CN101602867B - Modified chloroprene rubber V band and method for preparing same - Google Patents
Modified chloroprene rubber V band and method for preparing same Download PDFInfo
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- CN101602867B CN101602867B CN2009101005336A CN200910100533A CN101602867B CN 101602867 B CN101602867 B CN 101602867B CN 2009101005336 A CN2009101005336 A CN 2009101005336A CN 200910100533 A CN200910100533 A CN 200910100533A CN 101602867 B CN101602867 B CN 101602867B
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- 229920001084 poly(chloroprene) Polymers 0.000 title claims abstract description 58
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical class ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title abstract description 22
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- 239000005060 rubber Substances 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 35
- -1 chemical engineering Substances 0.000 claims abstract description 21
- 239000006229 carbon black Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 26
- 239000000654 additive Substances 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 24
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- 238000002360 preparation method Methods 0.000 claims description 18
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 3
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 33
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- 238000012986 modification Methods 0.000 abstract description 9
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- 229910001392 phosphorus oxide Inorganic materials 0.000 abstract 1
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- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
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- 238000001816 cooling Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
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- 239000011787 zinc oxide Substances 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- IHLDEDLAZNFOJB-UHFFFAOYSA-N 6-octoxy-6-oxohexanoic acid Chemical compound CCCCCCCCOC(=O)CCCCC(O)=O IHLDEDLAZNFOJB-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a modified chloroprene rubber V band and a method for preparing the same. The rubber matrix of the modified chloroprene rubber V band is prepared by mixing the following raw materials in portion by weight: 100 portions of chloroprene rubber, 20 to 50 portions of acid modification carbon nano-tube, 10 to 20 portions of carbon black, 2 to 10 portions of phosphorus oxide, 12 to 18 portions of sulfur, 0.3 to 5 portions of anti-aging agent, 1 to 5 portions of filler, 3 to 7 portions of softener, 2 to 10 portions of plasticizer, and 1 to 6 portions of promoter. The modified chloroprene rubber V band has good properties of heat resistance, oil corrosion resistance, static resistance and fire retardation, and can be widely applied to mechanical transmission systems under special operation environments in the industries such as coal mines, petroleum, chemical engineering, paper making and the like.
Description
Technical field
The present invention relates to rubber-like V band manufacture field, be specifically related to a kind of carbon nanotube composite additive modified chloroprene rubber V band and preparation method thereof.
Background technology
Existing V-shaped rubber belt is owing to mainly adopt rubber to make, in use be easy to generate static, can adsorb dust behind the electrostatic accumulation, skidding of aggravation V-shaped rubber belt, cause the static discharge phenomenon, be not suitable for being used for a particular job occasion that electrostatic accumulation easily causes discharge, and general transmission classical V-belt, main rubber adopts natural rubber and since the molecular structure of natural rubber be polyisoprene (--CH
2-C=CHCH
2(CH
3)-)
n, have in the molecular structure-CH
3And the effect of α-H, make-C=CH-double bond structure bond energy is low, and thermo-labile not oil resistant therefore based on the classical V-belt of natural rubber, only is applicable to that normal temperature below 70 ℃ uses, and has significant limitation.Therefore, people begin to seek V-shaped rubber belt are carried out modification to optimize its performance, enlarge its use range.At present, people generally adopt carbon black, nano material (as nano zine oxide, nano-calcium carbonate, carbon nanotube) etc. that V-shaped rubber belt is carried out modification, though obtained certain achievement, but still have weak point.
The classical V-belt of domestic production generally adopts spreader frictioning technology, and promptly canvas utilizes each roller linear differential of rolling press by rolling press, makes 70～90 ℃ rubber unvulcanizate, clips on the canvas.Because rubber is wiped on the canvas surface, can not immerse the canvas internal layer.So a little less than the bonding force of rubber and V ribbon matrix, the easy and matrix canvas disengaging of V belt surface rubber if come off, also can cause antistatic rubber not contact with the metal belt wheel, the static of accumulation can not obtain discharging, and has slackened the antistatic property of V band.
In order to improve the performance of rubber V, prior art has been done various improvement to base rubber (rubber and various auxiliary agent is mixing make), for example:
Application number is to disclose a kind of carbon nano-tube modification hydrogenated nitrile-butadiene rubber and preparation method thereof in 200310111660.9 the Chinese patent, by the carbon nanotube after the surface treatment and a kind of fluid rubber are mixed by ultrasonic wave, add then in the partial hydrogenation paracril and make master batch, in master batch, add remaining hydrogenated nitrile-butadiene rubber, carbon black, zinc oxide, vulcanizing agent, with mill or Banbury mixer said mixture is processed, obtain hydrogenated nitrile-butadiene rubber rubber unvulcanizate with carbon nano-tube modification, by sulfuration processing, obtain modified hydrogenated paracril.
Application number is to disclose a kind of nano material modified rubber V strip in 200610052468.0 the Chinese patent application, comprise rubber matrix, vulcanizing agent, promotor, stearic acid, anti-aging agent, tenderizer and carbon black, further comprise nano zine oxide and nano-calcium carbonate.
Application number is to disclose a kind of chloroprene rubber composition that is used for ultra low temperature sealing arrangement in 200810227576.6 the Chinese patent application, comprises chloroprene rubber, carbon black, ZnO and promotor, mixes that to place rubber mixing machine to carry out mixing.This chloroprene rubber composition have good process industrial art performance, with the heat bonding performance of metal; Have good media compatibility and reliable sealing performance under-196 ℃ of condition of ultralow temperature, withstand voltage scope has reached-0.1～35MPA.
But prior art is especially unsatisfactory at the improvement in performance effect of heat-resisting, oil resistant, static resistance to the improvement in performance of base rubber.
Summary of the invention
The invention provides a kind of carbon nanotube composite additive modified chloroprene rubber V band and preparation method thereof, employing comprises the composite additive of modified carbon nano-tube, carbon black and phosphorus series compound, the body material chloroprene rubber of V-shaped rubber belt is implemented the composite modified base rubber that obtains, and the V band enhancing made from this base rubber, heat-resisting, antistatic and flame retardant properties improve greatly.
A kind of modified chloroprene rubber V band, its base rubber is made through mixing by the raw material of following weight part:
100 parts of chloroprene rubbers, 20～50 parts of sour modified carbon nano-tubes, 10～20 parts of carbon blacks, 2～10 parts of phosphorus are oxide compound, 12～18 parts of sulphur, 0.3～5 part of anti-aging agent, 1～5 part of filler, 3～7 parts of tenderizers, 2～10 parts of softening agent and 1～6 part of promotor.
Described sour modified carbon nano-tube can be selected in the prior art carbon nanotube through hydrochloric acid, Nitric Acid Modified for use.
Because carbon nanotube has very high surface free energy, is in the thermodynamic instability state, easily reunite, as shown in Figure 1, the difficult dispersion, make its application in matrix material be subjected to certain restriction.Given this, need carbon nanotube is carried out processing such as surface modification and modification,, eliminate the enrichment region of carbon nanotube in the complex body, promote the over-all properties of complex body to improve the dispersiveness of carbon nanotube in rubber matrix.
The method that carbon nanotube is carried out modification can be selected the ordinary method of this area for use, such as: carbon nanotube with nitric acid circumfluence method purification process, is equipped with ultrasonic concussion.
Dense HNO
3Carbon nanotube there is strong oxidation erosion, can carry out graft modification to carbon nanotube, make its surface produce a large amount of oxygen-containing functional groups, obtain carrying the carbon nanotube of oxygen-containing functional group, as shown in Figure 2, these a large amount of oxygen-containing functional groups not only can reduce the activation energy of carbon nanotube, help the dispersion of carbon nanotube in the chloroprene rubber matrix, and help the absorption of carbon nanotube to other component in the composite additive.
With the main ingredient of functionalized carbon nanotube (promptly carrying the carbon nanotube of oxygen-containing functional group) as additive, produce composite additive, be because in matrices of composite material, functionalized carbon nanotube can be carried other binder component particle (carbon black and phosphorus are oxide compound), formation is the compound system of " skeleton " with carbon nanotube, as shown in Figure 3.
Described carbon black preferably is 5%～20% salt acid soak (soak at room temperature through mass percentage concentration, soak time does not have strict restriction) handle after, the carbon black that obtains in 10～60 ℃ of vacuum-dryings, this treated carbon blacksurface is fully activated, can be more stable attached to carbon nano tube surface, also make the finished product thermotolerance and ageing-resistant performance improve a lot.
Because functionalized carbon nanotube is dissolved in acid solvent, can adopt the wet method of this area routine or dry method to carry out compound to additive.
Described phosphorus is that oxide compound can be selected one or both in phosphorus trioxide, the Vanadium Pentoxide in FLAKES for use.
Described anti-aging agent can be selected this area anti-aging agent commonly used for use, and ' one or more in a pair of (2.2-dimethyl benzyl) pentanoic, sulfuration dipropionate, the phosphorous acid ester etc. can be selected suitable anti-aging agent as required for use as 4.4.
Described filler can be selected this area filler commonly used for use, as in potter's clay, lime carbonate, the mineral filler etc. one or more, can select suitable filler as required for use.
Described tenderizer can be selected this area tenderizer commonly used for use, as in stearic acid, the silicone oil etc. one or more, and preferred stearic acid.
Described softening agent can be selected this area softening agent commonly used for use, as in dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), Octyl adipate (DOA), the nylon acid diisobutyl ester (DIBA) one or more, pref-erable dioctyl phthalate.
Described promotor can be selected this area Thiourea accelerator commonly used for use, as N, and N '-diethyl thiourea, N, one or more in N '-di-n-butyl thiocarbamide etc.
The present invention also provides the preparation method of the base rubber of described modified chloroprene rubber V band, comprises the steps:
(1) is that oxide compound is compound with sour modified carbon nano-tube, carbon black and phosphorus, makes composite additive;
(2) chloroprene rubber is plasticated back is mixing with composite additive, sulphur, anti-aging agent, filler, tenderizer, softening agent and promotor, obtains base rubber.
Describedly plasticate, the mixing method that adopts this area routine, preferably adopt low temperature, pony roll apart from, lower volume thin-pass method.
Adopt existing technology, with base rubber and infantees and/or the compound modified chloroprene rubber V band that can be made into all size of fortifying fibre.
The temperature control of preferred twin-roll plastic mixing mill roller is at 45～55 ℃ when plasticating, 10～12 ℃ of the front and back roller temperature difference, and roll spacing 0.8～1.2mm, speed ratio 1: 1.27, time remaining 10～15min plasticates.Can more effectively obtain certain plasticity number like this, also can select certain hop count to plasticate, to guarantee the requirement of following process operation and product performance according to actual requirement.Chloroprene rubber after plasticating is left standstill in air, can carry out mixing after the cooling.
The temperature control of preferred twin-roll plastic mixing mill roller is at 40～50 ℃ when mixing, and mixing time is 10～20min.
Can at first add fine size, difficult dispersive sulphur and composite additive when mixing, be uniformly dispersed in a long time, add anti-aging agent, filler, tenderizer, softening agent and promotor more successively to guarantee it.When amount of filler more for a long time, softening agent and tenderizer can alternately add, thin-pass repeatedly makes each component be uniformly dispersed.
General base rubber is at first compound with infantees and/or fortifying fibre, can adopt the method for compressing tablet for example to adopt general spreader frictioning method to get final product, the spreader frictioning method is that canvas passes through rolling press, utilizes each roller linear differential of rolling press, make 70～90 ℃ rubber unvulcanizate, clip on the canvas.This method is owing to directly wipe rubber on the canvas surface, can not immerse the canvas internal layer, the bonding force of rubber and V ribbon matrix canvas a little less than, easy and the matrix canvas disengaging of V belt surface rubber, if come off, can cause antistatic rubber not contact with the metal belt wheel well, the static of accumulation can not be discharged well, has slackened the antistatic property of V band.
Therefore, compressing tablet among the preparation method of the present invention preferably adopts the impregnation pressed disc method, the impregnation pressed disc method is about to canvas by vertical cement dipping machine, by canvas being carried out impregnation, oven dry, impregnation, drying course more repeatedly, rubber master batches (being the rubber unvulcanizate that obtains after mixing) is immersed in the intrinsic fiber of canvas, with canvas matrix mortise together, thereby canvas and rubber are combined closely in the assurance V band, after even rubber topping comes off, can guarantee that still there is conductive channel in canvas, the static that accumulates in the use can leak to the earth by hardware.
Infantees can adopt prior art to coat as required.
Base rubber is auxilliary generally need be vulcanized after compound with infantees and/or fortifying fibre, and described sulfuration can be adopted the method for this area routine, preferably rubber unvulcanizate is added die cavity, utilizes the vulcanizing press sulfidization molding.For making rubber item obtain optimum performance, preferred curing temperature is 130～170 ℃, and pressure is 10～15Mpa, and curing time is the plateau cure condition of 30～40min.
The present invention has following beneficial effect:
The base rubber of V band of the present invention adopts and comprises that sour modified carbon nano-tube, carbon black and phosphorus are the composite additive of oxide compound, body material chloroprene rubber to V-shaped rubber belt is implemented composite modified, make the rubber of composite sulfuration have intrinsic " skeleton " structure, thereby has an intensity height, can be applicable to 150 ℃～180 ℃ high-temperature work environments, has good heat endurance, and the antistatic and flame-retarding characteristic of oil resistant burn into has also had significantly and has improved, and can be widely used in the industries such as colliery, oil, chemical industry and papermaking in the machine driven system under the special operation environment.
In addition, because the electrostatic energy that produces during this modified chloroprene rubber V band transmission effectively leaks, so V band itself can be as ignition source, and in case catch fire, the V band has from fiery self-extinguishing energy, can effectively reduce the harm of fire.Even the modified chloroprene rubber V band that adopts the common preparation method in this area to prepare also can be fit to different working conditions, be particularly useful for high temperature, high-risk occasion.
Description of drawings
Fig. 1 is the electron microscope photo scanning of carbon nanotube closely of reuniting;
Fig. 2 is the electron microscope photo scanning that carries the carbon nanotube of oxygen-containing functional group;
Fig. 3 is the electron microscope photo scanning of composite additive of the present invention.
Embodiment
Embodiment 1
With the carbon nanotube mass percentage concentration is 98% nitric acid backflow purification process, and is equipped with ultrasonic concussion, makes the Nitric Acid Modified carbon nanotube.
Get above-mentioned 20 weight part Nitric Acid Modified carbon nanotubes, 10 weight parts and be after 5% the hydrochloric acid immersion treatment again the carbon black that obtains 10 ℃ of vacuum-dryings and 2 weight part phosphorus trioxides through the compound composite additive that makes of wet method through mass percentage concentration.
100 weight part chloroprene rubbers are placed twin-roll plastic mixing mill, the roller temperature is 45 ℃, the front and back roller temperature difference is 10 ℃, roll spacing 1mm, front and back roller speed ratio 1: 1.27, plasticate and in air, leave standstill behind the 10min, the cooling back adds 15 weight part sulphur and above-mentioned composite additive, in the roller temperature is mixing in advance several minutes in 40 ℃ the twin-roll plastic mixing mill, add 0.3 weight part 4 again, 4 '-two (2.2-dimethyl benzyl) pentanoic, 3 weight part light calcium carbonates, 3 weight part stearic acid, 5 weight part DOP and 1 weight part N, the mixing 15min of N '-diethyl thiourea obtains base rubber, utilizes this base rubber to make the Type B modified chloroprene rubber V band again.
Embodiment 2
With the carbon nanotube mass percentage concentration is 98% nitric acid backflow purification process, and is equipped with ultrasonic concussion, makes the Nitric Acid Modified carbon nanotube.
Get above-mentioned 50 weight part Nitric Acid Modified carbon nanotubes, 10 weight parts and be after 20% the hydrochloric acid immersion treatment again the carbon black that obtains 20 ℃ of vacuum-dryings and 5 weight part phosphorus trioxides through the compound composite additive that makes of wet method through mass percentage concentration.
100 weight part chloroprene rubbers are placed twin-roll plastic mixing mill, the roller temperature is 50 ℃, the front and back roller temperature difference is 11 ℃, roll spacing 0.9mm, front and back roller speed ratio 1: 1.27, plasticate and in air, leave standstill behind the 15min, the cooling back adds 12 weight part sulphur and above-mentioned composite additive, in the roller temperature is mixing in advance several minutes in 50 ℃ the twin-roll plastic mixing mill, add 1 weight part 4 again, 4 '-two (2.2-dimethyl benzyl) pentanoic, 5 weight part light calcium carbonates, 5 weight part stearic acid, 2 weight part DOP and 3 weight part N, the mixing 15min of N '-diethyl thiourea obtains base rubber, utilizes this base rubber to make Type B modified chloroprene rubber V band and SPB type modified chloroprene rubber V band respectively.
Embodiment 3
With the carbon nanotube mass percentage concentration is 98% nitric acid backflow purification process, and is equipped with ultrasonic concussion, makes the Nitric Acid Modified carbon nanotube.
Getting above-mentioned 35 weight part Nitric Acid Modified carbon nanotubes, 20 weight parts is that 15% hydrochloric acid bubbles the carbon black that obtains 55 ℃ of vacuum-dryings again after handling and 2 weight part Vanadium Pentoxide in FLAKESs through the compound composite additive that makes of dry method through mass percentage concentration.
100 weight part chloroprene rubbers are placed twin-roll plastic mixing mill, the roller temperature is 55 ℃, the front and back roller temperature difference is 12 ℃, roll spacing 1.2mm, front and back roller speed ratio 1: 1.27, plasticate and in air, leave standstill behind the 15min, the cooling back adds 18 weight part sulphur and above-mentioned composite additive, in the roller temperature is mixing in advance several minutes in 50 ℃ the twin-roll plastic mixing mill, add 2 weight parts sulfuration dipropionate again, 3 weight part talcum powder, 7 weight part stearic acid, 5 weight part DOP and 1 weight part N, N '-mixing 15min of di-n-butyl thiocarbamide obtains base rubber, utilizes this base rubber to make A type modified chloroprene rubber V band respectively, the Type B modified chloroprene rubber V band, C type modified chloroprene rubber V band, SPA type modified chloroprene rubber V band and SPB type modified chloroprene rubber V band.
Embodiment 4
With the carbon nanotube mass percentage concentration is 98% hydrochloric acid reflux purification process, and is equipped with ultrasonic concussion, makes the hydrochloric acid modified carbon nano-tube.
Get above-mentioned 40 weight part hydrochloric acid modified carbon nano-tubes, 16 weight parts and be the carbon black that obtains 45 ℃ of vacuum-dryings again after 10% the hydrochloric acid immersion treatment, 10 weight part Vanadium Pentoxide in FLAKESs through the compound composite additive that makes of dry method through mass percentage concentration.
100 weight part chloroprene rubbers are placed twin-roll plastic mixing mill, the roller temperature is 45 ℃, the front and back roller temperature difference is 10 ℃, roll spacing 1mm, front and back roller speed ratio 1: 1.27, plasticate and in air, leave standstill behind the 10min, the cooling back adds 11 weight part sulphur and above-mentioned composite additive, in the roller temperature is mixing in advance several minutes in 40 ℃ the twin-roll plastic mixing mill, add 4 weight part phosphorous acid esters, 3 weight part potter's clay, 4 weight part stearic acid, 7 weight part DOP and 6 weight part N again, N '-mixing 15min of di-n-butyl thiocarbamide obtains base rubber, utilizes this base rubber to make the Type B modified chloroprene rubber V band.
Embodiment 5
With the carbon nanotube mass percentage concentration is 98% hydrochloric acid reflux purification process, and is equipped with ultrasonic concussion, makes the hydrochloric acid modified carbon nano-tube.
Get above-mentioned 30 weight part hydrochloric acid modified carbon nano-tubes, 18 weight parts and be after 15% the hydrochloric acid immersion treatment again the carbon black that obtains 25 ℃ of vacuum-dryings and 8 weight part Vanadium Pentoxide in FLAKESs through the compound composite additive that makes of wet method through mass percentage concentration.
100 weight part chloroprene rubbers are placed twin-roll plastic mixing mill, the roller temperature is 50 ℃, the front and back roller temperature difference is 10 ℃, roll spacing 1mm, front and back roller speed ratio 1: 1.27, plasticate and in air, leave standstill behind the 15min, the cooling back adds 15 weight part sulphur and above-mentioned composite additive, in the roller temperature is mixing in advance several minutes in 40 ℃ the twin-roll plastic mixing mill, add 0.5 weight part 4 again, 4 '-two (2.2-dimethyl benzyl) pentanoic, 1.5 weight part light calcium carbonate, 6 weight part stearic acid, 6 weight part DOP and 5 weight part N, the mixing 15min of N '-diethyl thiourea obtains base rubber, utilizes this base rubber to make the Type B modified chloroprene rubber V band.
Over-all properties detects
Type B modified chloroprene rubber V band to embodiment 1～5 preparation carries out performance test, test result such as table 1 respectively:
The performance of table 1 modified chloroprene rubber V band
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Shore hardness, Hs | 78 | 75 | 68 | 72 | 62 |
| Young's modulus, MPa | 7 | 4.4 | 4.4 | 3.8 | 4.4 |
| 300% stress at definite elongation, MPa | 10.5 | 12.4 | 10.4 | 9.8 | 7.5 |
| Tensile strength, MPa | 13.6 | 16.4 | 19.4 | 10.6 | 18.3 |
| Elongation at break, % | 200 | 404 | 470 | 311 | 534 |
| Tear strength, KN/m | 43.6 | 60.5 | 78.4 | 35.7 | 74.0 |
| Abrasion, Km/cm 3 | 0.049 | 0.110 | 0.112 | 0.118 | 0.137 |
| Volume specific resistance, Ω cm | 6.21×10 1 | 9.34×10 1 | 1.91×10 3 | 1.92×10 2 | 2.48×10 5 |
| The flame after flame time is arranged, s | 2 | 1 | 2 | 1 | 1 |
From The above results as can be seen, the over-all properties of the Type B modified chloroprene rubber V band of embodiment 3 preparations is better than the Type B modified chloroprene rubber V band of other embodiment preparation.
Physical and mechanical property detects
The modified chloroprene rubber V band of the various models of embodiment 3 preparations is carried out the physical and mechanical property detection, test result such as table 2:
Table 2
Antistatic property detects
With the modified chloroprene rubber V band of the various models of embodiment 2 preparation and the modified chloroprene rubber V band of the various models of embodiment 3 preparations is carried out antistatic property with the ISO1813 standard detect test result such as table 3:
Table 3
Flame retardant properties detects
After tested, all modified chloroprene rubber V band nonflame after flame times of embodiment 1～5 preparation are all near 0 second, and the nonflame after flame time is all less than 2 seconds.
Resistance toheat detects
Respectively all modified chloroprene rubber V bands of embodiment 1～5 preparation were placed under 120 ± 1 ℃ the temperature long run test 70 hours, at room temperature cooled off then 2 hours, with all modified chloroprene rubber V bands of cooled embodiment 1～5 preparation are pressed band on master bar normal bending direction bending, slight crack does not all appear in the V band.
Thermogravimetric analysis
All modified chloroprene rubber V bands of embodiment 3 preparations are carried out thermogravimetric analysis, and temperature of initial decomposition is 312 ℃, and maximum weightless temperature is 383 ℃, and stopping weightless temperature is 447 ℃.
Claims (7)
1. modified chloroprene rubber V band, it is characterized in that: its base rubber is made through mixing by the raw material of following weight part:
100 parts of chloroprene rubbers, 20～50 parts of sour modified carbon nano-tubes, 10～20 parts of carbon blacks, 2～10 parts of phosphorus are oxide compound, 12～18 parts of sulphur, 0.3～5 part of anti-aging agent, 1～5 part of filler, 3～7 parts of tenderizers, 2～10 parts of softening agent and 1～6 part of promotor;
The preparation method of the base rubber of described modified chloroprene rubber V band, comprise: with sour modified carbon nano-tube, carbon black and phosphorus is that oxide compound is compound, make composite additive, chloroprene rubber is plasticated the back with composite additive, sulphur, anti-aging agent, filler, tenderizer, softening agent with promotor is mixing makes.
2. modified chloroprene rubber V band as claimed in claim 1 is characterized in that: described phosphorus is that oxide compound is selected one or both in phosphorus trioxide, the Vanadium Pentoxide in FLAKES for use.
3. modified chloroprene rubber V band as claimed in claim 1 is characterized in that: described anti-aging agent selects 4 for use, one or both in 4 '-two (2, the 2-dimethyl benzyl) pentanoic, the phosphorous acid ester.
4. modified chloroprene rubber V band as claimed in claim 1 is characterized in that: described filler is selected one or both in potter's clay, the lime carbonate for use.
5. modified chloroprene rubber V band as claimed in claim 1 is characterized in that: described tenderizer is a stearic acid.
6. modified chloroprene rubber V band as claimed in claim 1 is characterized in that: described softening agent is a dioctyl phthalate (DOP).
7. modified chloroprene rubber V band as claimed in claim 1 is characterized in that: described promotor is selected N for use, N '-diethyl thiourea, N, one or both in N '-di-n-butyl thiocarbamide.
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| CN102408596A (en) * | 2011-09-13 | 2012-04-11 | 安徽盛运橡胶有限责任公司 | Acid and alkali resistant rubber coating layer of conveyor roller and preparation method thereof |
| CA2925929C (en) * | 2013-12-19 | 2018-12-04 | Soucy Techno Inc. | Rubber compositions and uses thereof |
| CN104072827B (en) * | 2014-06-27 | 2016-04-27 | 青岛大学 | A kind of oil-filled carbon nano-tube solution of filling is total to beta-rubber and preparation method thereof |
| CN104829894A (en) * | 2015-05-08 | 2015-08-12 | 尉氏县久龙橡塑有限公司 | Flame-retardant antistatic V-belt primer and preparation method thereof |
| CN104829895A (en) * | 2015-05-08 | 2015-08-12 | 尉氏县久龙橡塑有限公司 | Flame-retardant antistatic V-belt coating glue and preparation method thereof |
| CN105949552B (en) * | 2016-06-22 | 2018-05-15 | 张家港大塚化学有限公司 | Rubber and conveyer belt |
| CN106864614A (en) * | 2017-03-14 | 2017-06-20 | 上海帆煜自动化科技有限公司 | A kind of crawler belt of robot with anti-static function |
| CN115260618B (en) * | 2022-08-31 | 2023-10-20 | 三维控股集团股份有限公司 | Graphene modified chloroprene rubber and high-performance rubber V belt prepared from same |
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