CN104530508B - One brood lac core material and preparation method thereof - Google Patents
One brood lac core material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a brood lac core material, include following components nitrile rubber 80～120 parts, high abrasion furnace black 15～20 parts, semi-reinforcing furnace black 20～30 parts by weight, graphene composite material 10～30 parts, ultra-fine sulfide powder polrvinyl chloride 20～40 parts, stearic acid 0.8～1.5 parts, dioctyl phthalate 1.2～2 parts, dibutyl phthalate 1～1.8 parts, accelerator TT1～4 parts, accelerant CZ 0.5～3 parts, anti-aging agent RD 1～3 parts；The invention still further relates to the preparation method of above-mentioned glue core material.Graphene composite material in the present invention has preferable affinity, and the Graphene of honeycomb crystal lattice structure may advantageously facilitate the dispersion of other component, simultaneously, ultra-fine sulfide powder polrvinyl chloride also can promote that graphene composite material and other component are uniformly dispersed, thus between graphene composite material and ultra-fine sulfide powder polrvinyl chloride, produce synergism, give full play to the effect of each component, improve the benefit performance of glue core material comprehensively.
Description
Technical field
The present invention relates to the glue core material technical field of preventer, refer specifically to brood lac core material and preparation method thereof.
Background technology
Glue core is the key component of the omnipotent annular preventer of oil well, is for avoiding the occurrence of during carrying out well workover and completion etc.
Blowout and use close well head equipment, its structure is relatively simple, but acts on particularly important.
As the standard elastomer of oil resistant rubber goods, nitrile rubber is because having oil resistant, ageing-resistant, benzene resistance energy, heat-resisting
Property etc. excellent physical and mechanical properties and be widely used in automobile, weaving, Aero-Space, oil extraction, petrochemical industry,
The fields such as electric wire, printing and dyeing and packaging for foodstuff.Nitrile rubber along with the increase of acrylonitrile content, its oil resistivity, resistance to combustion
Material oiliness, benzene resistance, hot strength, hardness, wearability, thermostability etc. all increase, and resilience, low temperature resistant
The performance such as flexibility, compression set but can be along with decline.In prior art, preventing with nitrile rubber as main component
Spray apparatus glue core, because of its have good oil resistant, ageing-resistant performance and be widely used in oil exploitation and petrochemical industry neck
Territory.
But, in prior art, the glue core of nitrile rubber still suffers from many deficiencies in actual applications: upper table easily occur
Face cracking and layer bulk comes off, glue in-core wall bulk degumming, bottom glue core with piston contact at the phenomenon such as rubber cracking,
Causing glue core can not seal up shaft bottom high-pressure fluid, glue core also cannot be recovered in time, and the wearability of glue core material and
Thermostability has much room for improvement.Application publication number is Chinese invention patent application " a kind of high-strength high abrasion of CN104194240A
Rubber " (application number: 201410487400.X) add Graphene in elastomeric material, hard to improving elastomeric material
Degree, wearability and thermostability.Owing to Graphene has difficult stripping, its apparent density is relatively low, directly by Graphene
Join in other material, be easily caused Graphene skewness in the material, be substantially reduced the improvement performance of Graphene,
Although above-mentioned patent application has carried out modification to Graphene, to promote other material being uniformly dispersed in elastomeric material, with
Time play strengthen elastomeric material anti-wear performance effect.But, it is complicated to the modified technique of Graphene, and it promotes it
Its material being uniformly dispersed in elastomeric material is the feature that make use of Graphene specific surface area big, and if Graphene this in
Elastomeric material disperses uniform not, then directly affect Graphene facilitation finely dispersed to other material.
Therefore, for being currently based on the glue core material of nitrile rubber, await being improved further.
Summary of the invention
The technical problem to be solved is the present situation for prior art, it is provided that a kind of can be effectively improved the hard of material
Degree, elastic, wearability and the glue core material of thermostability.
To be solved by this invention another technical problem is that the present situation for prior art, it is provided that a kind of above-mentioned glue core material
Preparation method.
The present invention solves the technical scheme that above-mentioned technical problem used: a brood lac core material, it is characterised in that by weight
Count and include following components:
Wherein, described graphene composite material is the Graphene/SEBS through in-situ reducing
Complex, this Graphene/SEBS complex is obtained by following methods: will under ultrasound condition
Graphene oxide powder disperses in organic solvent, and Graphene to be oxidized forms unformed suspension in organic solvent
After, under stirring condition, in above-mentioned suspension, add hydrogenated styrene, butadiene and styrene reaction, react complete
After organic solvent dry is distilled off through decompression；By described Graphene/SEBS
Complex completes in-situ reducing after melt blending 25min～60min at 220 DEG C～230 DEG C and obtains described Graphene
Composite；
Described ultra-fine sulfide powder polrvinyl chloride is obtained by following methods: add cross-linking radiation in the emulsion of polrvinyl chloride
Auxiliary agent TMPTA carries out cross-linking radiation reaction, carries out being spray-dried i.e. obtain containing ultra-fine sulfuration after reaction 20h～30h
The ultra-fine sulfide powder polrvinyl chloride of particulate polyvinyl chloride.
As a further improvement on the present invention, in described Graphene/SEBS complex, graphite
Alkene is 1:1～1.2 with the weight ratio of SEBS system；Described hydrogenated styrene-butadiene-benzene
In ethylene system, the weight ratio of hydrogenated styrene, butadiene and styrene three is 1:0.5～0.8:1.7～2.In employing
State proportioning parameter, the problem solving Graphene charging difficulty, make Graphene be prone in the material and be evenly distributed, fully send out
Wave the effect of Graphene, on the one hand increase the wearability of material, on the other hand promote that other component is uniformly dispersed in the material,
Improve the overall performance of glue core material.
Further, in described nitrile rubber, acrylonitrile content is the 41% of nitrile rubber weight, to improve glue core
Oil resistance, heat resistance and the mechanical property of material.
As preferably, the mean diameter of described graphene oxide is 25～50 μm, and oxygen content is 30～40at.%, layer
Spacing is 0.74nm, and average specific surface area is 5～10m2/g。
The preparation method of a kind of above-mentioned glue core material, it is characterised in that comprise the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight 100 parts of graphene oxide powder are dispersed in 150～200 parts of organic solvents,
After Graphene to be oxidized forms unformed suspension in organic solvent, add in above-mentioned suspension under stirring condition
100 parts～120 parts of SEBS system mixture, hydrogenated styrene, fourth two in this mixture
The weight ratio of alkene and styrene three is 1:0.5～0.8:1.7～2；
Carrying out decompression distillation after reaction 1.5h～2h, removing organic solvent and be also dried, obtain Graphene/hydrogenated styrene-
Butadiene-styrene complex；
By described Graphene/SEBS complex melt blending at 220 DEG C～230 DEG C,
Carry out in-situ reducing reaction 25min～60min, react complete and i.e. obtain described graphene composite material；
(2) preparation of ultra-fine sulfide powder polrvinyl chloride:
In the emulsion of 100 parts of polrvinyl chloride, add 5～6 parts of cross-linking radiation auxiliary agent TMPTA by weight carry out irradiation
Cross-linking reaction, is spray-dried at 100～120 DEG C after reaction 20h～30h, is i.e. contained after being dried 5～8h
There is the ultra-fine sulfide powder polrvinyl chloride of ultra-fine vulcanized polyvinyl chloride particle；
(3) take 80～120 parts of nitrile rubber thin slice bag rollers, add Graphene prepared by 10～30 parts of steps (1) multiple
Condensation material, refines 10～30min at roller temperature is 30～45 DEG C；Be subsequently adding 1.2～2 parts of dioctyl phthalates,
1～1.8 part of dibutyl phthalate, 0.8～1.5 part of stearic acid, 1～3 part of anti-aging agent RD, 15～20 parts of high abrasions
Furnace black and 20～30 parts of semi-reinforcing furnace black, in banburying chamber's banburying at 95～100 DEG C, set banbury rotating speed as 45
Rad/min, pressurize 18MPa, and the refining time is 1.5～3.5h；Then constant temperature plasticizing 2～4h at 155～160 DEG C,
At 150～160 DEG C, binder removal makes masterbatch；
(4) add in the masterbatch that step (3) obtains 20～40 parts of ultra-fine sulfide powder polrvinyl chloride, 1～4 part
Accelerator TT and 0.5～3 part of accelerant CZ carry out banburying, set banbury rotating speed as 25rad/min, and pressurize 17MPa,
The refining time is 2～3.5h；Then carry out plastifying, binder removal.
Compared with prior art, it is an advantage of the current invention that:
(1) present invention with the addition of the Graphene through in-situ reducing/SEBS complex, should
Graphene composite material is easily dispersed, solve Graphene difficulty in prior art peel off, adding of causing because apparent density is low
Material difficult problem so that Graphene can be dispersed in glue core material, has given full play to the effect of Graphene, has effectively carried
The wearability of high glue core material and thermostability；
(2) present invention with the addition of ultra-fine sulfide powder polrvinyl chloride, and during cross-linking radiation, electron ray is to poly-record second
Alkene excites so that it is enters higher energy level or ionized state and intermolecular formation free radical, and then makes to be in adjacent chain
Two free radicals meet crosslinking, owing to crosslinking exists with chain rupture simultaneously so that formation between polrvinyl chloride molecule after crosslinking
Network structure, so that glue core material is provided with stronger interfacial tension, improves toughness and the hardness of glue core material；
Meanwhile, ultra-fine sulfide powder polrvinyl chloride also makes glue core material be provided with preferable dimensionally stable as a kind of exotic material
Property and heat stability；
(3) graphene composite material in the present invention has preferable affinity, and the Graphene of honeycomb crystal lattice structure
May advantageously facilitate the dispersion of other component, meanwhile, ultra-fine sulfide powder polrvinyl chloride also can promote graphene composite material and
Other component is uniformly dispersed, thus produces collaborative work between graphene composite material and ultra-fine sulfide powder polrvinyl chloride
With, give full play to the effect of each component, improve the benefit performance of glue core material comprehensively；
(4) high abrasion furnace black and semi-reinforcing furnace black are used in mixed way the elasticity being effectively increased glue material.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
The glue core material of the present embodiment includes following components by weight:
The preparation method of above-mentioned glue core material comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight 100 parts of graphene oxide powder are dispersed in 150 parts of oxolanes, treat oxygen
After functionalized graphene forms unformed suspension in oxolane, under stirring condition, in above-mentioned suspension, add 100
Part SEBS system mixture, hydrogenated styrene, butadiene and styrene three in this mixture
The weight ratio of person is 1:0.5:1.7；
Carry out decompression distillation after reaction 1.5h, remove organic solvent and be dried, obtaining Graphene/hydrogenated styrene-fourth two
Alkene-Styrene compounds；
By Graphene/SEBS complex melt blending at 220 DEG C, carry out in-situ reducing anti-
Answer 25min, react complete and i.e. obtain graphene composite material；
(2) preparation of ultra-fine sulfide powder polrvinyl chloride:
In the emulsion of 100 parts of polrvinyl chloride, add 5 parts of cross-linking radiation auxiliary agent TMPTA by weight carry out irradiation friendship
Connection reaction, is spray-dried at 110 DEG C after reaction 25h, i.e. obtains containing ultra-fine sulfuration polychlorostyrene second after being dried 6h
The ultra-fine sulfide powder polrvinyl chloride of alkene particle；
(3) take nitrile rubber thin slice bag roller, add graphene composite material prepared by 25 parts of steps (1), in roller temperature
It is refining 15min at 30 DEG C；It is subsequently adding dioctyl phthalate, dibutyl phthalate, stearic acid, prevents
Old agent RD, high abrasion furnace black and semi-reinforcing furnace black, in banburying chamber's banburying at 95 DEG C, set banbury rotating speed as 45
Rad/min, pressurize 18MPa, and the refining time is 1.8h；Then constant temperature plasticizing 2h at 160 DEG C, arranges at 150 DEG C
Masterbatch made by glue；
(4) in the masterbatch that step (3) obtains, 25 parts of ultra-fine sulfide powder polrvinyl chloride, accelerator TT are added
And accelerant CZ carries out banburying, setting banbury rotating speed as 25rad/min, pressurize 17MPa, and the refining time is 2.5h；
Then carry out plastifying, binder removal.
Embodiment 2:
The glue core material of the present embodiment includes following components by weight:
The preparation method of above-mentioned glue core material comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight 100 parts of graphene oxide powder are dispersed in 160 parts of oxolanes, treat oxygen
After functionalized graphene forms unformed suspension in oxolane, under stirring condition, in above-mentioned suspension, add 110
Part SEBS system mixture, hydrogenated styrene, butadiene and styrene three in this mixture
The weight ratio of person is 1:0.8:1.7；
Carry out decompression distillation after reaction 1.8h, remove organic solvent and be dried, obtaining Graphene/hydrogenated styrene-fourth two
Alkene-Styrene compounds；
By Graphene/SEBS complex melt blending at 225 DEG C, carry out in-situ reducing anti-
Answer 40min, react complete and i.e. obtain graphene composite material；
(2) preparation of ultra-fine sulfide powder polrvinyl chloride:
In the emulsion of 100 parts of polrvinyl chloride, add 5.5 parts of cross-linking radiation auxiliary agent TMPTA by weight carry out irradiation friendship
Connection reaction, is spray-dried at 120 DEG C after reaction 30h, i.e. obtains containing ultra-fine sulfuration polychlorostyrene second after being dried 5h
The ultra-fine sulfide powder polrvinyl chloride of alkene particle；
(3) take nitrile rubber thin slice bag roller, add graphene composite material prepared by 20 parts of steps (1), in roller temperature
It is refining 20min at 35 DEG C；It is subsequently adding dioctyl phthalate, dibutyl phthalate, stearic acid, prevents
Old agent RD, high abrasion furnace black and semi-reinforcing furnace black, in banburying chamber's banburying at 97 DEG C, set banbury rotating speed as 45
Rad/min, pressurize 18MPa, and the refining time is 2.5h；Then constant temperature plasticizing 4h at 155 DEG C, arranges at 155 DEG C
Masterbatch made by glue；
(4) in the masterbatch that step (3) obtains, 30 parts of ultra-fine sulfide powder polrvinyl chloride, accelerator TT are added
And accelerant CZ carries out banburying, setting banbury rotating speed as 25rad/min, pressurize 17MPa, and the refining time is 3.5h；
Then carry out plastifying, binder removal.
Embodiment 3:
The glue core material of the present embodiment includes following components by weight:
The preparation method of above-mentioned glue core material comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight 100 parts of graphene oxide powder are dispersed in 180 parts of oxolanes, treat oxygen
After functionalized graphene forms unformed suspension in oxolane, under stirring condition, in above-mentioned suspension, add 120
Part SEBS system mixture, hydrogenated styrene, butadiene and styrene three in this mixture
The weight ratio of person is 1:0.8:2；
Carrying out decompression distillation after reaction 2h, removing organic solvent and be also dried, obtain Graphene/hydrogenated styrene-butadiene-
Styrene compounds；
By Graphene/SEBS complex melt blending at 230 DEG C, carry out in-situ reducing anti-
Answer 50min, react complete and i.e. obtain graphene composite material；
(2) preparation of ultra-fine sulfide powder polrvinyl chloride:
In the emulsion of 100 parts of polrvinyl chloride, add 6 parts of cross-linking radiation auxiliary agent TMPTA by weight carry out irradiation friendship
Connection reaction, is spray-dried at 110 DEG C after reaction 20h, i.e. obtains containing ultra-fine sulfuration polychlorostyrene second after being dried 7h
The ultra-fine sulfide powder polrvinyl chloride of alkene particle；
(3) take nitrile rubber thin slice bag roller, add graphene composite material prepared by 30 parts of steps (1), in roller temperature
It is refining 10min at 40 DEG C；It is subsequently adding dioctyl phthalate, dibutyl phthalate, stearic acid, prevents
Old agent RD, high abrasion furnace black and semi-reinforcing furnace black, in banburying chamber's banburying at 100 DEG C, set banbury rotating speed as 45
Rad/min, pressurize 18MPa, and the refining time is 3.5h；Then constant temperature plasticizing 3h at 158 DEG C, arranges at 160 DEG C
Masterbatch made by glue；
(4) in the masterbatch that step (3) obtains, 35 parts of ultra-fine sulfide powder polrvinyl chloride, accelerator TT are added
And accelerant CZ carries out banburying, setting banbury rotating speed as 25rad/min, pressurize 17MPa, and the refining time is 2h；
Then carry out plastifying, binder removal.
Embodiment 4:
The glue core material of the present embodiment includes following components by weight:
The preparation method of above-mentioned glue core material comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight 100 parts of graphene oxide powder are dispersed in 170 parts of oxolanes, treat oxygen
After functionalized graphene forms unformed suspension in oxolane, under stirring condition, in above-mentioned suspension, add 120
Part SEBS system mixture, hydrogenated styrene, butadiene and styrene three in this mixture
The weight ratio of person is 1:0.5:2；
Carry out decompression distillation after reaction 1.7h, remove organic solvent and be dried, obtaining Graphene/hydrogenated styrene-fourth two
Alkene-Styrene compounds；
By Graphene/SEBS complex melt blending at 225 DEG C, carry out in-situ reducing anti-
Answer 60min, react complete and i.e. obtain graphene composite material；
(2) preparation of ultra-fine sulfide powder polrvinyl chloride:
In the emulsion of 100 parts of polrvinyl chloride, add 6 parts of cross-linking radiation auxiliary agent TMPTA by weight carry out irradiation friendship
Connection reaction, is spray-dried at 115 DEG C after reaction 27h, i.e. obtains containing ultra-fine sulfuration polychlorostyrene second after being dried 8h
The ultra-fine sulfide powder polrvinyl chloride of alkene particle；
(3) take nitrile rubber thin slice bag roller, add graphene composite material prepared by 10 parts of steps (1), in roller temperature
It is refining 30min at 45 DEG C；It is subsequently adding dioctyl phthalate, dibutyl phthalate, stearic acid, prevents
Old agent RD, high abrasion furnace black and semi-reinforcing furnace black, in banburying chamber's banburying at 98 DEG C, set banbury rotating speed as 45
Rad/min, pressurize 18MPa, and the refining time is 1.5h；Then constant temperature plasticizing 4h at 156 DEG C, arranges at 160 DEG C
Masterbatch made by glue；
(4) in the masterbatch that step (3) obtains, 20 parts of ultra-fine sulfide powder polrvinyl chloride, accelerator TT are added
And accelerant CZ carries out banburying, setting banbury rotating speed as 25rad/min, pressurize 17MPa, and the refining time is 2.8h；
Then carry out plastifying, binder removal.
Embodiment 5:
The glue core material of the present embodiment includes following components by weight:
The preparation method of above-mentioned glue core material comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight 100 parts of graphene oxide powder are dispersed in 200 parts of oxolanes, treat oxygen
After functionalized graphene forms unformed suspension in oxolane, under stirring condition, in above-mentioned suspension, add 120
Part SEBS system mixture, hydrogenated styrene, butadiene and styrene three in this mixture
The weight ratio of person is 1:0.6:1.9；
Carrying out decompression distillation after reaction 2h, removing organic solvent and be also dried, obtain Graphene/hydrogenated styrene-butadiene-
Styrene compounds；
By Graphene/SEBS complex melt blending at 225 DEG C, carry out in-situ reducing anti-
Answer 60min, react complete and i.e. obtain graphene composite material；
(2) preparation of ultra-fine sulfide powder polrvinyl chloride:
In the emulsion of 100 parts of polrvinyl chloride, add 5 parts of cross-linking radiation auxiliary agent TMPTA by weight carry out irradiation friendship
Connection reaction, is spray-dried at 110 DEG C after reaction 28h, i.e. obtains containing ultra-fine sulfuration polychlorostyrene second after being dried 7h
The ultra-fine sulfide powder polrvinyl chloride of alkene particle；
(3) take nitrile rubber thin slice bag roller, add graphene composite material prepared by 15 parts of steps (1), in roller temperature
It is refining 25min at 40 DEG C；It is subsequently adding dioctyl phthalate, dibutyl phthalate, stearic acid, prevents
Old agent RD, high abrasion furnace black and semi-reinforcing furnace black, in banburying chamber's banburying at 98 DEG C, set banbury rotating speed as 45
Rad/min, pressurize 18MPa, and the refining time is 2h；Then constant temperature plasticizing 3h, binder removal at 160 DEG C at 157 DEG C
Make masterbatch；
(4) in the masterbatch that step (3) obtains, 40 parts of ultra-fine sulfide powder polrvinyl chloride, accelerator TT are added
And accelerant CZ carries out banburying, setting banbury rotating speed as 25rad/min, pressurize 17MPa, and the refining time is 2.6h；
Then carry out plastifying, binder removal.
Comparative example 1:
The glue core material of this comparative example includes following components by weight:
The preparation method of above-mentioned glue core material comprises the following steps:
(1) take nitrile rubber thin slice bag roller, at roller temperature is 40 DEG C, refines 25min；It is subsequently adding phthalic acid two
Monooctyl ester, dibutyl phthalate, stearic acid, anti-aging agent RD, high abrasion furnace black and semi-reinforcing furnace black, in banburying chamber
Banburying at 98 DEG C, sets banbury rotating speed as 45rad/min, and pressurize 18MPa, and the refining time is 2h；Then exist
Constant temperature plasticizing 3h at 157 DEG C, at 160 DEG C, binder removal makes masterbatch；
(2) in the masterbatch that step (1) obtains, add accelerator TT and accelerant CZ carries out banburying, set close
Refining machine rotating speed is 25rad/min, and pressurize 17MPa, and the refining time is 2.6h；Then carry out plastifying, binder removal.
Comparative example 2:
The glue core material of this comparative example includes following components by weight:
The preparation method of above-mentioned glue core material comprises the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight 100 parts of graphene oxide powder are dispersed in 200 parts of oxolanes, treat oxygen
After functionalized graphene forms unformed suspension in oxolane, under stirring condition, in above-mentioned suspension, add 120
Part SEBS system mixture, hydrogenated styrene, butadiene and styrene three in this mixture
The weight ratio of person is 1:0.6:1.9；
Carrying out decompression distillation after reaction 2h, removing organic solvent and be also dried, obtain Graphene/hydrogenated styrene-butadiene-
Styrene compounds；
By Graphene/SEBS complex melt blending at 225 DEG C, carry out in-situ reducing anti-
Answer 60min, react complete and i.e. obtain graphene composite material；
(2) take nitrile rubber thin slice bag roller, add graphene composite material prepared by 15 parts of steps (1), in roller temperature
It is refining 25min at 40 DEG C；It is subsequently adding dioctyl phthalate, dibutyl phthalate, stearic acid, prevents
Old agent RD, high abrasion furnace black and semi-reinforcing furnace black, in banburying chamber's banburying at 98 DEG C, set banbury rotating speed as 45
Rad/min, pressurize 18MPa, and the refining time is 2h；Then constant temperature plasticizing 3h, binder removal at 160 DEG C at 157 DEG C
Make masterbatch；
(3) in the masterbatch that step (2) obtains, add accelerator TT and accelerant CZ carries out banburying, set close
Refining machine rotating speed is 25rad/min, and pressurize 17MPa, and the refining time is 2.6h；Then carry out plastifying, binder removal.
Comparative example 3:
The glue core material of this comparative example includes following components by weight:
The preparation method of above-mentioned glue core material comprises the following steps:
(1) preparation of ultra-fine sulfide powder polrvinyl chloride:
In the emulsion of 100 parts of polrvinyl chloride, add 5 parts of cross-linking radiation auxiliary agent TMPTA by weight carry out irradiation friendship
Connection reaction, is spray-dried at 110 DEG C after reaction 28h, i.e. obtains containing ultra-fine sulfuration polychlorostyrene second after being dried 7h
The ultra-fine sulfide powder polrvinyl chloride of alkene particle；
(2) take nitrile rubber thin slice bag roller, at roller temperature is 40 DEG C, refines 25min；It is subsequently adding phthalic acid two
Monooctyl ester, dibutyl phthalate, stearic acid, anti-aging agent RD, high abrasion furnace black and semi-reinforcing furnace black, in banburying chamber
Banburying at 98 DEG C, sets banbury rotating speed as 45rad/min, and pressurize 18MPa, and the refining time is 2h；Then exist
Constant temperature plasticizing 3h at 157 DEG C, at 160 DEG C, binder removal makes masterbatch；
(3) in the masterbatch that step (2) obtains, 40 parts of ultra-fine sulfide powder polrvinyl chloride, accelerator TT are added
And accelerant CZ carries out banburying, setting banbury rotating speed as 25rad/min, pressurize 17MPa, and the refining time is 2.6h；
Then carry out plastifying, binder removal.
Glue core material prepared by the various embodiments described above and comparative example is carried out performance test, and test result is as shown in table 1.
Table 1
High abrasion furnace black and semi-reinforcing furnace black in the various embodiments described above are bought from Shandong Ao Na white carbon black company limited, aoxidize stone
Ink alkene is bought from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences, and stearic acid is bought and reached double roc limited public affairs of science and technology from Shandong gold
Department, accelerator TT, accelerant CZ and anti-aging agent RD are bought from Linhai City Xinhua of Zhejiang Province chemical plant.
Claims (5)
1. a brood lac core material, it is characterised in that include following components by weight:
Wherein, described graphene composite material is the Graphene/SEBS through in-situ reducing
Complex, this Graphene/SEBS complex is obtained by following methods: will under ultrasound condition
Graphene oxide powder disperses in organic solvent, and Graphene to be oxidized forms unformed suspension in organic solvent
After, under stirring condition, in above-mentioned suspension, add hydrogenated styrene, butadiene and styrene reaction, react complete
After organic solvent dry is distilled off through decompression；By described Graphene/SEBS
Complex completes in-situ reducing after melt blending 25min～60min at 220 DEG C～230 DEG C and obtains described Graphene
Composite；
Described ultra-fine sulfide powder polrvinyl chloride is obtained by following methods: add cross-linking radiation in the emulsion of polrvinyl chloride
Auxiliary agent TMPTA carries out cross-linking radiation reaction, carries out being spray-dried i.e. obtain containing ultra-fine sulfuration after reaction 20h～30h
The ultra-fine sulfide powder polrvinyl chloride of particulate polyvinyl chloride.
Glue core material the most according to claim 1, it is characterised in that: described Graphene/hydrogenated styrene-fourth two
In alkene-Styrene compounds, Graphene is 1:1～1.2 with the weight ratio of SEBS system；
In described SEBS system, the weight ratio of hydrogenated styrene, butadiene and styrene three is 1:
0.5～0.8:1.7～2.
Glue core material the most according to claim 2, it is characterised in that: in described nitrile rubber, acrylonitrile content is
The 41% of nitrile rubber weight.
Glue core material the most according to claim 1, it is characterised in that: the mean diameter of described graphene oxide is
25～50 μm, oxygen content is 30～40at.%, and interfloor distance is 0.74nm, and average specific surface area is 5～10m2/g。
5. the preparation method of glue core material described in a claim 3, it is characterised in that comprise the following steps:
(1) preparation of graphene composite material:
Under ultrasound condition, by weight 100 parts of graphene oxide powder are dispersed in 150～200 parts of organic solvents,
After Graphene to be oxidized forms unformed suspension in organic solvent, add in above-mentioned suspension under stirring condition
100 parts～120 parts of SEBS system mixture, hydrogenated styrene, fourth two in this mixture
The weight ratio of alkene and styrene three is 1:0.5～0.8:1.7～2；
Carrying out decompression distillation after reaction 1.5h～2h, removing organic solvent and be also dried, obtain Graphene/hydrogenated styrene-
Butadiene-styrene complex；
By described Graphene/SEBS complex melt blending at 220 DEG C～230 DEG C,
Carry out in-situ reducing reaction 25min～60min, react complete and i.e. obtain described graphene composite material；
(2) preparation of ultra-fine sulfide powder polrvinyl chloride:
In the emulsion of 100 parts of polrvinyl chloride, add 5～6 parts of cross-linking radiation auxiliary agent TMPTA by weight carry out irradiation
Cross-linking reaction, is spray-dried at 100～120 DEG C after reaction 20h～30h, is i.e. contained after being dried 5～8h
There is the ultra-fine sulfide powder polrvinyl chloride of ultra-fine vulcanized polyvinyl chloride particle；
(3) take 80～120 parts of nitrile rubber thin slice bag rollers, add Graphene prepared by 10～30 parts of steps (1) multiple
Condensation material, refines 10～30min at roller temperature is 30～45 DEG C；Be subsequently adding 1.2～2 parts of dioctyl phthalates,
1～1.8 part of dibutyl phthalate, 0.8～1.5 part of stearic acid, 1～3 part of anti-aging agent RD, 15～20 parts of high abrasions
Furnace black and 20～30 parts of semi-reinforcing furnace black, in banburying chamber's banburying at 95～100 DEG C, set banbury rotating speed as 45
Rad/min, pressurize 18MPa, and the refining time is 1.5～3.5h；Then constant temperature plasticizing 2～4h at 155～160 DEG C,
At 150～160 DEG C, binder removal makes masterbatch；
(4) add in the masterbatch that step (3) obtains 20～40 parts of ultra-fine sulfide powder polrvinyl chloride, 1～4 part
Accelerator TT and 0.5～3 part of accelerant CZ carry out banburying, set banbury rotating speed as 25rad/min, and pressurize 17MPa,
The refining time is 2～3.5h；Then carry out plastifying, binder removal.
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| CN1415657A (en) * | 2002-11-12 | 2003-05-07 | 上海氯碱化工股份有限公司 | Radiation crosslinking polyvinyl chloride material and its prepn. method |
| CN103509212A (en) * | 2013-05-13 | 2014-01-15 | 河北博路天宝石油设备制造有限公司 | Nitrile rubber composite capable of improving mechanical property |
| CN104194108A (en) * | 2014-08-11 | 2014-12-10 | 广州加士特密封技术有限公司 | Hydrogenated butadiene-acrylonitrile rubber vulcanized rubber with high strength, high pressure resistance and hydrogen sulfide corrosion resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1415657A (en) * | 2002-11-12 | 2003-05-07 | 上海氯碱化工股份有限公司 | Radiation crosslinking polyvinyl chloride material and its prepn. method |
| CN103509212A (en) * | 2013-05-13 | 2014-01-15 | 河北博路天宝石油设备制造有限公司 | Nitrile rubber composite capable of improving mechanical property |
| CN104194108A (en) * | 2014-08-11 | 2014-12-10 | 广州加士特密封技术有限公司 | Hydrogenated butadiene-acrylonitrile rubber vulcanized rubber with high strength, high pressure resistance and hydrogen sulfide corrosion resistance |
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