CN101643564B - Rubber and preparation method thereof - Google Patents
Rubber and preparation method thereof Download PDFInfo
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- CN101643564B CN101643564B CN200810142272XA CN200810142272A CN101643564B CN 101643564 B CN101643564 B CN 101643564B CN 200810142272X A CN200810142272X A CN 200810142272XA CN 200810142272 A CN200810142272 A CN 200810142272A CN 101643564 B CN101643564 B CN 101643564B
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Abstract
The present invention discloses a rubber, which is prepared from a first component containing ethylene propylenediene rubber and a second component containing acrylonitrile-butadiene rubber in the presence of a vulcanizing agent, an accelerant and an activating agent. The rubber is characterized in that: the brittleness temperature, measured according to GB/T1682-94, of the rubber is -33 to 55 DEG C; the hardness change, measured according to GB/T 3512-2001, of the rubber is 3 to 8.8HA, the tensile strength change measured according to GB/T 3512-2001 is 1 to 4 MPa and the break elongation change measured according to GB/T 3512-2001 is -15 to -30 percent; and the hardness change, measured according to GB/T 1690-2006, of the rubber is -10 to -20HA and the volume change rate is 40 to 80 percent. The rubber of the invention is very excellent in cryogenic property, oil resistance and thermal aging resistance.
Description
[technical field]
The present invention relates to a kind of rubber, especially a kind of Ethylene Propylene Terpolymer/butyronitrile blended rubber and preparation method thereof.
[background technology]
Terpolymer EP rubber (EPDM) is a kind of saturated superpolymer,, and is introduced the inferior vinyl norbornene of the 3rd monomer (ENB) and is polymerized through solution copolymerization by ethene, propylene.The ageing-resistant performance of terpolymer EP rubber is very good, its weathering resistance, chemical resistance, insulativity and low-temperature performance are all better, be widely used in fields such as ageing-resistant, water-fast, corrosion-resistant and electrical apparatus insulation, for example light tire side, heat resistance conveyor belt, cable, electric wire, sealed loop-pad, door and window sealing strip, household electrical appliance and some daily necessitiess etc.But the oil-proofness of terpolymer EP rubber is poor.
Paracril (NBR) has excellent oil resistance, but it is heat-resisting, ozone-resistant aging property is relatively poor.In the prior art terpolymer EP rubber and paracril are carried out the blend processing, the oil-proofness of the rubber after blend is handled has obtained certain improvement.Yet, because terpolymer EP rubber is a non-polar rubber, paracril is a polar rubber, still there are some problems in the rubber of the two blend preparation, after nonpolar terpolymer EP rubber rubber and the blend of polar paracril, because structure and polar difference, the consistency between the two-phase that terpolymer EP rubber rubber and paracril form is bad.In order to improve the consistency between the two-phase, in blended rubber, introduce ethylene-vinyl acetate copolymer (EVA) usually.
The introducing of ethylene-vinyl acetate copolymer has improved terpolymer EP rubber rubber and paracril biphase consistency, make the mechanical property of rubber also obtain certain raising, but its low-temperature performance, oil resistance and heat aging property is still undesirable.
[summary of the invention]
In order to overcome the problems referred to above, the invention discloses a kind of rubber, described rubber has excellent low-temperature performance, oil resistance and heat aging property when keeping the good mechanical performance.
The invention discloses a kind of rubber, made under the condition that vulcanizing agent, promotor and promoting agent exist by first component that contains the Ethylene Propylene Terpolymer rubber and second component that contains the butyronitrile rubber, it is characterized in that: the temperature limit of brittleness of the described rubber that is recorded by GB/T1682-94 is-33～-55 ℃; The changes in hardness of the described rubber that is recorded by GB/T3512-2001 is 3～8.8HA, and tensile strength is changed to 1～4MPa, and elongation at break is changed to-15～-30%.The changes in hardness of the described rubber that is recorded by GB/T1690-2006 is-10～-20HA, volume change is 40～80%.
Described first component also contains properties-correcting agent, and described properties-correcting agent is salt, 2-benzothiazolyl mercaptan ring one or more in ammonium salt, the 2-mercaptothiazoline of 2-benzothiazolyl mercaptan, 2-benzothiazolyl mercaptan.
The invention also discloses the preparation method of above-mentioned rubber, comprise the steps:
A, the Ethylene Propylene Terpolymer rubber mixed with properties-correcting agent obtain the modified EPT rubber precursor, then the modified EPT rubber precursor is heat-treated, obtain modified EPT rubber;
B, modified EPT rubber is mixed with vulcanizing agent and promotor, obtain the Ethylene Propylene Terpolymer rubber unvulcanizate, the butyronitrile rubber is mixed with vulcanizing agent and promotor, obtain the butyronitrile rubber unvulcanizate;
C, described Ethylene Propylene Terpolymer rubber unvulcanizate and butyronitrile rubber unvulcanizate are mixed with promoting agent.
By the rubber of method for preparing, the temperature limit of brittleness of the described rubber that is recorded by GB/T1682-94 is-33～-55 ℃; The changes in hardness of the described rubber that is recorded by GB/T3512-2001 is 3～8.8HA, and tensile strength is changed to 1～4MPa, and elongation at break is changed to-15～-30%.The changes in hardness of the described rubber that is recorded by GB/T1690-2006 is-10～-20HA, volume change is 40～80%.
The present invention carries out modification by adopting properties-correcting agent to the Ethylene Propylene Terpolymer rubber, respectively modified EPT rubber and butyronitrile rubber is mixed with vulcanizing agent and promotor then, vulcanizes in the presence of promoting agent at last.The low-temperature performance of rubber disclosed by the invention, oil resistance and heat aging property are all very excellent.The disclosed temperature limit of brittleness that records by GB/T1682-94 can embody the low-temperature performance of rubber among the present invention; Changes in hardness, the tensile strength that records by GB/T3512-2001 changes, elongation at break changes the heat aging property that can embody rubber; The changes in hardness of the rubber that records by GB/T1690-2006 and the oil resistance that volume change can embody rubber.
[description of drawings]
Profile scanning electron microscope (SEM) figure of the rubber product D2 that Fig. 1 makes for Comparative Examples 2;
Profile scanning electron microscope (SEM) figure of the rubber product A2 that Fig. 2 makes for embodiment 2.
[embodiment]
The invention discloses a kind of rubber, made under the condition that vulcanizing agent, promotor and promoting agent exist by first component that contains the Ethylene Propylene Terpolymer rubber and second component that contains the butyronitrile rubber, it is characterized in that: the temperature limit of brittleness of the described rubber that is recorded by GB/T1682-94 is-33～-55 ℃; The changes in hardness of the described rubber that is recorded by GB/T3512-2001 is 3～8.8HA, and tensile strength is changed to 1～4MPa, and elongation at break is changed to-15～-30%.The changes in hardness of the described rubber that is recorded by GB/T1690-2006 is-10～-20HA, volume change is 40～80%.
Described promotor being used for can be improved sulfuration efficient, and described vulcanizing agent is used to form chemically crosslinked, and described promoting agent is used to activate promotor and sulphur system, improves vulcanization rate and efficient greatly.
Above-mentioned GB and testing method are conventionally known to one of skill in the art, and the data that record are reaction and change the degree change value.
According to the present invention, described Ethylene Propylene Terpolymer rubber is conventionally known to one of skill in the art, and for example, weight-average molecular weight is 200,000～400,000.Above-mentioned Ethylene Propylene Terpolymer rubber can be commercially available, and produces ethylene-propylene diene copolymer Keltan4903 as Dutch DSM N. V..Described butyronitrile rubber is conventionally known to one of skill in the art, and for example, the weight-average molecular weight of described butyronitrile rubber is 100,000～500,000, and the butyronitrile rubber that meets above-mentioned requirements can be commercially available, the butyronitrile rubber 230S that for example Japanese JSR company produces.
Described Ethylene Propylene Terpolymer rubber and butyronitrile rubber weight ratio are 1:1～4:1, are preferably 2:1～3:1.
Described first component and second component all contain vulcanizing agent and promotor, and described first component can be identical with vulcanizing agent in second component, also can be different; Described first component also contains properties-correcting agent.
Described properties-correcting agent is salt, 2-benzothiazolyl mercaptan ring one or more in ammonium salt, the 2-mercaptothiazoline of 2-benzothiazolyl mercaptan, 2-benzothiazolyl mercaptan.The salt of described 2-benzothiazolyl mercaptan can be zinc 2-mercaptobenzothiazole salt.Described properties-correcting agent can be commercially available, as the 2-benzothiazolyl mercaptan of Huangyan East Zhejiang province rubber ingredients company limited production.
Process properties-correcting agent processing disclosed by the invention prepares extremely important to follow-up rubber, very favourable to the Ethylene Propylene Terpolymer/heat-proof aging of paracril product and the raising of oil resistance that make at last.
Described promoting agent is this area promoting agent commonly used, as zinc oxide and stearic mixture or Zinic stearas.Be elected to when zinc oxide and stearic mixture are arranged, oxidisability and stearic weight ratio are 5:1.Described promoting agent can be commercially available, as the oxidisability and the stearic acid of company of polite chemical industry company limited of Liuzhou zinc product company limited and Hong Kong production.
The vulcanizing agent that contains in described first component and second component is this area vulcanizing agent commonly used, as sulphur, 4,4 ＇-dimorpholinyl disulfide and 2,4, and one or more in the 6-tri-thiol s-triazine.Described promotor is octadecyl sec.-propyl dithiocar-bamate, as zinc octadecylisopropyldithiocarbamate, octadecyl sec.-propyl nabam, octadecyl sec.-propyl dithiocarbamic acid potassium.Under the preferable case, described vulcanizing agent is a sulphur, and described promotor is zinc octadecylisopropyldithiocarbamate.Described vulcanizing agent and promotor can be commercially available, as the zinc octadecylisopropyldithiocarbamate of Huangyan East Zhejiang province rubber ingredients company limited production.
The contriver finds, handle the modified EPT rubber and the butyronitrile rubber that obtain by properties-correcting agent disclosed by the invention and handle through above-mentioned promotor and vulcanizing agent again, the heat-proof aging and the oil resistance of the Ethylene Propylene Terpolymer/paracril product that makes are at last increased substantially.
In described first component, be benchmark with Ethylene Propylene Terpolymer rubber content, described vulcanizing agent content is that 0.5～1.5wt%, accelerator content are that 2～5wt%, modifier content are 1～4wt%; In described second component, be benchmark with butyronitrile rubber content, described vulcanizing agent content is that 0.5～1.5wt%, accelerator content are 1.5～4wt%; With Ethylene Propylene Terpolymer rubber content is benchmark, and described active agent content is 5～8wt%.Under the preferable case, be benchmark with Ethylene Propylene Terpolymer rubber content, described vulcanizing agent content is that 0.5～1wt%, accelerator content are that 2～3wt%, modifier content are 2～3wt%; In described second component, be benchmark with butyronitrile rubber content, described vulcanizing agent content is that 0.5～1wt%, accelerator content are 2～3wt%; With Ethylene Propylene Terpolymer rubber content is benchmark, and described active agent content is 5～6wt%.
Strengthening agent and softening agent can also be contained in above-mentioned first component, strengthening agent, anti-aging agent and softening agent can also be contained in second component.Described strengthening agent, anti-aging agent and softening agent have been conventionally known to one of skill in the art, strengthening agent can be carbon black as described, described anti-aging agent can be Ursol D class or quinoline, and described softening agent can be in coumarone indene resin, paraffin oil or the dioctyl phthalate (DOP) one or more.Above-mentioned strengthening agent, anti-aging agent and softening agent all can be commercially available, and as the paraffin oil of Kelamayi petrochemical industry branch office of CNPC, model is the coumarone indene resin of KP6030 and Shanxi chemical institute.
In described first component, be benchmark with Ethylene Propylene Terpolymer rubber content, described strengthening agent content is that 30～60wt%, plasticizer loading are 5～15wt%; In described second component, be benchmark with butyronitrile rubber content, described strengthening agent content is that 30～50wt%, anti-aging agent content are that 1～3wt%, plasticizer loading are 5～10wt%.
The invention also discloses the preparation method of above-mentioned rubber, comprise the steps:
A, the Ethylene Propylene Terpolymer rubber mixed with properties-correcting agent obtain the modified EPT rubber precursor, then the modified EPT rubber precursor is heat-treated, obtain modified EPT rubber;
B, modified EPT rubber is mixed with vulcanizing agent and promotor, obtain the Ethylene Propylene Terpolymer rubber unvulcanizate, the butyronitrile rubber is mixed with vulcanizing agent and promotor, obtain the butyronitrile rubber unvulcanizate;
C, described Ethylene Propylene Terpolymer rubber unvulcanizate and butyronitrile rubber unvulcanizate are mixed with promoting agent.
Described properties-correcting agent, promoting agent, vulcanizing agent, promotor describe at preamble, do not repeat them here.
Describedly with Ethylene Propylene Terpolymer rubber and properties-correcting agent blended method be: with Ethylene Propylene Terpolymer rubber weight is benchmark, the properties-correcting agent of 1～4wt% placed in the mill with the Ethylene Propylene Terpolymer rubber mix, mixing condition is: roll spacing is 0.5～1mm, under 50～60 ℃, open refining 7～15min, obtain modified EPT rubber.
In order to reach better effect, can before mixing, open refining 5～10min to the Ethylene Propylene Terpolymer rubber earlier.
Described heat treating method is for to keep 40～70min with the modified EPT rubber precursor in 80～100 ℃.Described thermal treatment can be carried out in Equipment for Heating Processing commonly used, as baking oven.
By the modified EPT rubber precursor is heat-treated, help to form space precrosslink reticulated structure, can limit to a certain extent strengthening agent, softening agent, vulcanizing agent and promotor to the polarity butadiene-acrylonitrile rubber mutually in the migration, evenly sulfuration and two-phase interface formation covulcanization is crosslinked mutually to guarantee each, thereby comprehensively the excellent properties of each phase is all highly beneficial to the resistance toheat and the oil resistance that improve rubber item.
Modified EPT rubber and vulcanizing agent and promotor are carried out the blended method is: with Ethylene Propylene Terpolymer rubber weight is benchmark, the vulcanizing agent of 0.5～1.5wt% and the promotor of 2～5wt% are added in the Banbury mixer, adjustment mixing condition is: the closed-smelting machine rotor rotating speed is 20～40rpm, floating weight pressure is 4～7MPa, mixing time is 350～450s, be warming up to 140 ℃ then and stop warehouse discharging, obtain the Ethylene Propylene Terpolymer rubber unvulcanizate.
Butyronitrile rubber and vulcanizing agent and promotor are carried out the blended method is: with butyronitrile rubber weight is benchmark, the vulcanizing agent of 0.5～1.5wt% and the promotor of 1.5～4wt% are added in the Banbury mixer, adjustment mixing condition is: the closed-smelting machine rotor rotating speed is 20～40rpm, floating weight pressure is 4～7MPa, mixing time is 350～450s, be warming up to 120 ℃ then and stop warehouse discharging, obtain the butyronitrile rubber unvulcanizate.
Described Ethylene Propylene Terpolymer rubber unvulcanizate and butyronitrile rubber unvulcanizate and promoting agent are carried out the blended method is: with Ethylene Propylene Terpolymer rubber weight is benchmark, the promoting agent of 5～8wt% placed in the mill with described Ethylene Propylene Terpolymer rubber unvulcanizate and butyronitrile rubber unvulcanizate mix, described blending means is, roll spacing is 0.5～1mm, under 50～60 ℃, open refining 7～15min, obtain rubber product.
Under the preferable case, described Ethylene Propylene Terpolymer rubber unvulcanizate and butyronitrile rubber unvulcanizate and promoting agent are carried out the blended method is: be 0.5～1mm with described Ethylene Propylene Terpolymer rubber unvulcanizate in roll spacing earlier, open refining 5～10min under 50～60 ℃, divide 1～4 time then and add the butyronitrile rubber unvulcanizate, open refining 5～10min.Adding with Ethylene Propylene Terpolymer rubber weight at last is benchmark, and the promoting agent of 5～8wt% is opened refining 5～10min.The weight of each butyronitrile rubber unvulcanizate that adds can be the same or different, and the weight of butyronitrile rubber unvulcanizate that is preferably each adding is identical.When the amount of each adding not simultaneously, each amount that adds does not require.The timed interval between adjacent twice adding butyronitrile rubber unvulcanizate is 40～100s.
By the above-mentioned butyronitrile rubber unvulcanizate that makes is divided into 1～4 part, divide in the Ethylene Propylene Terpolymer rubber unvulcanizate that adds in the mill for 1～4 time, add promoting agent at last, help improving the heat-proof aging and the oil resistance of rubber product.The contriver finds that the timed interval between adjacent twice adding butyronitrile rubber unvulcanizate can make the heat-proof aging of rubber product and oil resistance be further enhanced when being 40～100s.
Before not adding promoting agent, though contain vulcanizing agent and promotor in above-mentioned butyronitrile rubber unvulcanizate and the Ethylene Propylene Terpolymer rubber unvulcanizate, owing to do not add promoting agent, the ring texture of S atom is difficult to be opened, and sulfuration is difficult to take place.After adding promoting agent, under it caused, through the effect of vulcanizing agent disclosed by the invention and promotor, the inner vulcanization reaction that takes place of rubber obtained having good low temperature performance, the rubber of heat-proof aging and oil resistance.
When preparation Ethylene Propylene Terpolymer rubber unvulcanizate, can also add strengthening agent and softening agent.When preparation butyronitrile rubber unvulcanizate, can also add strengthening agent, anti-aging agent and softening agent.The kind of described strengthening agent, anti-aging agent and softening agent and addition do not repeat them here as mentioned before.
The present invention is further illustrated below by embodiment.
Embodiment 1
Present embodiment is used to illustrate rubber disclosed by the invention and preparation method thereof.
(Dutch DSM N. V. produces ethylene-propylene diene copolymer Keltan4903 with 100 weight part Ethylene Propylene Terpolymer rubbers, weight-average molecular weight is 250,000) place in the mill with 2 weight part 2-benzothiazolyl mercaptans (Huangyan East Zhejiang province rubber ingredients company limited), the adjustment roll spacing is 0.5mm, under 50 ℃, open refining 10min, obtain the modified EPT rubber precursor, place 80 ℃ baking oven to keep 50min the modified EPT rubber precursor then, obtain modified EPT rubber.
With the sulphur (Huangyan East Zhejiang province rubber ingredients company limited) of above-mentioned modified EPT rubber and 1.1 weight parts and the zinc octadecylisopropyldithiocarbamate (Huangyan East Zhejiang province rubber ingredients company limited) of 4 weight parts, 50 parts by weight of carbon black (sea, Guangdong seal chemical industry company limited, model is ring star N550), paraffin oil (the KP6030 of 8 weight parts, Kelamayi petrochemical industry branch office of CNPC) adds in the Banbury mixer (iceberg, Dalian rubber and plastics machine company limited), adjusting the closed-smelting machine rotor rotating speed is 40rpm, floating weight pressure is 5MPa, mixing time is 360s, be warming up to 140 ℃ then and stop warehouse discharging, obtain the Ethylene Propylene Terpolymer rubber unvulcanizate.
With 40 weight part butyronitrile rubbers (the butyronitrile rubber 230S that Japanese JSR company produces) and the sulphur (Huangyan East Zhejiang province rubber ingredients company limited) of 0.44 weight part and the zinc octadecylisopropyldithiocarbamate (Huangyan East Zhejiang province rubber ingredients company limited) of 1.6 weight parts, 20 parts by weight of carbon black (sea, Guangdong seal chemical industry company limited, model is ring star N550), the coumarone indene resin of 4 weight parts (Shanxi chemical institute), 1.2 the Ursol D of weight part (available from Shijiazhuang space in morning economy and trade company limited) adds in the Banbury mixer, adjusting the closed-smelting machine rotor rotating speed is 40rpm, floating weight pressure is 5MPa, mixing time is 360s, be warming up to 120 ℃ then and stop warehouse discharging, obtain the butyronitrile rubber unvulcanizate.
Promoting agent (5 weight part Liuzhou zinc product company limited technical grade zinc oxide with 6 weight parts, 1 weight part Hong Kong polite chemical industry company limited stearic acid, trade mark SA1801) places in the mill with above-mentioned Ethylene Propylene Terpolymer rubber unvulcanizate and butyronitrile rubber unvulcanizate, the adjustment roll spacing is 0.5mm, under 55 ℃, open refining 10min, obtain rubber product A1.
Embodiment 2
Present embodiment is used to illustrate rubber disclosed by the invention and preparation method thereof.
(Dutch DSM N. V. produces ethylene-propylene diene copolymer Keltan4903 with 100 weight part Ethylene Propylene Terpolymer rubbers, weight-average molecular weight is 300,000) place in the mill with 2 weight part 2-benzothiazolyl mercaptans (Huangyan East Zhejiang province rubber ingredients company limited) and 1 weight part zinc 2-mercaptobenzothiazole salt (Huangyan East Zhejiang province rubber ingredients company limited), the adjustment roll spacing is 0.8mm, under 55 ℃, open refining 12min, obtain the modified EPT rubber precursor, place 100 ℃ baking oven to keep 60min the modified EPT rubber precursor then, obtain modified EPT rubber.
Sulphur (Huangyan East Zhejiang province rubber ingredients company limited) with above-mentioned modified EPT rubber and 0.7 weight part, the zinc octadecylisopropyldithiocarbamate of 2 weight parts (Huangyan East Zhejiang province rubber ingredients company limited), 40 parts by weight of carbon black (sea, Guangdong seal chemical industry company limited, model is ring star N550), paraffin oil (the KP6030 of 5 weight parts, Kelamayi petrochemical industry branch office of CNPC) adds in the Banbury mixer (iceberg, Dalian rubber and plastics machine company limited), adjusting the closed-smelting machine rotor rotating speed is 40rpm, floating weight pressure is 5MPa, mixing time is 360s, be warming up to 140 ℃ then and stop warehouse discharging, obtain the Ethylene Propylene Terpolymer rubber unvulcanizate.
With 50 weight part butyronitrile rubbers (the butyronitrile rubber 230S that Japanese JSR company produces) and the sulphur (Huangyan East Zhejiang province rubber ingredients company limited) of 0.35 weight part and the zinc octadecylisopropyldithiocarbamate (Huangyan East Zhejiang province rubber ingredients company limited) of 1 weight part, 25 parts by weight of carbon black (sea, Guangdong seal chemical industry company limited, model is ring star N550), the coumarone indene resin of 5 weight parts (Shanxi chemical institute), 1.5 the Ursol D of weight part (available from Shijiazhuang space in morning economy and trade company limited) adds in the Banbury mixer, adjusting the closed-smelting machine rotor rotating speed is 40rpm, floating weight pressure is 6MPa, mixing time is 380s, be warming up to 120 ℃ then and stop warehouse discharging, obtain the butyronitrile rubber unvulcanizate.
Promoting agent (5 weight part Liuzhou zinc product company limited technical grade zinc oxide with 6 weight parts, 1 weight part Hong Kong polite chemical industry company limited stearic acid, trade mark SA1801) places in the mill with above-mentioned Ethylene Propylene Terpolymer rubber unvulcanizate and butyronitrile rubber unvulcanizate, the adjustment roll spacing is 0.8mm, under 55 ℃, open refining 12min, obtain rubber product A2.
Embodiment 3
Present embodiment is used to illustrate rubber disclosed by the invention and preparation method thereof.
(Dutch DSM N. V. produces ethylene-propylene diene copolymer Keltan4903 with 100 weight part Ethylene Propylene Terpolymer rubbers, weight-average molecular weight is 300,000) place in the mill with 3 weight part 2-benzothiazolyl mercaptans (Huangyan East Zhejiang province rubber ingredients company limited), the adjustment roll spacing is 0.6mm, under 58 ℃, open refining 12min, obtain the modified EPT rubber precursor, place 100 ℃ baking oven to keep 60min the modified EPT rubber precursor then, obtain modified EPT rubber.
Sulphur (Huangyan East Zhejiang province rubber ingredients company limited) with above-mentioned remodeling terpolymer EP rubber and 0.8 weight part, the zinc octadecylisopropyldithiocarbamate of 3 weight parts (Huangyan East Zhejiang province rubber ingredients company limited), 45 parts by weight of carbon black (sea, Guangdong seal chemical industry company limited, model is ring star N550), paraffin oil (the KP6030 of 10 weight parts, Kelamayi petrochemical industry branch office of CNPC) adds in the Banbury mixer (iceberg, Dalian rubber and plastics machine company limited), adjusting the closed-smelting machine rotor rotating speed is 40rpm, floating weight pressure is 6MPa, mixing time is 400s, be warming up to 140 ℃ then and stop warehouse discharging, obtain the Ethylene Propylene Terpolymer rubber unvulcanizate.
With 50 weight part butyronitrile rubbers (the butyronitrile rubber 230S that Japanese JSR company produces) and the sulphur (Huangyan East Zhejiang province rubber ingredients company limited) of 0.4 weight part and the zinc octadecylisopropyldithiocarbamate (Huangyan East Zhejiang province rubber ingredients company limited) of 1.5 weight parts, 25 parts by weight of carbon black (sea, Guangdong seal chemical industry company limited, model is ring star N550), the coumarone indene resin of 5 weight parts (Shanxi chemical institute), 1.4 the Ursol D of weight part (available from Shijiazhuang space in morning economy and trade company limited) adds in the Banbury mixer, adjusting the closed-smelting machine rotor rotating speed is 40rpm, floating weight pressure is 6MPa, mixing time is 400s, be warming up to 140 ℃ then and stop warehouse discharging, obtain the butyronitrile rubber unvulcanizate.
Above-mentioned Ethylene Propylene Terpolymer rubber unvulcanizate is placed in the mill, and the adjustment roll spacing is 0.6mm, opens refining 6min under 58 ℃.Above-mentioned butyronitrile rubber unvulcanizate is divided into 2 parts by weight, divides then to add for 2 times in the mill, the timed interval of 2 addings is 80s.After having added, opens the butyronitrile rubber unvulcanizate refining 6min.The promoting agent (5 weight part Liuzhou zinc product company limited technical grade zinc oxide, 1 weight part Hong Kong polite chemical industry company limited stearic acid, trade mark SA1801) that adds 6 weight parts is then opened refining 10min, obtains rubber product A3.
Embodiment 4
Present embodiment is used to illustrate rubber disclosed by the invention and preparation method thereof.
Preparation modified EPT rubber is with embodiment 3, and different is:
The Ethylene Propylene Terpolymer rubber is opened refining add properties-correcting agent again behind the 8min.
The butyronitrile rubber unvulcanizate is divided into 3 parts by weight, divides 3 times and add in the mill, the timed interval of adjacent twice adding is 60s.
Obtain rubber product A4.
Comparative Examples 1
This Comparative Examples is used to illustrate rubber of the prior art and preparation method thereof.
The raw material and the content of preparation rubber are identical with embodiment 3, and different is:
Respectively with Ethylene Propylene Terpolymer rubber and butyronitrile rubber in mill, the adjustment roll spacing is 0.5mm, opens refining 10min under 50 ℃.
Add in the Banbury mixer opening Ethylene Propylene Terpolymer rubber after the refining and butyronitrile rubber and carbon black, paraffin oil, coumarone indene resin, adjusting the closed-smelting machine rotor rotating speed is 40rpm, and floating weight pressure is 5MPa, and mixing time is 360s, be warming up to 120 ℃ then and stop warehouse discharging, obtain banburying glue.
Above-mentioned banburying glue is chilled to 40 ℃ in the mill windward.
Above-mentioned cooled banburying glue is added in the Banbury mixer with sulphur and zinc octadecylisopropyldithiocarbamate, and adjusting the closed-smelting machine rotor rotating speed is 40rpm, and floating weight pressure is 5MPa, and mixing time is 360s, stops warehouse discharging then, obtains rubber product D1.
Comparative Examples 2
This Comparative Examples is used to illustrate rubber of the prior art and preparation method thereof.
The preparation method is identical with Comparative Examples 1, different is, also adds ethylene-vinyl acetate copolymer (company is contained in the Jinchang, Guangzhou) when preparation banburying glue, is 100 weight parts in the content of Ethylene Propylene Terpolymer rubber, described ethylene-vinyl acetate copolymer content is 10 weight parts, obtains rubber product D2.
Performance test
Above-mentioned rubber product A1～A4, D1 that makes and D2 are carried out following performance test:
1, hardness test
Adopt the hardness of GB/T528-92 method working sample;
2, tensile strength test
Adopt the tensile strength of GB/T528-92 method working sample;
3, elongation at break test
Adopt the elongation at break of GB/T528-92 method working sample;
4, low-temperature performance test
Adopt the temperature limit of brittleness of GB/T1682-94 method working sample;
5, heat aging performance test
Adopt the heat aging performance of GB/T3512-2001 method working sample, comprise that changes in hardness, tensile strength change and elongation at break changes;
6, oil resistance test
Adopt the heat aging performance of GB/T1690-2006 method working sample, comprise changes in hardness and volume change;
7, rubber fractograph analysis
The square blob of viscose of intercepting one 5mm * 5mm is attached on the copper tray then in the middle of rubber product A2 that makes from embodiment 2 and Comparative Examples 2 with the blade of cleaning and the D2, and handle and vacuum-drying through metal spraying on the surface.(NEC, JSM-5610) cross-section morphology of observation A2 and D2 is specifically seen Fig. 1 and Fig. 2 by scanning electronic microscope then.
Above-mentioned every performance test the results are shown in Table 1.
Table 1
Profile scanning electron microscope (SEM) figure of the rubber product D2 that Fig. 1 makes for Comparative Examples 2; Profile scanning electron microscope (SEM) figure of the rubber product A2 that Fig. 2 makes for embodiment 2.Comparative analysis Fig. 1 and Fig. 2, its section degree of roughness differs and not quite.The section degree of roughness has illustrated the consistency quality between inner each component of rubber, and section is coarse more, and consistency is poor more, and section is smooth more, and consistency is good more.Fig. 1 and Fig. 2 illustrate that the consistency between each component of inside of D2 and A2 is all relatively good, are more or less the same.
In conjunction with the accompanying drawings 1 and the test result of D1, D2 as can be seen, after in Ethylene Propylene Terpolymer/butyronitrile blended rubber, adding ethylene-vinyl acetate copolymer (EVA), consistency between inner each composition of rubber is better, causes mechanical property, low-temperature performance, heat-proof aging and the oil resistance of rubber product all to obtain certain raising.
By the Ethylene Propylene Terpolymer/butyronitrile blended rubber of method preparation disclosed by the invention, as A1～A4, than the rubber by prior art for preparing, its low-temperature performance, heat-proof aging and oil resistance are significantly improved.And the test result of comparative analysis A1, A2 and A3, A4 as can be known, and the gradation of butyronitrile rubber unvulcanizate is joined in the Ethylene Propylene Terpolymer rubber unvulcanizate, helps further improving its low-temperature performance, heat-proof aging and oil resistance.
Claims (9)
1. rubber, prepare under the condition that vulcanizing agent, promotor and promoting agent exist by first component that contains the Ethylene Propylene Terpolymer rubber and second component that contains the butyronitrile rubber, wherein, the temperature limit of brittleness of the described rubber that is recorded by GB/T 1682-94 is-33～-55 ℃; The changes in hardness of the described rubber that is recorded by GB/T 3512-2001 is 3～8.8HA, and tensile strength is changed to 1～4MPa, and elongation at break is changed to-15～-30%; Described first component also contains properties-correcting agent, and described properties-correcting agent is the salt of 2-benzothiazolyl mercaptan, 2-benzothiazolyl mercaptan, in the 2-mercaptothiazoline one or more; Described Ethylene Propylene Terpolymer rubber and butyronitrile rubber weight ratio are 1: 1～4: 1; In described first component, be benchmark with Ethylene Propylene Terpolymer rubber content, described vulcanizing agent content is that 0.5～1.5wt%, accelerator content are that 2～5wt%, modifier content are 1～4wt%; In described second component, be benchmark with butyronitrile rubber content, described vulcanizing agent content is that 0.5～1.5wt%, accelerator content are 1.5～4wt%; With Ethylene Propylene Terpolymer rubber content is benchmark, and described active agent content is 5～8wt%; The method of described preparation comprises the Ethylene Propylene Terpolymer rubber mixed with properties-correcting agent and obtains the modified EPT rubber precursor, then the modified EPT rubber precursor is heat-treated, and obtains modified EPT rubber; Then modified EPT rubber is mixed with vulcanizing agent and promotor, obtain the Ethylene Propylene Terpolymer rubber unvulcanizate, the butyronitrile rubber is mixed with vulcanizing agent and promotor, obtain the butyronitrile rubber unvulcanizate; Again described Ethylene Propylene Terpolymer rubber unvulcanizate and butyronitrile rubber unvulcanizate are mixed with promoting agent.
2. rubber according to claim 1, the changes in hardness of the described rubber that is recorded by GB/T 1690-2006 is-10～-20HA, volume change is 40～80%.
3. rubber according to claim 1 and 2 is characterized in that: described first component also contains properties-correcting agent, and described properties-correcting agent is one or more in 2-benzothiazolyl mercaptan, cyclohexylamine salt of 2-mercaptobenzothiazole, the 2-mercaptothiazoline.
4. rubber according to claim 1 is characterized in that: described promoting agent is zinc oxide and stearic mixture or Zinic stearas; Described vulcanizing agent be sulphur, 4,4 '-dimorpholinyl disulfide and 2,4, one or more in the 6-tri-thiol s-triazine; Described promotor is octadecyl sec.-propyl dithiocar-bamate.
5. rubber according to claim 1 is characterized in that: also contain strengthening agent and softening agent in first component, contain strengthening agent, anti-aging agent and softening agent in second component; In described first component, be benchmark with Ethylene Propylene Terpolymer rubber content, described strengthening agent content is that 30～60wt%, plasticizer loading are 5～15wt%; In described second component, be benchmark with butyronitrile rubber content, described anti-aging agent content is that 1～3wt%, strengthening agent content are that 30～50wt%, plasticizer loading are 5～10wt%.
6. the preparation method of a rubber as claimed in claim 1 or 2 comprises the steps:
A, the Ethylene Propylene Terpolymer rubber mixed with properties-correcting agent obtain the modified EPT rubber precursor, then the modified EPT rubber precursor is heat-treated, obtain modified EPT rubber;
B, modified EPT rubber is mixed with vulcanizing agent and promotor, obtain the Ethylene Propylene Terpolymer rubber unvulcanizate, the butyronitrile rubber is mixed with vulcanizing agent and promotor, obtain the butyronitrile rubber unvulcanizate;
C, described Ethylene Propylene Terpolymer rubber unvulcanizate and butyronitrile rubber unvulcanizate are mixed with promoting agent;
Described properties-correcting agent is the salt of 2-benzothiazolyl mercaptan, 2-benzothiazolyl mercaptan, in the 2-mercaptothiazoline one or more; Described Ethylene Propylene Terpolymer rubber and butyronitrile rubber weight ratio are 1: 1～4: 1; With Ethylene Propylene Terpolymer rubber content is benchmark, and described modifier content is 1～4wt%, and described active agent content is 5～8wt%; With Ethylene Propylene Terpolymer rubber content is benchmark, and the described and vulcanizing agent content modified EPT rubber mix is 0.5～1.5wt%, and accelerator content is 2～5wt%; With butyronitrile rubber content is benchmark, and described and butyronitrile rubber blended vulcanizing agent content is 0.5～1.5wt%, and accelerator content is 1.5～4wt%.
7. preparation method according to claim 6 is characterized in that: described heat treating method is for to keep 40～70min with the modified EPT rubber precursor in 80～100 ℃.
8. preparation method according to claim 6, it is characterized in that: described Ethylene Propylene Terpolymer rubber unvulcanizate and butyronitrile rubber unvulcanizate and promoting agent blended method are in mill, add the Ethylene Propylene Terpolymer rubber unvulcanizate earlier, divide 1～4 time then and add the butyronitrile rubber unvulcanizate, add promoting agent at last and open refining.
9. according to any described preparation method in the claim 6,7 or 8, it is characterized in that: described properties-correcting agent is one or more in 2-benzothiazolyl mercaptan, cyclohexylamine salt of 2-mercaptobenzothiazole, the 2-mercaptothiazoline; Described promoting agent is zinc oxide and stearic mixture or Zinic stearas; Described vulcanizing agent be sulphur, 4,4 '-dimorpholinyl disulfide and 2,4, one or more in the 6-tri-thiol s-triazine; Described promotor is octadecyl sec.-propyl dithiocar-bamate.
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| CN103799581A (en) * | 2014-03-13 | 2014-05-21 | 苏州市相城区明达复合材料厂 | Rubber gloves with sterilizing function |
| CN105524313B (en) * | 2016-01-28 | 2017-10-17 | 青岛科技大学 | A kind of high-low temperature resistant nitrile rubber |
| CN106633421A (en) * | 2016-10-09 | 2017-05-10 | 芜湖瑞德机械科技有限公司 | Antiaging rubber sealing gasket and preparation method thereof |
| CN106398001A (en) * | 2016-10-09 | 2017-02-15 | 芜湖瑞德机械科技有限公司 | Tension-resistant rubber gasket and preparation method thereof |
| CN106763789A (en) * | 2017-01-13 | 2017-05-31 | 东莞市瑞拓五金橡塑有限公司 | Rubber seal |
| CN107141617A (en) * | 2017-06-27 | 2017-09-08 | 南京金三力高分子科技有限公司 | A kind of oil resistant ethylene propylene diene monomer (EPDM) material and preparation method thereof |
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| WO2003011963A1 (en) * | 2001-07-31 | 2003-02-13 | Bayer Inc. | Covulcanisation of polymers |
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| CN1314432A (en) * | 1995-05-24 | 2001-09-26 | 三井化学株式会社 | Valcanized rubber prepared from ethylene-/alpha-alkene/non-conjugated polynee tripoly rubber composition |
| WO2003011963A1 (en) * | 2001-07-31 | 2003-02-13 | Bayer Inc. | Covulcanisation of polymers |
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