CN101613495B - Rubber composition containing carbon nano-tube - Google Patents
Rubber composition containing carbon nano-tube Download PDFInfo
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- CN101613495B CN101613495B CN200910150258.9A CN200910150258A CN101613495B CN 101613495 B CN101613495 B CN 101613495B CN 200910150258 A CN200910150258 A CN 200910150258A CN 101613495 B CN101613495 B CN 101613495B
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Abstract
The invention provides a curing composition containing a particular hydrogenated nitrile-butadiene rubber, at least one crosslinking agent, and a carbon nano-tube, a method for preparing the composition and applications for preparing curing rubber products. The curing rubber products show excellent thermal performance, oil resistivity and mechanical strength.
Description
Technical field
The present invention relates to comprise the curable composition of a kind of specific hydrogenated nitrile-butadiene rubber, a kind of linking agent and CNT (carbon nano-tube), for the preparation of a kind of method of such 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 widely machinery, character chemistry and physics of domination.Paracril (NBR) and its hydrogenated products, namely hydrogenated nitrile-butadiene rubber also is abbreviated as " HNBR ", represents this type of specialty elastomer.HNBR has 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 stricter to the requirement of the annex (functional rubbery accessory) of functional rubber.Being necessary that to seek makes new curable compound that specialty elastomer is combined with additive with the performance of 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 effectively improve the mechanical property of matrix 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 simultaneously 1000 or the tubule of the form of higher very high length-to-diameter ratio.Although the density of these CNT is low, they still are considered to cause high-intensity a kind of zero defect structure as single molecule.
Two kinds of basic forms are arranged concerning CNT (carbon nano-tube), from a kind of single graphite flake layer production those, be called single-walled nanotube (SWNT), and be called many walls nanotube (MWNT) by those nanotubes that some concentric lamellas are made.SWNT is by about some relevant summaries of this theme and produced sizable interest in academia, these summaries comprise following everybody do those, such 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 for the production of them of having developed occurred.Iijima (Nature, 1991,354,56) at first observes many walls nanotube.After several years, the people (Nature, 1993,363,605) such as the 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 vapour deposition (CVD) (the AppliedPhysics Letters that begins from hydro carbons, 1999,75,1086; Science, 1998,282,1105).Need subsequently purification step to separate these pipes.These gas phase process are tending towards producing the nanotube with impurity still less and are easier to extensive the processing.Up to now, although do not have low cost, large-scale production method, traditional method further developed and novel method for example fluidized-bed reactor just studied to produce a kind of CNT supply stable, moderate price.Low CNT availability and its high price have limited the realization of polymkeric substance-CNT matrix material for many practical applications.
The standby hydrogenated carboxylated nitrile rubber (also being abbreviated as " HXNBR ") of selection Hydrogenation by carboxyl nitrile-conjugated diene rubber (also being abbreviated as " XNBR ", is to comprise at least a conjugated diolefine, at least a unsaturated nitrile, at least a carboxylated monomer and a kind of multipolymer of the repeating unit of other comonomer optionally) 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 other field, also in automobile (sealing member, flexible pipe, supporting pad), oil (stator, wellhead sealing spare, valve block), electric power (cable sheath), mechanical engineering (tire, roller) and shipbuilding (conduit seals, joint), be widely used just not at all surprising.
Method for the preparation of the HXNBR polymkeric substance has been described among the 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 inquires into not yet in detail 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 at present research 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 when carbon nano-particle is used for the silicone base elastomerics impact on the sample mechanical property that obtains.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 the decline of final performance.
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 on the curing of HNBR and the impact of mechanical property.Two kinds of methods are for the preparation of 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 compound 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 wave and disperse.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 then added 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 at a roll-type mixing roll or a banbury; And then by solidification treatment, produced the hydrogenated nitrile-butadiene rubber of CNT (carbon nano-tube) modification.
US 2006/0061011 has taught a kind of thermal conductivity dependency relevant with the orientation of these CNT (carbon nano-tube) of polymkeric substance-nanometer carbon pipe composite material.The polymeric matrix of recommending comprises styrene butadiene rubbers (SBR), paracril (NBR) and hydrogenated nitrile-butadiene rubber (HNBR).These polymkeric substance-nanometer carbon pipe composite materials have been used to produce for motor vehicle pneumatic tyre and tire.
CA 2,530, and 471 have described the method for the production of 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: the polyisobutene of the polyisoprene of polysiloxane, polyisoprene, polyhutadiene, polyisobutene, halogenation, the polyhutadiene of halogenation, halogenation, low temperature epoxies, EPDM, polyacrylonitrile, acrylonitrile butadiene rubber, styrene butadiene rubbers, EPM and other alpha-olefin copolymers, 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 the steady demand to elastomer compounds, the purpose of this invention is to provide the new curable compound that specialty elastomer is combined with additive.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, such 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 for the preparation of a kind of method of the curable composition of this kind and relate to the solidification treatment of such composition and for the preparation of the purposes of 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, term " hydrogenation carboxyl nitrile polymer " or the HXNBR meaning refer to 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 other copolymerization optionally, 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 greater than 90% RDB, more preferably will carry out greater than 95% RDB hydrogenation and most preferably will carry out hydrogenation greater than 99% 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, possible example such as 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, Tert-butyl Methacrylate, 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 in addition preferred embodiment, use is 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 like this them add up 100 weight percents.
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 like this them add up 100 weight percents.
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 like this them add up 100 weight percents.
In an alternate embodiment, might use except 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 the polyreaction of above-mentioned these monomers 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.
Typically has mooney viscosity in from 5 to 90, preferably from 65 to 85 scopes (at 100 ℃ time, ML 1+4) according to the present invention for the preparation of the hydrogenation carboxyl nitrile polymer of curable composition.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 in the present invention hydrogenation preferably is understood 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 for the preparation of hydrogenated carboxylated nitrile rubber.Yet preferred HXNBR is easy to obtain in the present invention, 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 in addition so-called ' chirality '.These pipes are ' armchair ' pipes (' arm-chair ' tubes), because be in an armchair around these atoms of circumference.Consider the atomic configuration along circumference, so these nanotubes are called ' zigzag ' (' zigzag ').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 Multi-layer 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 (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 be so that can't bear based on the cost of the nanotube of matrix material.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) for growing nano-tube provide maximum Potential feasibility to the amplification of the nanotube production that is used for composite processing.
Typically comprise in each case based on 100 parts hydrogenated carboxylated nitrile rubber by weight by weight 1-50 part, preferred by weight 1-20 part and the more preferably CNT (carbon nano-tube) of 1-10 part 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 linking agent.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 by weight 4 parts to 8 parts at least a linking agent, and
C) based on 100 parts HXNBR by weight, 1 part to 50 parts by weight, preferred by weight 1 part to 20 parts and more preferably 1 part to 10 parts carbon nanotube by weight.
Weighting agent:
Composition of the present invention further optionally comprises at least a weighting agent.This weighting agent can be weighting agent a kind of activation or inactive or its a kind of mixture.
This weighting agent specifically can be
-high dispersive silica, for example the flame hydrolysis of the 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; Optionally, 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, calcium carbonate and zinc carbonate;
-metal hydroxides, for example aluminium hydroxide and magnesium hydroxide;
-carbon black; Be to prepare by dim, furnace black or channel black method at this carbon black for subsequent use, and preferably have 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 etc. for example.These mineral grains have oh group on their surface, and it is hydrophilic and oleophobic causing them.This makes and reaches good interactional difficulty strengthened between filling agent particle and rubber.For multiple purpose, preferred mineral are silicas, the silica of especially 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.Less than 5 microns or greater than 50 microns less than the agglomerated particle of 10 per-cents by volume preferably.The silica of the unbodied drying 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 in the DBP absorption (measuring according to DIN 53601) in 150 grams/100 gram silicas and 400 grams/100 gram silica scopes, and the drying loss in by weight from 0 per-cent to 10 percentage range (measuring according to DIN ISO 787/11).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 ancillary compound 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 accelerated 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 in molecule, has the two keys of, two or more carbon, 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 in its molecule.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 especially zinc acrylate resin, dizinc acrylate resin or zinc dimethacrylate or a kind of liquid methacrylate, 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.Often particularly advantageous is to use the 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).
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 optionally 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 normal circumstances, mixing time be no more than 1 hour and the time in the 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) does not occur.
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 for is attached to a supporting pad on the crawler belt of a tracked vehicle.
These can be compared tensile strength and the modulus properties that demonstrates enhancing and keep elongation when the fracture with emergent property by solidifying the curing rubber goods that obtain according to composition of the present invention with HXNBR.
Example:
The details of used raw material is summarized in the following table 1 in following instance.
Curable composition produced according to the present invention
Use Banbury mixer with 9: 1 ratio by weight HXNBR and MWNT to be mixed.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 under 10 ℃.
Test step/method:
Tensile strength test is to carry out at Instron 4465 tension testing machines (Instron Co., UK) 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) is to use DMA 242C (NETZSCH, Germany) to carry out with the heating rate of 5 ℃/min and with the frequency of 1Hz under-60 ℃ to 40 ℃ temperature under nitrogen.
In following table 2, all amount is that umber in per 100 parts of HXNBR by weight provides as condition.
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 when 100% strain (MPa) | 1,9 | 2,2 | 2,6 | 3,5 |
| Modulus when 200% strain (MPa) | 3,4 | 4,2 | 5,2 | 7,3 |
| Modulus when 300% strain (MPa) | 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 large benefit and the value that character strengthens 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 (17)
1. curable composition, comprise a kind of hydrogenated carboxylated nitrile rubber HXNBR, at least a linking agent and CNT (carbon nano-tube), wherein, the scope at the mooney viscosity under ML 1+4 under 100 ℃ that described hydrogenated carboxylated nitrile rubber HXNBR has is 65 to 85, and wherein, described CNT (carbon nano-tube) is based on by weight 100 parts hydrogenated carboxylated nitrile rubber and exists with the amount of 1-10 part by weight.
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. each described curable composition in 2 according to claim 1, wherein these CNT (carbon nano-tube) have a mean diameter between 5nm and 30nm.
4. each described curable composition in 2 according to claim 1, wherein this hydrogenated carboxylated nitrile rubber 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,
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
C) repeating unit of from 0.1 to 30 weight percent, these repeating units be derived from one or more monomers with at least one carboxylic group or its a kind of derivative,
Wherein these three kinds of unit a), b) and c) must in given scope, select, make like this them add up 100 weight percents.
5. each described curable composition in 2 according to claim 1, wherein this linking agent or a kind of superoxide, a kind of compound or sulphur that discharges superoxide.
6. each described curable composition in 2 according to claim 1 comprises
1) 100 parts HXNBR by weight
2) based on 100 parts HXNBR by weight, 1 part to 10 parts at least a linking agent by weight, and
3) based on by weight 100 parts HXNBR, by weight 1 part to 10 parts carbon nanotube.
7. curable composition according to claim 4, described conjugated diolefine is divinyl, described α, alpha, beta-unsaturated nitriles are vinyl cyanide.
8. curable composition according to claim 4, described c) repeating unit of from 0.1 to 30 weight percent is derived from a kind of α, β-undersaturated list-or dicarboxylic acid.
9. curable composition according to claim 4, described c) repeating unit of from 0.1 to 30 weight percent is derived from toxilic acid, n-butyl acrylate, isobutyl acrylate or tert-butyl acrylate.
10. curable composition according to claim 6, described at least a linking agent is 4 parts to 8 parts by weight.
11. for the preparation of a kind of method of each described curable composition in 10 according to claim 1, wherein HXNBR, these CNT (carbon nano-tube) and this linking agent are mixed.
12. method according to claim 11, wherein this mixing is to carry out under a temperature in 20 ℃ to 200 ℃ scope.
13. according to claim 11 or 12 described methods, wherein this mixing is carried out in the presence of a kind of solvent, and then this solvent is removed after mixing.
14. comprising, a kind of method of preparation multiple polymers curing rubber goods, the method make according to claim 1 that each described composition stands a solidification treatment in 10.
15. method according to claim 14, described solidification treatment is carried out in the injection molding process.
16. a polymer cure rubber item, this polymer cure rubber item can obtain by method according to claim 14.
17. polymer cure rubber item according to claim 16, this polymer cure rubber item is in following form: sealing member, roll covers, a band, a stator or be used for is attached to a supporting pad on the crawler belt of an endless-track vehicle.
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| JP6137899B2 (en) * | 2013-03-26 | 2017-05-31 | 日信工業株式会社 | Carbon fiber composite material and method for producing the same |
| US10538641B2 (en) | 2014-07-25 | 2020-01-21 | Zeon Corporation | Crosslinkable rubber composition and crosslinked rubber |
| CN107709503B (en) * | 2015-06-26 | 2019-06-18 | 日本瑞翁株式会社 | Gas sealant member composition and gas sealant member |
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| CN1550517A (en) * | 2003-05-08 | 2004-12-01 | Rubber mixture containing nitrile rubber | |
| CN1554693A (en) * | 2003-12-26 | 2004-12-15 | 江汉石油钻头股份有限公司 | Modified hydrogenated nitrile-butadiene rubber and its preparing method |
| CN1990541A (en) * | 2005-09-30 | 2007-07-04 | 兰爱克谢斯德国有限责任公司 | Crosslinkabe elastomer compositions, process for preparation, and use thereof |
| 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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| CN1550517A (en) * | 2003-05-08 | 2004-12-01 | Rubber mixture containing nitrile rubber | |
| CN1554693A (en) * | 2003-12-26 | 2004-12-15 | 江汉石油钻头股份有限公司 | Modified hydrogenated nitrile-butadiene rubber and its preparing method |
| CN1990541A (en) * | 2005-09-30 | 2007-07-04 | 兰爱克谢斯德国有限责任公司 | Crosslinkabe elastomer compositions, process for preparation, and use thereof |
| 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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