part, the content of described vulcanization leveller system is 5-7 weight part, the content of described promotor is 4-9 weight part, the content of described toughener is 75-85 weight part, the content of described softening softening agent is 45-55 weight part, and described component A and stearic weight ratio are 4-6:1.
3. terpolymer EP rubber according to claim 1, wherein, described second promotor be selected from vulkacit D TDC, captax, accelerator CBS one or more.
4. terpolymer EP rubber according to claim 3, wherein, described second promotor is captax.
5. the terpolymer EP rubber according to claim 1,3 or 4, wherein, the weight ratio of described first promotor and the second promotor is 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 % by weight.
7. terpolymer EP rubber according to claim 6, wherein, described insoluble sulfuy to be insoluble sulphur content be 60 % by weight insoluble sulfuy IS60.
8. 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.
9. terpolymer EP rubber according to claim 1 and 2, wherein, the median size of described active zinc flower is 1-100nm.
10. terpolymer EP rubber according to claim 9, wherein, the median size of described active zinc flower is 1-50nm.
11. terpolymer EP rubbers according to claim 1 and 2, wherein, described toughener be selected from carbon black, white carbon black, staple fibre, calcium carbonate and aluminium carbonate one or more; Described softening softening agent be selected from paraffin oil, aromatic hydrocarbon oil, naphthenic oil one or more.
12. terpolymer EP rubbers according to claim 11, wherein, described toughener is carbon black; Described softening softening agent is ASTM103# oil.
13. terpolymer EP rubbers according to claim 1, wherein, described mixing temperature is 30-40 DEG C; Time is 15-30 minute; The temperature of described sulfuration is 140-180 DEG C; Pressure is 10-20MPa; Time is 5-55 minute.
14. terpolymer EP rubbers according to claim 13, wherein, described mixing temperature is 32-38 DEG C; Time is 18-24 minute; The temperature of described sulfuration is 140-180 DEG C; Pressure is 12-18MPa; Time is 10-50 minute.
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| CN103601986B (en) * | 2013-11-13 | 2016-04-06 | 四川明星电缆股份有限公司 | A kind of midium voltage cable second third Insulation Material |
| CN104387677A (en) * | 2014-11-05 | 2015-03-04 | 安徽龙川橡塑科技有限公司 | Anti-aging rubber |
| CN104389949B (en) * | 2014-11-25 | 2016-08-24 | 阮益谊 | V-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 |
| 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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