CN109096560A - A kind of high-low temperature resistant oiliness nitrile rubber pipe and preparation method thereof - Google Patents
A kind of high-low temperature resistant oiliness nitrile rubber pipe and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The present invention relates to field of material processings, a kind of high-low temperature resistant oiliness nitrile rubber pipe and preparation method thereof is disclosed, which includes the composition of following parts by weight: 65 ~ 85 parts of nitrile rubber, 40 ~ 60 parts of hydrogenated nitrile-butadiene rubber, 20 ~ 40 parts of fast extrude in carbon black, 8 ~ 12 parts of zinc oxide, 0.5 ~ 1.5 part of stearic acid, 0.5 ~ 1.5 part of anti-aging agent RD, 1 ~ 2 part of organosilicon processing aid, 2 ~ 4 parts of plasticizer TP, 1 ~ 3 part of crosslink agent DCP, 0.3 ~ 0.7 part of altax, 0.3 ~ 0.7 part of sulphur.The present invention improves the heat-resisting quantity of rubber using fast extrude in carbon black as filler, and nitrile rubber itself has good lower temperature resistance, and hydrogenated nitrile-butadiene rubber has good solvent resistance.Nitrile rubber pipe prepared by the method for the present invention has good resistant of high or low temperature and oil resistivity, is suitble to large-scale production.
Description
Technical field
The present invention relates to field of material processing more particularly to a kind of high-low temperature resistant oiliness nitrile rubber pipe and its preparation sides
Method.
Background technique
Rubber product is many kinds of, and physical mechanical property is good, and elasticity is high, is widely used in the various components of automobile, including
Tire, sebific duct, transmission belt, sealing article, yielding rubber part and security article.In recent years, with the quick hair of auto industry
Exhibition, higher and higher to the performance requirement of rubber product, the resistant of high or low temperature of the rubber material on existing market more and more comes can not
Meets the needs of market.Therefore, it is badly in need of developing a kind of automobile air conditioner rubber hose high-low temperature resistant rubber material.Nitrile rubber is propylene
The random copolymer of nitrile and butadiene has excellent oil resistivity.Increase with its polarity of the increase of acrylonitrile content, oil resistivity is bright
It is aobvious to improve, but cold tolerance declines.Hydrogenated butyl rubber since main chain tends to saturation state, have excellent oil resistivity, elasticity,
Heat resistance, acid resistance and resistance to ag(e)ing.After nitrile rubber is blended with hydrogenated butyl rubber, the rubber of preparation has excellent resistance to
High and low temperature and solvent resistance.However, its intensity and wear-resisting property need to further increase.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of high-low temperature resistant oiliness nitrile rubber pipe and its preparation sides
Method.There is excellent resistant of high or low temperature, solvent resistance and wear-resisting property, and preparation process using the nitrile rubber of this method production
Simply, production cost is low.
The specific technical proposal of the invention is: a kind of high-low temperature resistant oiliness nitrile rubber pipe, including following parts by weight
Composition: 65~85 parts of nitrile rubber, 40~60 parts of hydrogenated nitrile-butadiene rubber, 20~40 parts of fast extrude in carbon black, 8~12 parts of zinc oxide,
0.5~1.5 part of stearic acid, 1~2 part of organosilicon processing aid, 2~4 parts of plasticizer TP, is handed over 0.5~1.5 part of anti-aging agent RD
Join 1~3 part of agent DCP, 0.3~0.7 part of altax, 0.3~0.7 part of sulphur.
Nitrile rubber is the random copolymer of acrylonitrile and butadiene, has excellent oil resistivity.With acrylonitrile content
Increase the increase of its polarity, oil resistivity significantly improves, but cold tolerance declines.Hydrogenated butyl rubber tends to be saturated shape due to main chain
State has excellent oil resistivity, elasticity, heat resistance, acid resistance and resistance to ag(e)ing.Nitrile rubber is blended with hydrogenated butyl rubber
Afterwards, the rubber of preparation has excellent resistant of high or low temperature and solvent resistance.Fast extrude in carbon black partial size is larger, and structure is higher, can assign
The good processing performance of sizing material and higher stress at definite elongation are given, heat is small and thermal conductivity is good, and high temperature resistance is superior, by it
The high temperature resistance of nitrile rubber can be dramatically increased as the filler of nitrile rubber.
Preferably, the partial size of the fast extrude in carbon black is 40~45nm.
Preferably, the organosilicon processing aid is vinyltriethoxysilane, vinyltrimethoxysilane, second
At least one of alkenyl three (beta-methoxy ethyoxyl) silane.
Preferably, a kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the following steps are included:
(1) weigh in parts by weight nitrile rubber, hydrogenated nitrile-butadiene rubber, fast extrude in carbon black, zinc oxide, stearic acid, anti-aging agent RD,
Organosilicon processing aid, plasticizer TP, crosslink agent DCP, promotor, sulphur and remaining other components, carry out after mixing
It is kneaded, obtains rubber compound；
(2) rubber compound is squeezed out with extruder, obtains high-low temperature resistant oiliness nitrile rubber pipe.
Preferably, the mixing is in two stages, the first stage is in 150~170 DEG C of 10~30min of mixing, second-order
Section is in 180~220 DEG C of 1~2h of mixing.
Preferably, the mixing pressure is 10~12KN, banbury rotating speed is 45~55r/min.
Preferably, further include in the component of the high-low temperature resistant oiliness nitrile rubber pipe parts by weight be 10~15 parts
The modified halloysite nanotubes of silicon fluoride, preparation method are as follows: halloysite nanotubes are dispersed in water and are made 1~3mg/ml's
Dispersion liquid, the silicon fluoride solution that hydrolysis is added are uniformly mixed, wherein the quality of silicon fluoride and halloysite nanotubes in mixed solution
Than sufficiently reacting 1h~60h under 25 DEG C~90 DEG C stirring conditions, obtaining silicon fluoride surface modification galapectite nanometer for 1:1~8
Pipe aqueous solution；It is cooling, it is so dry that be modified halloysite nanotubes after suction filtration.
Preferably, the silicon fluoride is trifluoromethyl trimethyl silyl, γ-trifluoro propyl methyl polysiloxane, three
Fluoropropyl methyl cyclotrisiloxane, two (3,3,3- trifluoro propyl) dimethoxysilanes, ten trifluoro octyl trimethoxy silanes, ten
At least one of difluoro heptyl propyl trimethoxy silicane.
Preferably, further include in the component of the high-low temperature resistant oiliness nitrile rubber pipe parts by weight be 10~15 parts
Modified carbon nano-tube, modified carbon nano-tube are the carbon nanotube that amino modified partial size is 800~900nm, method of modifying are as follows: will
Carbon nanotube is added in the concentrated nitric acid that concentration is 60~70wt%, every 1g carbon nanotube 50~90ml concentrated nitric acid, 100~
2~6h is handled under conditions of 140 DEG C, cooling, filtering is in neutrality to filtrate wash with distilled water, and it is dry, obtain the carbon nanometer of acidification
Pipe；Ultrasonic disperse 20~40min, every 1g carbon nanotube 50~120ml DMF in DMF solvent is added in the carbon nanotube of acidification
Solvent takes the DMF solution of DCC, DMAP and PAA to be added in the DMF suspension of carbon nanotube, carbon nanotube and DCC, DMAP,
The amount ratio of PAA is 1:3~5:0.1~0.5:8~12, cold in 80~100 DEG C of reaction 18~30h under inert atmosphere protection
But, filter, be in neutrality wash with distilled water to filtrate, it is dry, obtain the carbon nanotube of carboxylated；The carbon nanotube of carboxylated is added
Enter 20~40min of ultrasonic disperse in DMF solvent, then it is more that more ethylene are added in every 1g carbon nanotube 50~120ml DMF solvent
Amine, the carbon nanotube of carboxylated and the mass ratio of polyethylene polyamine are 1:1~3, react 18 at 20~30 DEG C in an inert atmosphere
~30h, cooling, filtering, is in neutrality to filtrate wash with distilled water, obtains amino modified carbon nanotube after dry.
Preferably, further include in the component of the high-low temperature resistant oiliness nitrile rubber pipe parts by weight be 10~25 parts
White carbon black, the specific surface area of the white carbon black are 70-200m2/g。
The rubber that nitrile rubber and hydrogenated nitrile-butadiene rubber are mixed with has resistant of high or low temperature, solvent resistance, however, it is strong
Degree and wearability are ideal not enough.Carbon black or carbon nanotube are added during preparing rubber can increase the wearability of rubber,
But it since carbon black and carbon nanotube are easy to reunite in rubber, can affect to the intensity of rubber.Individually with an angstrom Lip river
When filler of the stone nanotube as rubber, the bad dispersibility in rubber, the poor compatibility with rubber, it is difficult to it is excellent to obtain performance
Good rubber.When individually using carbon nanotube as the filler of rubber, bad dispersibility in rubber is easy to reunite, with rubber
Poor compatibility, it is difficult to obtain the rubber that thermal conductivity and intensity can be excellent.The present inventor is it is discovered by experiment that carbon nanotube is changed
Property after when being used as the filler of rubber together with halloysite nanotubes and white carbon black modified with silicon fluoride, the rubber of preparation is shown
Excellent resistant of high or low temperature, while there is good wear-resisting property.
Dispersibility of the halloysite nanotubes in rubber can be improved with the modified halloysite nanotubes of silicon fluoride, increase by two
The compatibility of person.The silicon fluoride modified some hydroxyls of halloysite nanotubes surface residual and carboxyl；After carbon nano-tube modification, surface
Contain amino；White carbon black surface also has hydroxyl group；By the modified halloysite nanotubes of silicon fluoride, modified carbon nano-tube and white
When carbon black is used as the filler of rubber together, the amino of modified carbon nano tube pipe surface can be with the halloysite nanotubes of silicon fluoride modification
Complicated three-dimensional net structure is formed between the hydroxy or carboxy on surface and the hydroxyl on white carbon black surface, so that in the rubber of preparation
Simultaneously containing there are three types of different networks composition, network structure, the carbon nanotube itself having including halloysite nanotubes itself have
What halloysite nanotubes, modified carbon nano-tube and the silica gel that some network structures and white carbon black are modified with silicon fluoride were formed answers
Miscellaneous reticular structure.The network structure of halloysite nanotubes and carbon nanotube itself has very big rigidity, this complexity of formation
Three-dimensional net structure can significantly increase rubber abrasive-resistance, while the complex network structures in the rubber prepared can be used as rubber
Skeleton, significantly improve the intensity and intensity of rubber.Meanwhile halloysite nanotubes and carbon modified that white carbon black and silicon fluoride are modified
Nanotube problem easy to reunite when can solve three separately as filler after combining increases modified angstrom of white carbon black, silicon fluoride
The dispersibility of Lip river stone nanotube and modified carbon nano-tube in rubber.
Be compared with the prior art, the beneficial effects of the present invention are: the present invention using the modified halloysite nanotubes of silicon fluoride,
Modified carbon nano-tube and white carbon black are used as filler to prepare nitrile rubber together, the rubber of preparation have good resistant of high or low temperature and
Wearability, and preparation process is simple, is suitble to large-scale production.
Specific embodiment
The present invention will be further described with reference to the examples below.Related device, connection structure in the present invention
And method, if being device well known in the art, connection structure and method without refering in particular to.
Embodiment 1
A kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the following steps are included:
(1) 75 parts of nitrile rubber, 50 parts of hydrogenated nitrile-butadiene rubber, the fast extrude in carbon black that partial size is 40~45nm are weighed in parts by weight
30 parts, 10 parts of zinc oxide, 1 part of stearic acid, 1 part of anti-aging agent RD, 1.5 parts of vinyltriethoxysilane, 3 parts of plasticizer TP,
2 parts of crosslink agent DCP, 0.5 part of altax, 0.5 part of sulphur, after mixing in 160 DEG C of mixing 20min, then at 200 DEG C
It is kneaded 1.5h, mixing pressure is 11KN, and banbury rotating speed 50r/min obtains rubber compound.
(2) rubber compound is squeezed out with extruder, obtains nitrile rubber pipe.
Embodiment 2
A kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the following steps are included:
(1) the modified halloysite nanotubes of 75 parts of nitrile rubber, 50 parts of hydrogenated nitrile-butadiene rubber, silicon fluoride are weighed in parts by weight
12.5 parts, partial size be 800~900nm 12.5 parts of modified carbon nano-tube, specific surface area 130m2White carbon black 17 part, of/g
Diameter is 30 parts of the fast extrude in carbon black of 40~45nm, 10 parts of zinc oxide, 1 part of stearic acid, 1 part of anti-aging agent RD, vinyl triethoxyl
1.5 parts of silane, 3 parts of plasticizer TP, 2 parts of crosslink agent DCP, 0.5 part of altax, 0.5 part of sulphur, after mixing 160
DEG C it is kneaded 20min, then in 200 DEG C of mixings 1.5h, mixing pressure is 11KN, and banbury rotating speed 50r/min obtains rubber compound.
(2) rubber compound is squeezed out with extruder, obtains nitrile rubber pipe.
Wherein, the modified halloysite nanotubes of silicon fluoride the preparation method comprises the following steps: halloysite nanotubes are dispersed in water system
At the dispersion liquid of 2mg/ml, the trifluoro propyl methyl cyclotrisiloxane solution that hydrolysis is added is uniformly mixed, wherein mixed solution
The mass ratio of middle trifluoro propyl methyl cyclotrisiloxane and halloysite nanotubes is 1:5, is sufficiently reacted under 45 DEG C of stirring conditions
30h obtains silicon fluoride surface modification halloysite nanotubes aqueous solution；It is cooling, dry the modified galapectite of silicon fluoride after suction filtration
Nanotube.
Modified carbon nano-tube the preparation method comprises the following steps: by carbon nanotube be added concentration be 65wt% concentrated nitric acid in, every 1g carbon
The effective 70ml concentrated nitric acid of nanometer handles 4h under conditions of 120 DEG C, and cooling, filtering is in neutrality to filtrate wash with distilled water,
It is dry, obtain the carbon nanotube of acidification；Ultrasonic disperse 30min in DMF solvent, every 1g carbon nanotube is added in the carbon nanotube of acidification
With 90ml DMF solvent, the DMF solution of DCC, DMAP and PAA is taken to be added in the DMF suspension of carbon nanotube, carbon nanotube with
The amount ratio of DCC, DMAP, PAA are 1:4:0.3:10, are reacted for 24 hours under inert atmosphere protection at 90 DEG C, cooling, filtering, with steaming
Distilled water is cleaned to filtrate and is in neutrality, dry, obtains the carbon nanotube of carboxylated；The carbon nanotube of carboxylated is added in DMF solvent
Then polyethylene polyamine, the carbon nanotube of carboxylated is added in ultrasonic disperse 30min, every 1g carbon nanotube 90ml DMF solvent
Mass ratio with polyethylene polyamine is 1:2, reacts cooling, filtering for 24 hours at 25 DEG C in an inert atmosphere, wash with distilled water extremely
Filtrate is in neutrality, and obtains amino modified carbon nanotube after dry.
Embodiment 3
A kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the following steps are included:
(1) the modified halloysite nanotubes 15 of 85 parts of nitrile rubber, 60 parts of hydrogenated nitrile-butadiene rubber, silicon fluoride are weighed in parts by weight
Part, 15 parts of modified carbon nano-tube, 12.9 parts of white carbon black, partial size is 20 parts of the fast extrude in carbon black of 40~45nm, 8 parts of zinc oxide, hard
0.5 part of resin acid, 1 part of vinyltrimethoxysilane, 2 parts of plasticizer TP, 1 part of crosslink agent DCP, promotees 0.5 part of anti-aging agent RD
Into 0.3 part of agent DM, 0.3 part of sulphur, after mixing in 170 DEG C of mixing 10min, then in 220 DEG C of mixing 1h, it is kneaded pressure
Rubber compound is obtained for 12KN, banbury rotating speed 45r/min.
(2) rubber compound is squeezed out with extruder, obtains nitrile rubber pipe.
Wherein, the modified halloysite nanotubes of silicon fluoride the preparation method comprises the following steps: halloysite nanotubes are dispersed in water system
At the dispersion liquid of 3mg/ml, γ-trifluoro propyl methyl polysiloxane solution that hydrolysis is added is uniformly mixed, wherein mixed solution
The mass ratio of middle γ-trifluoro propyl methyl polysiloxane and halloysite nanotubes is 1:8, is sufficiently reacted under 85 DEG C of stirring conditions
20h obtains silicon fluoride surface modification halloysite nanotubes aqueous solution；It is cooling, dry the modified galapectite of silicon fluoride after suction filtration
Nanotube.
Modified carbon nano-tube the preparation method comprises the following steps: by carbon nanotube be added concentration be 70wt% concentrated nitric acid in, every 1g carbon
The effective 90ml concentrated nitric acid of nanometer handles 2h under conditions of 140 DEG C, and cooling, filtering is in neutrality to filtrate wash with distilled water,
It is dry, obtain the carbon nanotube of acidification；Ultrasonic disperse 40min in DMF solvent, every 1g carbon nanotube is added in the carbon nanotube of acidification
With 120ml DMF solvent, the DMF solution of DCC, DMAP and PAA is taken to be added in the DMF suspension of carbon nanotube, carbon nanotube
Amount ratio with DCC, DMAP, PAA is 1:5:0.5:12, and in 100 DEG C of reaction 18h under inert atmosphere protection, cooling is filtered,
It is in neutrality wash with distilled water to filtrate, it is dry, obtain the carbon nanotube of carboxylated；It is molten that DMF is added in the carbon nanotube of carboxylated
Ultrasonic disperse 40min in agent, every 1g carbon nanotube 120ml DMF solvent, is then added polyethylene polyamine, and the carbon of carboxylated is received
The mass ratio of mitron and polyethylene polyamine is 1:3, and in an inert atmosphere in 30 DEG C of reaction 18h, cooling, filtering is clear with distilled water
It is washed till filtrate to be in neutrality, obtains amino modified carbon nanotube after dry.
Embodiment 4
A kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the following steps are included:
(1) the modified halloysite nanotubes 10 of 65 parts of nitrile rubber, 60 parts of hydrogenated nitrile-butadiene rubber, silicon fluoride are weighed in parts by weight
Part, partial size be 800~900nm 15 parts of modified carbon nano-tube, specific surface area 200m225 parts of white carbon black, the partial size 40 of/g
20 parts of the fast extrude in carbon black of~45nm, 11 parts of zinc oxide, 1.1 parts of stearic acid, 1.5 parts of anti-aging agent RD, three (beta-methoxy of vinyl
Ethyoxyl) 1 part of silane, 4 parts of plasticizer TP, 2 parts of crosslink agent DCP, 0.5 part of altax, 0.4 part of sulphur, after mixing
In 150 DEG C of mixing 30min, then in 180 DEG C of mixing 2h, mixing pressure is 10KN, and banbury rotating speed 55r/min must be kneaded
Glue.
(2) rubber compound is squeezed out with extruder, obtains nitrile rubber pipe.
Wherein, the modified halloysite nanotubes of silicon fluoride the preparation method comprises the following steps: halloysite nanotubes are dispersed in water system
At the dispersion liquid of 1.5mg/ml, the trifluoro propyl methyl cyclotrisiloxane solution that hydrolysis is added is uniformly mixed, wherein mixing is molten
The mass ratio of trifluoro propyl methyl cyclotrisiloxane and halloysite nanotubes is 1:1 in liquid, sufficiently anti-under 40 DEG C of stirring conditions
60h is answered, silicon fluoride surface modification halloysite nanotubes aqueous solution is obtained；It is cooling, dry the modified Ai Luo of silicon fluoride after suction filtration
Stone nanotube.
Modified carbon nano-tube the preparation method comprises the following steps: modified carbon nano-tube the preparation method comprises the following steps: concentration is added in carbon nanotube
For in the concentrated nitric acid of 60wt%, every 1g carbon nanotube 50ml concentrated nitric acid handles 6h under conditions of 100 DEG C, and cooling is filtered,
It is in neutrality wash with distilled water to filtrate, it is dry, obtain the carbon nanotube of acidification；The carbon nanotube of acidification is added in DMF solvent
Ultrasonic disperse 20min, every 1g carbon nanotube 50ml DMF solvent take the DMF solution of DCC, DMAP and PAA to be added to carbon nanometer
In the DMF suspension of pipe, the amount ratio of carbon nanotube and DCC, DMAP, PAA are 1:3:0.1:8, under inert atmosphere protection
80 DEG C of reaction 30h, cooling, filtering, are in neutrality to filtrate wash with distilled water, dry, obtain the carbon nanotube of carboxylated；By carboxyl
Ultrasonic disperse 20min in DMF solvent is added in the carbon nanotube of change, then every 1g carbon nanotube 50ml DMF solvent is added more
The mass ratio of ethylene polyamine, the carbon nanotube of carboxylated and polyethylene polyamine is 1:1, in an inert atmosphere in 20 DEG C of reaction 30h,
Cooling, filtering, is in neutrality to filtrate wash with distilled water, obtains amino modified carbon nanotube after dry.
Comparative example 1
A kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the difference is that, do not add hard charcoal during the preparation process
Black, the total amount for preparing all components of Viton is same as Example 2, other preparation methods are same as Example 2.
Comparative example 2
A kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the difference is that, do not add modification during the preparation process
Carbon nanotube, the total amount for preparing all components of Viton is same as Example 2, other preparation methods with 2 phase of embodiment
Together.
Comparative example 3
A kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the difference is that, do not add fluorine silicon during the preparation process
The modified halloysite nanotubes of alkane, the total amount for preparing all components of Viton is same as Example 2, other preparation methods are equal
It is same as Example 2.
Comparative example 4
A kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the difference is that, do not add hard charcoal during the preparation process
The modified halloysite nanotubes of black and silicon fluoride, the total amount for preparing all components of Viton is same as Example 2, other systems
Preparation Method is same as Example 2.
Comparative example 5
A kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the difference is that, do not add hard charcoal during the preparation process
Black and modified carbon nano-tube, the total amount for preparing all components of Viton is same as Example 2, other preparation methods with reality
It is identical to apply example 2.
Comparative example 6
A kind of preparation method of high-low temperature resistant oiliness nitrile rubber pipe the difference is that, do not add fluorine silicon during the preparation process
Alkane modified halloysite nanotubes and modified carbon nano-tube, the total amount for preparing all components of Viton is same as Example 2,
Other preparation methods are same as Example 2.
To super wear resistance energy Viton pipe prepared by Examples 1 to 4 and comparative example 1~6, testing standard are as follows: GB/T
15256-1994, GB/T 15256-1994, GB/T 528-2009, GB/T 528-2009, GB/T 528-2009 and GB/T
9867-1988 tests its brittleness temperature, flow temperature, elongation at break, tearing strength, tensile strength and wear resistance respectively.
As a result as shown in table 1 below.
Table 1
As can be seen from Table 1, the nitrile rubber pipe of preparation has excellent resistant of high or low temperature, and the addition of fast extrude in carbon black makes butyronitrile
Rubber tube has excellent heat-resisting quantity.When the modified halloysite nanotubes of the addition silicon fluoride in rubber, modified carbon nano-tube
When with white carbon black, tearing toughness, tensile strength and the wear-resisting property of rubber are obviously improved.In comparative example 1~6, respectively
The total amount of kind component is identical as the total amount of each component of embodiment 2, but its wear-resisting property and intensity all exist compared with Example 2
Very big gap.It can be seen that when only adding the modified halloysite nanotubes of silicon fluoride, modified carbon nano-tube in rubber
It is all unable to reach good abrasion resistant effect when with one or both of white carbon black, it only could when three kinds of fillers all add
Show excellent wearability and intensity.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent structure transformation to the above embodiments, still fall within skill of the present invention
The protection scope of art scheme.
Claims (10)
1. a kind of high-low temperature resistant oiliness nitrile rubber pipe, it is characterised in that the composition including following parts by weight: nitrile rubber 65 ~
85 parts, it is 40 ~ 60 parts of hydrogenated nitrile-butadiene rubber, 20 ~ 40 parts of fast extrude in carbon black, 8 ~ 12 parts of zinc oxide, 0.5 ~ 1.5 part of stearic acid, anti-old
0.5 ~ 1.5 part of agent RD, 1 ~ 2 part of organosilicon processing aid, 2 ~ 4 parts of plasticizer TP, 1 ~ 3 part of crosslink agent DCP, altax
0.3 ~ 0.7 part, 0.3 ~ 0.7 part of sulphur.
2. a kind of high-low temperature resistant oiliness nitrile rubber pipe as described in claim 1, it is characterised in that: the fast extrude in carbon black
Partial size is 40 ~ 45nm.
3. a kind of high-low temperature resistant oiliness nitrile rubber pipe as described in claim 1, it is characterised in that: the organosilicon processing helps
Agent be vinyltriethoxysilane, vinyltrimethoxysilane, in vinyl three (beta-methoxy ethyoxyl) silane at least
It is a kind of.
4. a kind of high-low temperature resistant oiliness nitrile rubber pipe as described in claim 1, it is characterised in that: the nitrile rubber pipe
Preparation method the following steps are included:
(1) weigh in parts by weight nitrile rubber, hydrogenated nitrile-butadiene rubber, fast extrude in carbon black, zinc oxide, stearic acid, anti-aging agent RD,
Organosilicon processing aid, plasticizer TP, crosslink agent DCP, promotor, sulphur and remaining other components, carry out after mixing
It is kneaded, obtains rubber compound；
(2) rubber compound is squeezed out with extruder, obtains high-low temperature resistant oiliness nitrile rubber pipe.
5. a kind of high-low temperature resistant oiliness nitrile rubber pipe as claimed in claim 4, it is characterised in that: the mixing is divided to two ranks
Section, first stage are in 150 ~ 170 DEG C of 10 ~ 30min of mixing, and second stage is in 180 ~ 220 DEG C of 1 ~ 2h of mixing.
6. a kind of high-low temperature resistant oiliness nitrile rubber pipe as described in claim 4 or 5, it is characterised in that: the mixing pressure
For 10 ~ 12KN, banbury rotating speed is 45 ~ 55r/min.
7. a kind of high-low temperature resistant oiliness nitrile rubber pipe as described in Claims 1-4 is any, it is characterised in that: the resistance to height
It further include the parts by weight halloysite nanotubes modified for 10 ~ 15 parts of silicon fluoride in the component of low temperature oiliness nitrile rubber pipe,
Preparation method are as follows: halloysite nanotubes are dispersed in water to the dispersion liquid that 1 ~ 3mg/ml is made, the silicon fluoride that hydrolysis is added is molten
Liquid is uniformly mixed, wherein the mass ratio of silicon fluoride and halloysite nanotubes is 1:1 ~ 8 in mixed solution, is stirred at 25 DEG C ~ 90 DEG C
Under the conditions of sufficiently react 1h ~ 60h, obtain silicon fluoride surface modification halloysite nanotubes aqueous solution；It is cooling, it is so dry that change after suction filtration
Property halloysite nanotubes.
8. a kind of high-low temperature resistant oiliness nitrile rubber pipe as claimed in claim 7, it is characterised in that: the silicon fluoride is trifluoro
Methyl trimethoxy base monosilane, γ-trifluoro propyl methyl polysiloxane, trifluoro propyl methyl cyclotrisiloxane, two (3,3,3- trifluoros
Propyl) dimethoxysilane, ten trifluoro octyl trimethoxy silanes, at least one in ten difluoro heptyl propyl trimethoxy silicanes
Kind.
9. a kind of high-low temperature resistant oiliness nitrile rubber pipe as claimed in claim 7, it is characterised in that: the high-low temperature resistant oiliness
It further include the modified carbon nano-tube that parts by weight are 10 ~ 15 parts in the component of nitrile rubber pipe, modified carbon nano-tube changes for amino
Property partial size be 800 ~ 900nm carbon nanotube, method of modifying are as follows: by carbon nanotube be added concentration be 60 ~ 70wt% concentrated nitric acid
In, every 1g carbon nanotube 50 ~ 90ml concentrated nitric acid handles 2 ~ 6h under conditions of 100 ~ 140 DEG C, and distilled water is used in cooling, filtering
Cleaning to filtrate is in neutrality, dry, obtains the carbon nanotube of acidification；Ultrasonic disperse in DMF solvent is added in the carbon nanotube of acidification
20 ~ 40min, every 1g carbon nanotube 50 ~ 120ml DMF solvent, takes the DMF solution of DCC, DMAP and PAA to be added to carbon nanometer
In the DMF suspension of pipe, the amount ratio of carbon nanotube and DCC, DMAP, PAA are 1:3 ~ 5:0.1 ~ 0.5:8 ~ 12, in inert atmosphere
In 80 ~ 100 DEG C of 18 ~ 30h of reaction under protection, cooling, filtering is in neutrality to filtrate wash with distilled water, dry, obtains carboxylated
Carbon nanotube；The carbon nanotube of carboxylated is added 20 ~ 40min of ultrasonic disperse in DMF solvent, every 1g carbon nanotube with 50 ~
Then polyethylene polyamine is added in 120ml DMF solvent, the carbon nanotube of carboxylated and the mass ratio of polyethylene polyamine are 1:1 ~ 3,
In an inert atmosphere in 20 ~ 30 DEG C of 18 ~ 30h of reaction, cooling, filtering is in neutrality to filtrate, after drying wash with distilled water to obtain the final product
To amino modified carbon nanotube.
10. a kind of high-low temperature resistant oiliness nitrile rubber pipe as claimed in claim 9, it is characterised in that: the high-low temperature resistant oil
Property nitrile rubber pipe component in further include parts by weight be 10 ~ 25 parts of white carbon black, the specific surface area of the white carbon black is 70-
200m2/g。
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| CN113667197A (en) * | 2021-07-29 | 2021-11-19 | 中国海洋石油集团有限公司 | Sizing material, preparation thereof and application thereof in marine flexible joint internal elastomer |
| CN117430877A (en) * | 2023-10-11 | 2024-01-23 | 六安市金赛特橡塑制品有限公司 | Antibacterial sealing rubber for water delivery pipeline of dish washer and production process |
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| CN109181170A (en) * | 2018-08-07 | 2019-01-11 | 浙江久运汽车零部件有限公司 | A kind of wear-resisting type Viton pipe and preparation method thereof |
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| CN113667197A (en) * | 2021-07-29 | 2021-11-19 | 中国海洋石油集团有限公司 | Sizing material, preparation thereof and application thereof in marine flexible joint internal elastomer |
| CN117430877A (en) * | 2023-10-11 | 2024-01-23 | 六安市金赛特橡塑制品有限公司 | Antibacterial sealing rubber for water delivery pipeline of dish washer and production process |
| CN117430877B (en) * | 2023-10-11 | 2024-05-31 | 六安市金赛特橡塑制品有限公司 | Antibacterial sealing rubber for water delivery pipeline of dish washer and production process |
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