CN101613495A - The rubber combination that contains CNT (carbon nano-tube) - Google Patents
The rubber combination that contains CNT (carbon nano-tube) Download PDFInfo
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- CN101613495A CN101613495A CN200910150258A CN200910150258A CN101613495A CN 101613495 A CN101613495 A CN 101613495A CN 200910150258 A CN200910150258 A CN 200910150258A CN 200910150258 A CN200910150258 A CN 200910150258A CN 101613495 A CN101613495 A CN 101613495A
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Abstract
The invention provides the curable composition that comprises a kind of special hydrogenated nitrile-butadiene rubber, at least a linking agent and CNT (carbon nano-tube), the purposes that is used to prepare a kind of method of this kind composition and is used to prepare the curing rubber goods.Described curing rubber goods demonstrate excellent thermal characteristics, oil-proofness and physical strength.
Description
Technical field
The present invention relates to comprise a kind of curable composition of specific hydrogenated nitrile-butadiene rubber, a kind of linking agent and CNT (carbon nano-tube), be used to prepare a kind of method of this based composition, solidification treatment and uses thereof.
Background technology
In principle, have been found that the widespread use of elastomerics in extensive application.Further say, can obtain many specialty elastomers, they have can be for machinery widely, character chemistry and physics of domination.Paracril (NBR) and its hydrogenated products, promptly hydrogenated nitrile-butadiene rubber also is abbreviated as " HNBR ", represents this type of specialty elastomer.HNBR has the ozone and the chemical resistance of very good thermotolerance, excellence and also has excellent oil-proofness specifically.HNBR is used for sealing member, flexible pipe, belt and the clamping element of (for example) automotive field, also be used for stator, oil well sealing member and the valve sealing element in oily extraction field, and be used for many parts of aircraft industry, electronic industry, mechanical engineering and shipbuilding.
Yet along with the development of technology, modern industry becomes strict more to the requirement of the annex (functional rubbery accessory) of functional rubber.Necessary is to seek to make the performance of the new curable compound of specialty elastomer and additive bonded with the improvement elastomer material.Since having found CNT (carbon nano-tube) (CNT), because machinery, electricity and the thermal properties of its excellence, they have just attracted many investigators' attention.Can improve the mechanical property of matrix effectively as the CNT that is incorporated into elastomeric reinforcing filler.
CNT (carbon nano-tube) can be thought the soccerballene (Nature, 1985, Vol.318,162) that extends.Be similar to soccerballene, CNT (carbon nano-tube) is by hexagon, only make with pentagon endways.On the structure, the shape of a CNT can be imagined into a mono-layer graphite sheet and be rolled into and have terminal seamless lid, have 1000 or the tubule of the form of higher very high length-to-diameter ratio simultaneously.Although the density of these CNT is low, they still are considered to cause high-intensity a kind of zero defect structure as one molecule.
Two kinds of basic forms are arranged concerning CNT (carbon nano-tube),, be called single-walled nanotube (SWNT), and be called many walls nanotube (MWNT) by those nanotubes that some concentric lamellas are made from a kind of single graphite flake layer production those.SWNT is by about some relevant summaries of this theme and produced sizable interest in academia, these summaries comprise following everybody done those, as Bahr ﹠amp; Tour (J.Mater.Chem., 2002,12,1952), Hirsch (Angewandte Chemie-International Edition, 2002,41,1853), Colbert (Plastics Additives ﹠amp; Compounding, January/February2003,18) and Baughman ﹠amp; Heer (Science, 2002,297,787).
Before two more than ten years, found since the CNT (carbon nano-tube), the multiple technology of having developed that is used to produce them occurred.Iijima (Nature, 1991,354,56) at first observes many walls nanotube.After several years, people (Nature, 1993,363,605) such as people such as Iijima and Bethune have reported the synthetic of single-walled nanotube independently.The main synthetic method that is used for list and multiple-wall carbon nanotube comprises arc-over (Nature, 1997,388,756), laser ablation (Applied Physics A:Materials Science ﹠amp; Processing, 1998,67,29), gas phase catalysis growth (the Chemical Physics Letters that begins from carbon monoxide, 1999,313,91) and chemical vapor deposition (CVD) (the AppliedPhysics Letters that begins from hydro carbons, 1999,75,1086; Science, 1998,282,1105).Need purification step to separate these pipes subsequently.These gas phase process are tending towards producing the nanotube with impurity still less and are easier to extensive the processing.Up to now, though do not have low cost, large-scale production method, traditional method further developed and novel method for example fluidized-bed reactor be studied to produce a kind of CNT supply stable, moderate price.Low CNT availability and its high price have limited polymkeric substance-CNT matrix material and have been used for the realization of many practical applications.
The hydrogenated carboxylated nitrile rubber (also being abbreviated as " HXNBR ") of the selection hydrogenation preparing by carboxyl nitrile-conjugated diene rubber (also being abbreviated as " XNBR ", is a kind of multipolymer that comprises the repeating unit of at least a conjugated diolefine, at least a unsaturated nitrile, at least a carboxylated monomer and comonomer that can be randomly other) is the specialty elastomer with very good thermotolerance, excellent ozone and chemical resistance and excellent oil-proofness.Together with the high-caliber mechanical property (particularly high abrasion resistance) of this rubber therefore find XNBR and HXNBR except that other field, also in automobile (sealing member, flexible pipe, supporting pad), oil (stator, well head sealing member, valve block), electric power (cable sheath), mechanical engineering (tire, roller) and shipbuilding (conduit seals, joint), obtained using widely just not at all surprising.
The method that is used for preparing the HXNBR polymkeric substance has been described in WO-A-2001/077185, simultaneously some other patent applications that with regard to the HXNBR polymkeric substance, relate to the different composite technology have been submitted to, for example as WO-A-2005/080493 and WO-A-2005/080492.
CNT (carbon nano-tube) is considered to " limit " fiber sometimes, has different and significant application.One that does not inquire in detail as yet is the problem of these pipes being mixed elastomer material.So far, solvent, melt-mixing and spray-drying process are prepared some rubber/CNT matrix material as treatment process.Rubber matrix in research at present comprises natural rubber (NR), styrene butadiene rubbers (SBR), neoprene, silicon rubber, fluothane elastomerics (FKM) and hydrogenated acrylonitrile rubber (HNBR).
At Composites Science ﹠amp; Technology in 2003,63,1647, has studied the sample machinery Effect on Performance to obtaining when carbon nano-particle is used for the silicone base elastomerics.Use Single Walled Carbon Nanotube or more the nanometer fibril of volume carbon caused raising as the initial modulus of the resulting sample of a function of weighting agent load, yet, be attended by final performance decrease.
For many kinds of polymkeric substance for example siloxanes, synthetic polyisoprene, paracril, fluoropolymer (FKM) and hydrogenated nitrile-butadiene rubber (HNBR), inquired into CNT (carbon nano-tube) has been mixed in the polymeric matrix.
At Journal of Material Science, 2006,41, p.2541 in, MWNT has been described to the curing of HNBR and the influence of mechanical property.Two kinds of methods are used to prepare nano composite material.In first method, at 50 ℃ CNT and a kind of solidifying agent directly are mixed into 10min among the HNBR in twin-screw extruder, and then corresponding compounds are passed through hot-press solidifying T90 at 170 ℃.Second method comprises the liquid HNBR of low molecule (LHNBR) at first is dissolved in the acetone, subsequently, the CNT of surface modification added this solution, and then this mixture is carried out ultrasonic dispersing.Remove acetone by vacuum-drying from this mixture, obtained to have the compound that is pre-dispersed in the CNT among the LHNBR.When using this solvent method, the high tensile of HNBR/MWNT-matrix material (having 25phrMWNT content) is 18.6MPa.
CN 1554693 has disclosed by CNT (carbon nano-tube) modification HNBR to improve thermotolerance, wearability and the physical strength of HNBR.For preparation HNBR composite rubber material, at first partially hydrogenated paracril is mixed and added then to CNT (carbon nano-tube) and liquid rubber ultrasonically to prepare a kind of masterbatch; Then this masterbatch is mixed with hydrogenated nitrile-butadiene rubber, carbon black, zinc oxide and the vulcanizing agent of residual content.This mixture is carried out blend on a roll-type mixing roll or a banbury; And by solidification treatment, produced the hydrogenated nitrile-butadiene rubber of CNT (carbon nano-tube) modification then.
US 2006/0061011 has taught a kind of polymkeric substance-thermal conductivity of the CNT (carbon nano-tube) matrix material dependency relevant with the orientation of these CNT (carbon nano-tube).The polymeric matrix of recommending comprises styrene butadiene rubbers (SBR), paracril (NBR) and hydrogenated nitrile-butadiene rubber (HNBR).These polymkeric substance-CNT (carbon nano-tube) matrix material has been used to produce for motor vehicle pneumatic tyre and tire.
CA 2,530, and 471 have described the method that is used for production CNT (carbon nano-tube)-elastic composite.The tensile modulus that it has further disclosed this type of matrix material has been enhanced.As elastomerics, what mention is: polysiloxane, polyisoprene, polyhutadiene, polyisobutene, halogenated polyisoprene, halogenated polyhutadiene, halogenated polyisobutene, low temperature epoxies, EPDM, polyacrylonitrile, acrylonitrile butadiene rubber, styrene butadiene rubbers, EPM and other alpha-olefin copolymer things, and some fluorinated copolymers particularly.
JP 2003/322216 has taught a kind of production of dentate band, and wherein the surface of this dentate band comprises a kind of polymer latex, for example styrene butadiene rubbers, neoprene, paracril and hydrogenated nitrile-butadiene rubber.These polymer composites produce by mix CNT (carbon nano-tube) in the presence of resorcinol formaldehyde resin.
Consider steady demand, the purpose of this invention is to provide and make specialty elastomer and the new curable compound of additive bonded elastomer compounds.Hydrogenation carboxylated acrylonitrile divinyl rubber (" HXNBR ") itself has had and has comprised oil-proofness, wear resistance and to the attractive characteristic distribution profile (profile) of the good bounding force of metal.Yet, because the content of concrete carboxylic group is not also at length studied as other commodity elastomericss among the HXNBR, so its character in any composition is based on these may be that obtainable result is unpredictable concerning other more typical elastomericss.Yet, because the application that may be fit to for HXNBR is a little fars (rare) application, as special of oil well, high-performance belt and roll covers, for improving and still having the space based on the novel composition of HXNBR.
Summary of the invention
The present invention relates to comprise a kind of curable composition of a kind of hydrogenated carboxylated nitrile rubber, at least a linking agent and CNT (carbon nano-tube), relate to and be used to prepare a kind of method of the curable composition of this kind and the purposes that relates to the solidification treatment of this based composition and be used to prepare moulded products.
Embodiment
Curable composition according to the present invention comprises a kind of hydrogenated carboxylated nitrile rubber, at least a linking agent and CNT (carbon nano-tube).
As run through this specification sheets and use, the term " hydrogenation carboxyl nitrile polymer " or the HXNBR meaning are meant and comprise a kind of polymkeric substance with a plurality of repeating units, these repeating units are derived from a) at least a conjugated diolefine, b) at least a α, alpha, beta-unsaturated nitriles, c) have at least a monomer of at least one carboxylic group or its a kind of derivative, and d) but the monomer of one or more copolymerization that can be randomly other, wherein, the polymkeric substance that will be present in the initial carboxyl nitrile polymer greater than 50% residual double bonds (RDB) carries out hydrogenation, preferably will carry out hydrogenation, more preferably will carry out hydrogenation greater than 95% RDB and most preferably will carry out hydrogenation greater than 99% RDB greater than 90% RDB.
Conjugated diolefine can be any character.Preferred (the C that uses
4-C
6) conjugated diene.Particularly preferably be 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene or their mixture.Very particularly preferably be 1,3-butadiene and isoprene or their mixture.Especially preferred is 1,3-butadiene.
As α, alpha, beta-unsaturated nitriles might use any known α, alpha, beta-unsaturated nitriles, preferably a kind of (C
3-C
5) α, alpha, beta-unsaturated nitriles is vinyl cyanide, methacrylonitrile, ethyl acrylonitrile or their mixture for example.Particularly preferably be vinyl cyanide.
As a kind of monomer with at least one carboxylic group or its a kind of derivative, might use for example α, β-unsaturated monocarboxylic acid or dicarboxylic acid, their ester class or amides.
As α, β-unsaturated monocarboxylic acid or dicarboxylic acid, preferably fumaric acid, toxilic acid, vinylformic acid and methacrylic acid.
As α, the ester class of beta-unsaturated carboxylic acid is preferably used their alkyl esters and alkoxy alkyl class.Particularly preferred α, the alkyl esters of beta-unsaturated carboxylic acid are methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, ethyl acrylate, methacrylic acid-2-ethylhexyl and Octyl acrylate.Particularly preferred α, the alkoxy alkyl class of beta-unsaturated carboxylic acid is (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester and (methyl) vinylformic acid methoxyl group ethyl ester.Also might use the mixture of alkyl esters (for example, above-mentioned those) and alkoxy alkyl class (for example, with above-mentioned those form).
In a preferred embodiment, use is based on a kind of hydrotrimer of vinyl cyanide, divinyl and toxilic acid.In an other embodiment preferred, use based on vinyl cyanide, divinyl and α a kind of hydrogenation terpolymer of a kind of alkyl ester of beta-unsaturated carboxylic acid (particularly n-butyl acrylate, isobutyl acrylate and tert-butyl acrylate).
Typically, this hydrogenation carboxyl nitrile polymer comprises in the following scope
A) repeating unit of from 40 to 85 weight percents, these repeating units be derived from one or more conjugated diolefines, preferred divinyl,
B) repeating unit of from 15 to 60 weight percents, these repeating units be derived from one or more α, β-undersaturated nitrile, and preferred vinyl cyanide, and
C) repeating unit of from 0.1 to 30 weight percent, these repeating units are derived from one or more monomers with at least one carboxylic group or its a kind of derivative, preferably derived from a kind of α, β-undersaturated monobasic-or di-carboxylic acid, and more preferably toxilic acid, n-butyl acrylate, isobutyl acrylate or tert-butyl acrylate
Wherein these three kinds of unit a), b) and c) must in given scope, select, make them add up 100 weight percents like this.
Preferably, this hydrogenation carboxyl nitrile polymer comprises in the following scope
A) repeating unit of from 55 to 75 weight percents, these repeating units be derived from one or more conjugated diolefines, preferred divinyl,
B) repeating unit of from 25 to 40 weight percents, these repeating units be derived from one or more α, alpha, beta-unsaturated nitriles, and preferred vinyl cyanide, and
C) repeating unit of from 1 to 7 weight percent, these repeating units are derived from one or more monomers with at least one carboxylic group or its a kind of derivative, preferably derived from a kind of α, β-undersaturated monobasic-or di-carboxylic acid, and more preferably toxilic acid, n-butyl acrylate, isobutyl acrylate or tert-butyl acrylate
Wherein these three kinds of unit a), b) and c) must in given scope, select, make them add up 100 weight percents like this.
More preferably, this hydrogenation carboxyl nitrile polymer comprises in the following scope
A) repeating unit of from 55 to 75 weight percents, these repeating units be derived from one or more conjugated diolefines, preferred divinyl,
B) repeating unit of from 25 to 40 weight percents, these repeating units be derived from one or more α, alpha, beta-unsaturated nitriles, and preferred vinyl cyanide, and
C) repeating unit of from 1 to 30 weight percent, these repeating units are derived from one or more monomers with at least one carboxylic group or its a kind of derivative, preferably derived from a kind of α, β-undersaturated monobasic-or di-carboxylic acid, and more preferably toxilic acid, n-butyl acrylate, isobutyl acrylate or tert-butyl acrylate
Wherein these three kinds of unit a), b) and c) must in given scope, select, make them add up 100 weight percents like this.
In an alternate embodiment, might use except that conjugated diolefine, α, but alpha, beta-unsaturated nitriles and have the monomer of at least one carboxylic group or the monomer of one or more the other copolymerization outside its a kind of derivative.But the monomer of this type of copolymerization is known to those skilled in the art.Therefore, but this hydrogenation carboxyl nitrile polymer may further include the repeating unit of the monomer (for example alkyl acrylate or vinylbenzene) derived from one or more copolymerization.But will substitute α in this paracril by the repeating unit of the monomer derived of the other copolymerization of this class, alpha, beta-unsaturated nitriles or conjugated diolefine part, and be apparent that for a person skilled in the art above-mentioned numeral must be through adjusting to reach 100 weight percents.
Those skilled in the art fully understand by above-mentioned these monomeric polyreactions and hydrogenation subsequently and prepare hydrogenation carboxyl nitrile polymer, and this are had comprehensive explanation in the polymkeric substance document.This type hydrogenation carboxyl nitrile polymer is prepared by free-radical emulsion polymerization typically.Hydrogenation carboxyl nitrile polymer also is commercially available, for example as, by name from the commodity of Lanxess Deutschland GmbH
The product of product scope.
The hydrogenation carboxyl nitrile polymer that is used to prepare curable composition according to the present invention typically has mooney viscosity in from 5 to 90, preferably from 65 to 85 scopes (at 100 ℃ time, ML 1+4).The weight-average molecular weight M that this is corresponding
wIn the scope of 50000-500000, preferably in the scope of 200000-450000.And used hydrogenated carboxylated nitrile rubber also has a kind of polymolecularity PDI=M
w/ M
n, M wherein
wBe weight-average molecular weight and M
nBe number-average molecular weight, be in the scope of 1.7-6.0 and preferably be in the scope of 2.0-3.0.
The determining of mooney viscosity (in the time of 100 ℃, ML 1+4) carries out according to ASTM standard D 1646.
The residual double bonds (RDB) greater than 50% that hydrogenation in the present invention preferably is understood that to be present among initial nitrile polymer/NBR is hydrogenated, be preferably greater than 90% RDB and be hydrogenated, the RDB more preferably greater than 95% is hydrogenated and most preferably is hydrogenated greater than 99% RDB.
The invention is not restricted to a kind of specific method that is used to prepare hydrogenated carboxylated nitrile rubber.Yet preferred in the present invention HXNBR is easy to obtain, as disclosed in the WO-A-01/077185.Jurisdiction for allowing this operation is combined in this with WO-A-01/77185 by reference.
Curable composition comprises Single Walled Carbon Nanotube (SWNT) or multiple-wall carbon nanotube (MWNT) according to the present invention.
A kind of SWNT is a kind of molecular level silk screen with two key structure parameters.By a mono-layer graphite sheet is bent into a right cylinder, the beginning and end of a lattice vector on the mono-layer graphite plane is coupled together.These indexes are determined the diameter of nanotube, and so-called in addition ' chirality '.These pipes are ' armchair ' pipes (' arm-chair ' tubes), because be in an armchair around these atoms of circumference.Consider atomic configuration, so these nanotubes are called ' zigzag ' (' zigzag ') along circumference.The other types of nanotube are chiralitys, wherein hexagonal these rows along the coiling of the axis of nanotube (Surface Science, 2002,500 (1-3), p.218).
Many walls nanotube (MWNT) comprises that self rolled-up multilayer graphite is to form the shape of a pipe.
This type of CNT (carbon nano-tube) is commercially available or according to preparing from the known method of prior art: the main synthetic method that is used for list and multiple-wall carbon nanotube comprises arc discharge method (Nature, 1991,354, p.56), laser ablation method (Applied Physics A:Materials Science ﹠amp; Processing, 1998,67 (1), p.29), from gas phase catalysis growth method (Chemical Physics Letters, 1999,313 that carbon monoxide begins, p.91) and chemical Vapor deposition process (CVD) (the Applied Physics Letters that begins from hydro carbons, 1999,75 (8), p.1086; Science, 1998,282, p.1105).Be applying nano carbon pipe in matrix material, need a large amount of nanotubes, and arc-over and the laser ablation limit of amplifying will make the cost based on the nanotube of matrix material to bear.These gas phase process are tending towards producing the nanotube with impurity still less and are more suitable in extensive processing.It is believed that some gaseous techniques (for example CVD) of being used for growing nano-tube provide maximum potential possibility to the amplification of the nanotube production that is used for matrix material processing.
Typically comprise in each case based on 100 parts hydrogenated carboxylated nitrile rubber by weight 1-50 part, preferred 1-20 part by weight and the more preferably CNT (carbon nano-tube) of 1-10 part by weight by weight according to composition of the present invention.
Curable composition according to the present invention comprises one or more linking agents in addition.The present invention is not limited to a kind of specific cross linker.Based on the linking agent of superoxide and can be separately or even use with mixture based on the linking agent of sulphur.Preferably peroxide cross-linking agent or original position discharge the linking agent of superoxide.
The present invention is not limited to a kind of specific peroxide cross-linking agent.For example, inorganic or organo-peroxide all is fit to.Organo-peroxide dialkyl peroxide for example preferably, the ketal superoxide, aromatic alkyl superoxide, the superoxide ethers, and superoxide ester class, for example: ditertiary butyl peroxide, two-(t-butyl peroxy sec.-propyl)-benzene, dicumyl peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexane, 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexene-(3), 1,1-pair-(t-butyl peroxy)-3,3,5-trimethylammonium-hexanaphthene, benzoyl peroxide, tertiary butyl cumyl peroxide, TBPB tertiary butyl perbenzoate, and zinc peroxide.This type of superoxide is easy to be purchased.
Usually the amount of linking agent and the concrete superoxide in curable composition is in the scope of 1phr to 10phr (=each hundred parts of rubber, i.e. HXNBR), preferably in the scope of 4phr to 8phr.Superoxide may advantageously be used with the form of bonding polymkeric substance.The system that is fit to is commercially available, for example from polydispersion body T (VC) D-40P of Rhein ChemieRheinau GmbH, and D (the di-t-butyl peroxide-isopropyl benzene of=bonding polymkeric substance).
In one embodiment, this curable composition comprises
A) 100 parts HXNBR by weight
B) based on 100 parts HXNBR by weight, 1 part to 10 parts by weight, preferred 4 parts to 8 parts at least a linking agent by weight, and
C) based on 100 parts HXNBR by weight, 1 part to 50 parts by weight, preferred 1 part to 20 parts and more preferably 1 part to 10 parts carbon nanotube by weight by weight.
Weighting agent:
Composition of the present invention further can randomly comprise at least a weighting agent.This weighting agent can be a kind of activatory or inactive weighting agent or its a kind of mixture.
This weighting agent specifically can be
-high dispersive silica, for example the flame hydrolysis of precipitation by silicate solutions or silicon halide prepares, and has from 5m
2/ g to 1000m
2Specific surface area in the/g scope, and have at the primary particle diameter in 10nm to 400nm scope; Can be randomly, these silicas also can with other metal oxide for example Al, Mg, Ca, Ba, Zn, Zr and Ti those and exist as mixed oxide;
-synthetic silicate, for example pure aluminium silicate and alkaline earth metal silicate be as Magnesium Silicate q-agent or Calucium Silicate powder, has from 20m
2/ g to 400m
2BET specific surface area and primary particle diameter in/the g scope are in 10nm to 400nm scope;
-natural silicate, for example kaolin and other naturally occurring silicas;
-glass fibre and glass fiber product (felt piece (matting), extrudate) or glass microsphere;
-metal oxide, for example zinc oxide, calcium oxide, magnesium oxide and aluminum oxide; Magnesium oxide preferably;
-metal carbonate, for example magnesiumcarbonate, lime carbonate and zinc carbonate;
-metal hydroxides, for example aluminium hydroxide and magnesium hydroxide;
-carbon black; At this standby carbon black is to prepare by dim, furnace black or channel black method, and preferably has from 20m
2/ g is to 200m
2BET (DIN 66 131) specific surface area in the/g scope, for example, SAF, ISAF, HAF, FEF or GPF carbon black;
-rubber gels is especially based on those of polyhutadiene, butadiene/styrene copolymers, butadiene/acrylonitrile copolymer and sovprene;
Or their mixture.
The example of preferred mineral filler comprises silica, and silicate, clay is wilkinite, gypsum, aluminum oxide, titanium dioxide, talcum, these mixture or the like for example.These mineral grains have oh group on their surface, causing them is hydrophilic and oleophobic.This makes and reaches good interactional difficulty strengthened between filling agent particle and rubber.For multiple purpose, preferred mineral are silicas, especially the silica of making by the carbonic acid gas precipitation of water glass.The dry amorphous silica granule that be fit to use according to the present invention can have from 1 micron average agglomeration particle diameter in 100 micrometer ranges, preferably between 10 microns and 50 microns and most preferably between 10 microns and 25 microns.Be less than 5 microns or greater than 50 microns less than the agglomerated particle of 10 per-cents by volume preferably.The unbodied exsiccant silica that is fit to has in addition usually the BET surface-area in 50 meters squared per gram to 450 meters squared per gram scopes (measuring according to DIN (Deutsche Industry Norm) 66131), and having, and the drying loss in by weight from 0 per-cent to 10 percentage range (measuring) according to DIN ISO 787/11 in the DBP absorption (measuring) in 150 grams/100 gram silicas and 400 grams/100 gram silica scopes according to DIN 53601.Silica filled dose that is fit to is with trade mark from PPG Industries Inc.
210,
233 and
243 is obtainable.Also be fit to from LanxessDeutschland GmbH
S and
N.
Often, advantageously use carbon black as weighting agent.Usually, carbon black in polymer composites with by weight from 20 parts to 200 parts, preferred 30 parts to 150 parts by weight, more preferably the amount in 40 parts to 100 parts the scope exists by weight.In addition, maybe advantageously in polymer composites of the present invention, use the combination of carbon black and mineral filler.In this combination, the ratio of mineral filler and carbon black is normally from 0.05 to 20, in preferred 0.1 to 10 the scope.
Other ancillary compound
Can further comprise the ancillary compound that is used for rubber according to polymkeric substance-nano-carbon tube composition of the present invention, for example auxiliary agent, antioxidant, pore forming material, antiaging agent, thermo-stabilizer, photostabilizer, ozone stablizer, processing aid, softening agent, tackifier, whipping agent, dyestuff, pigment, wax, extender, organic acid, inhibitor, metal oxide are quickened in reaction promotor, curing catalyst, curing, and activator such as trolamine, polyoxyethylene glycol, hexanetriols etc., these are known to rubber industry circle.
These rubber ingredients can be measured use routinely, and except other things, this depends on predetermined purposes.Convention amount be for example based on rubber from 0.1wt.% to 50wt.%.Preferably, said composition is included in a kind of organic aliphatic acid in 0.1phr to the 20phr scope as subsidiary material, a kind of unsaturated fatty acids that preferably has the two keys of, two or more carbon at intramolecularly, more preferably, this lipid acid comprises by weight 10% or more a kind of conjugated diolefine acid, and this conjugated diolefine acid has at least one conjugation carbon-to-carbon double bond at its intramolecularly.Preferred these lipid acid have at 8-22, the more preferably carbon atom in 12-18 the scope.Example comprise stearic acid, palmitinic acid and oleic acid and their calcium-, zinc-, magnesium-, potassium-and ammonium salt.
In other embodiments, curable composition can comprise that a kind of acrylate in 5phr to the 50phr scope is as a kind of subsidiary material.The acrylate that is fit to is from EP-A1-0319320, and p.3 concrete is, 1.16 to 35, and from US-5208294, that concrete is Col.2, known in 1.25 to 40, and from US-4983678, that concrete is Col.2,1.45 to 62.Mention zinc acrylate resin, dizinc acrylate resin or zinc dimethacrylate or a kind of liquid methacrylate especially, for example trihydroxy methyl propane trimethyl acrylate (TRIM), tetramethylene dimethacrylate (BDMA) and Ethylene glycol dimethacrylate (EDMA).Maybe advantageously use the combination of different acrylate and/or their metal-salt.The often particularly advantageous acrylate metal salt that makes up with a kind of scorch retarder (sterically hindered phenol for example, the aminoalkylphenols of methyl-replacements for example, particularly 2,6-di-t-butyl-4-dimethylaminomethyl phenol) that is to use.
Curable composition produced according to the present invention
Another object of the present invention is to prepare curable composition, wherein with HXNBR, CNT (carbon nano-tube) and linking agent and randomly any other composition of said composition mix.
Typically this mixture is to carry out under the temperature of the raising in 20 ℃ to 200 ℃ scope.
This mixing can further be carried out in the presence of a kind of solvent, and then, this solvent is removed after mixing.
Under the normal circumstances, mixing time be no more than 1 hour and the time in scope from 2 minutes to 30 minutes normally enough.
This mixing is adapted at carrying out in the intermingling apparatus, and for example a Banbury mixer is as banbury or Haake or Brabender miniature internal mixer.A twin-screw extruder also provides CNT (carbon nano-tube) and the good distribution of other optional additives in elastomerics.A forcing machine also provides good mixing, and makes mixing time shorter.Might mix in two or more stages, and can mix in different devices, for example, a stage is in Banbury mixer, and a stage is in forcing machine.Yet, should be noted in the discussion above that at mix stages undesirable precrosslink (=burn) do not take place.
Mixing and solidification treatment can be carried out according to any method known to those skilled in the art (for example referring to Encyclopedia of Polymer Science and Engineering, Vol.4, p.66 et seq (Compounding) and Vol.17, p.666 et seq. (Vulcanization)).Typically this solidification treatment is to carry out under the temperature from 100 ℃ to 200 ℃, in preferred 130 ℃ to the 180 ℃ scopes.In one embodiment, a kind of preparation of polymer cure rubber is included in and makes composition of the present invention stand a solidification treatment in the process of injection molding.
Therefore another object of the present invention is to obtain a kind of curing rubber after solidification treatment, preferably be in the form of moulded products, for example sealing member, roll covers, belt, a stator or be used to is attached to a supporting pad on the crawler belt of a tracked vehicle.
These can compare with HXNBR and demonstrate enhanced tensile strength and modulus properties and kept elongation when the fracture with emergent property by solidifying the curing rubber goods that obtain according to composition of the present invention.
Example:
The details of used raw material is summarized in the following table 1 in following example.
Curable composition produced according to the present invention
Use Banbury mixer HXNBR and MWNT to be mixed with 9: 1 ratio by weight.Use masterbatch that a twin-screw extruder will contain 10wt%MWNT to be diluted to the MWNT of different concns.MWNT ultimate density in HXNBR is 0 part, 1 part, 2 parts and 4 parts (referring to table 2) among each hundred parts of (phr) HXNBR.After HXNBR/MWNT plasticates 5min, add solidifying agent DCP.At last, the HXNBR mixture is solidified 20min down at 10 ℃.
Test step/method:
Tensile strength test is that (Instron Co. carries out on UK) at Instron 4465 tension testing machines under the pinblock speed (crosshead speed) at 500mm/min.The dumb-bell shape sample is that 75mm is long, 1mm is thick and 4mm is wide.Xiao A hardness is to measure according to ASTM D2240-97 by the Xiao A hardness meter of manual type.After 5 seconds, the result is read.Dynamic mechanical analysis (DMA) be to use DMA 242C (NETZSCH, Germany) under nitrogen under-60 ℃ to 40 ℃ the temperature with the heating rate of 5 ℃/min and carry out with the frequency of 1Hz.
In following table 2, all amount is to be that condition provides with the umber among per 100 parts of HXNBR by weight.
Table 2
| Sample | X1 (contrast) | ??X2 | ??X3 | ??X4 |
| ??HXNBR | ?100 | ??100 | ??100 | ??100 |
| ??MWNT | ?- | ??1 | ??2 | ??4 |
| ??MgO | ?5 | ??5 | ??5 | ??5 |
| ??DCP | ?3 | ??3 | ??3 | ??3 |
| Hardness, Shore A | ?61 | ??63 | ??65 | ??67 |
| Tensile strength (MPa) | ?26,5 | ??28,2 | ??35.3 | ??37.1 |
| Elongation at break (%) | ?440 | ??434 | ??456 | ??424 |
| Modulus (MPa) when 100% strain | ?1,9 | ??2,2 | ??2,6 | ??3,5 |
| Modulus (MPa) when 200% strain | ?3,4 | ??4,2 | ??5,2 | ??7,3 |
| Modulus (MPa) when 300% strain | ?6,8 | ??8,1 | ??9,4 | ??13,2 |
| Tension set (%) | ?5 | ??5 | ??8 | ??8 |
As from table 2 as seen, MWNT added to produce significantly among the HXNBR strengthens.The adding of the concrete MWNT that physical properties is produced quite big benefit and character enhanced value should be be included in composite-material formula in the level of CNT (carbon nano-tube) relevant.Benefit concerning polymer composites includes, but are not limited to the increase of tensile strength, the increase of polymer composites modulus under 100%, 200% and 300% strain, and the increase of final polymer composites hardness.
Claims (12)
1. a curable composition comprises a kind of hydrogenated carboxylated nitrile rubber (HXNBR), at least a linking agent and CNT (carbon nano-tube).
2. curable composition according to claim 1, wherein these CNT (carbon nano-tube) or a kind of Single Walled Carbon Nanotube or a kind of multiple-wall carbon nanotube.
3. curable composition according to claim 1 and 2, wherein these CNT (carbon nano-tube) be based on by weight 100 parts hydrogenated carboxylated nitrile rubber with 1-50 part by weight, preferred 1-20 part by weight and more preferably by weight 1-10 part exist.
4. according to one in the claim 1 to 3 or multinomial described curable composition, wherein these CNT (carbon nano-tube) have a mean diameter between 5nm and 30nm.
5. according to one in the claim 1 to 4 or multinomial described curable composition, wherein this hydrogenation carboxyl nitrile polymer comprises in the following scope
A) repeating unit of from 40 to 85 weight percents, these repeating units be derived from one or more conjugated diolefines, preferred divinyl,
B) repeating unit of from 15 to 60 weight percents, these repeating units be derived from one or more α, alpha, beta-unsaturated nitriles, and preferred vinyl cyanide, and
C) repeating unit of from 0.1 to 30 weight percent, these repeating units are derived from one or more monomers with at least one carboxylic group or its a kind of derivative, preferably derived from a kind of α, β-undersaturated list-or dicarboxylic acid, and more preferably toxilic acid, n-butyl acrylate, isobutyl acrylate or tert-butyl acrylate, wherein these three kinds of unit a), b) and c) must in given scope, select, make them add up 100 weight percents like this.
6. according to one in the claim 1 to 5 or multinomial described curable composition, wherein this linking agent or a kind of superoxide, a kind of compound or sulphur that discharges superoxide.
7. according to one in the claim 1 to 6 or multinomial described curable composition, comprise
1) 100 parts HXNBR by weight
2) based on 100 parts HXNBR by weight, 1 part to 10 parts by weight, preferred 4 parts to 8 parts at least a linking agent by weight, and
3) based on 100 parts HXNBR by weight, 1 part to 50 parts by weight, preferred 1 part to 20 parts and more preferably 1 part to 10 parts carbon nanotube by weight by weight.
8. be used for preparing a kind of method, wherein HXNBR, these CNT (carbon nano-tube) and this linking agent mixed according to one of claim 1 to 7 or multinomial described curable composition.
9. method according to claim 8, wherein this mixing is to carry out under a temperature in 20 ℃ to 200 ℃ scope.
10. according to Claim 8 or 9 described methods, wherein this mixing is carried out in the presence of a kind of solvent, and this solvent is removed after mixing then.
11. comprising making according to one in the claim 1 to 7 or multinomial described composition, a kind of method of preparation multiple polymers curing rubber goods, this method stand a solidification treatment, preferably in the injection molding process.
12. polymer cure rubber item, this polymer cure rubber item can obtain by method according to claim 11, particularly is in following form: sealing member, roll covers, a band, a stator or be used to is attached to a supporting pad on the crawler belt of an endless-track vehicle.
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| CN200910150258.9A CN101613495B (en) | 2008-06-23 | 2009-06-23 | Rubber composition containing carbon nano-tube |
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| CN102702591A (en) * | 2012-06-25 | 2012-10-03 | 青岛科技大学 | Hydrogenated nitrile rubber/carbon nanotube composite material and preparation method thereof |
| JP2014189578A (en) * | 2013-03-26 | 2014-10-06 | Nissin Kogyo Co Ltd | Carbon fiber composite material and method for producing the same |
| CN106661280A (en) * | 2014-07-25 | 2017-05-10 | 日本瑞翁株式会社 | Cross-linkable rubber composition and cross-linked rubber |
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| CA2428222A1 (en) * | 2003-05-08 | 2004-11-08 | Bayer Inc. | Rubber compound comprising nitrile rubbers |
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| DE102005047115A1 (en) * | 2005-09-30 | 2007-04-05 | Lanxess Deutschland Gmbh | Crosslinkable compositions, processes for their preparation and their use |
| DE102007042496A1 (en) * | 2006-09-01 | 2008-05-15 | Continental Aktiengesellschaft | Producing a vulcanizable rubber mixture, e.g. for tire treads, comprises dispersing a modified phyllosilicate filler in a polar rubber and mixing the resulting masterbatch with another rubber |
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| CN102702591A (en) * | 2012-06-25 | 2012-10-03 | 青岛科技大学 | Hydrogenated nitrile rubber/carbon nanotube composite material and preparation method thereof |
| CN102702591B (en) * | 2012-06-25 | 2013-11-27 | 青岛科技大学 | Hydrogenated nitrile rubber/carbon nanotube composite material and preparation method thereof |
| JP2014189578A (en) * | 2013-03-26 | 2014-10-06 | Nissin Kogyo Co Ltd | Carbon fiber composite material and method for producing the same |
| CN106661280A (en) * | 2014-07-25 | 2017-05-10 | 日本瑞翁株式会社 | Cross-linkable rubber composition and cross-linked rubber |
| US10538641B2 (en) | 2014-07-25 | 2020-01-21 | Zeon Corporation | Crosslinkable rubber composition and crosslinked rubber |
| CN107709503A (en) * | 2015-06-26 | 2018-02-16 | 日本瑞翁株式会社 | Gas sealant member composition and gas sealant member |
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| CN112562471B (en) * | 2020-12-03 | 2023-09-19 | 西安医学院 | Manufacturing method of children oral teaching operation model |
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