CA2416635A1 - Silica-filled elastomeric compounds - Google Patents
Silica-filled elastomeric compounds Download PDFInfo
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- CA2416635A1 CA2416635A1 CA 2416635 CA2416635A CA2416635A1 CA 2416635 A1 CA2416635 A1 CA 2416635A1 CA 2416635 CA2416635 CA 2416635 CA 2416635 A CA2416635 A CA 2416635A CA 2416635 A1 CA2416635 A1 CA 2416635A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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Abstract
The invention provides a process for preparing a filled halobutyl elastomer, which comprises mixing a halobutyl elastomer, mineral filler and a silazane compound or mixture of a silazane compound and an additive which contains at least one hydroxyl group and at least one substituents which bears a basic amine group, and curing the filled elastomer with sulfur or other curative systems. This invention has the advantages of (a) not evolving alcohol either during the manufacture or subsequent use of the article manufactured from the compound, (b) improving the scorch safety of filled halobutyl elastomer compounds which employ silica as the mineral filler and a hydroxyl- and amine-containing additive as a dispersing aid and (c) significantly reducing the cost of the compound compared to analogous compounds currently known in the art.
Description
POS I I IO CA CON
Silica-Filled elastomeric compounds Field of the invention The present invention relates to silica-filled halogenated k>utyl s elastomers, in particular bromobutyl elastomers (BIIR).
Background of the invention:
It is known that reinforcing fillers such as carbon black and silica greatly improve the strength and fatigue properties of elastomeric compounds.
io It is also known that chemical interaction occurs between the elastomer and the filler. For example, good interaction between carbon black and highly unsaturated elastomers such as polybutadiene (BR) and styrene butadiene copolymers (SBR) occurs because of the large number of carbon-carbon double bonds present in these copolymers. Butyl elastomers may have only Is one tenth, or fewer, of the carbon-carbon double bonds found in BR or SBR, and compounds made from butyl elastomers are known to interact poorly with carbon black. For example, a compound prepared by mixing carbon black with a combination of BR and butyl elastomers results in domains of BR, which contain most of the carbon black, and butyl domains which contain very 20 little carbon black. It is also known that butyl compounds have poor abrasion resistance.
Canadian Patent Application 2,293,149 shows that it is possible to produce filled butyl elastomer compositions with much improved properties by combining halobutyl elastomers with silica and specific silanes. These silanes 2s act as dispersing and bonding agents between the halogenated butyl elastomer and the filler. However, one disadvantage of the use of silanes is the evolution of alcohol during the process of manufacture and potentially during the use of the manufactured article produced by this process.
Additionally, silanes significantly increase the cost of the resulting 3o manufactured article.
Co-pending Canadian Patent Application 2,339,080 discloses milled halobutyl elastomeric compounds comprising certain organic compounds containing at least one basic nitrogen-containing group and at least one I
hydroxyl group enhance the interaction of halobutyl elastomers with carhon-black and mineral fillers, resulting in improved compound properties suci'n as tensile strength and abrasion (DIN).
s Summary of the Inventiion:
The present invention provides a process for preparing compositions comprising halobutyl elastomers, at feast one mineral filler and at least one silazane compound. The invention also provides filled halobutyl elastc~mer compositions comprising halobutyl elastomers, at least one mineral filler and to at least one silazane compound. In particular it provides a means to produce such filled compositions without the evolution of alcohol, and at significantly reduced cast, compared t~ processes known in the art.
Surprisingly, it has tPeen discovered that silazane compounds enhance the interaction of halobuityl elastomers with mineral fillers, resulting in is improved compound properties such as tensile strength and abrasion (DIN).
Silazane compounds are believed to disperse and bond the silica to the halogenated elastomers.
Accordingly, in another aspect the present invention provides a process which comprises mixing a halobutyl elastomer with at least one 2o mineral filler, in the presence of at least one silazane compound, and cuiring the resulting filled halobutyl elastomer. The resuilting composition, having improved properties, forms another aspect of the invention.
Additionally, it has been found that mixtures of silazane compounds and an additive containing at least one hydroxyl group and a functional group 2s containing a basic amine enhance the interaction of halobutyl elastomers with mineral fillers, resulting in improved compound properties such as tensile strength and abrasion resistance (DIN).
Accordingly, in another aspect the present invention provide, a process which comprises mixing a halobutyl elastomer with at least one 3o mineral filler, in the presence of at least one silazane compound and one additive containing at least one hydroxyl group and a functional group containing a basic amine, .and curing the resulting filled halobutyl elastorner.
The resulting composition, having improved properties, forms another aspect of the invention.
Silica-Filled elastomeric compounds Field of the invention The present invention relates to silica-filled halogenated k>utyl s elastomers, in particular bromobutyl elastomers (BIIR).
Background of the invention:
It is known that reinforcing fillers such as carbon black and silica greatly improve the strength and fatigue properties of elastomeric compounds.
io It is also known that chemical interaction occurs between the elastomer and the filler. For example, good interaction between carbon black and highly unsaturated elastomers such as polybutadiene (BR) and styrene butadiene copolymers (SBR) occurs because of the large number of carbon-carbon double bonds present in these copolymers. Butyl elastomers may have only Is one tenth, or fewer, of the carbon-carbon double bonds found in BR or SBR, and compounds made from butyl elastomers are known to interact poorly with carbon black. For example, a compound prepared by mixing carbon black with a combination of BR and butyl elastomers results in domains of BR, which contain most of the carbon black, and butyl domains which contain very 20 little carbon black. It is also known that butyl compounds have poor abrasion resistance.
Canadian Patent Application 2,293,149 shows that it is possible to produce filled butyl elastomer compositions with much improved properties by combining halobutyl elastomers with silica and specific silanes. These silanes 2s act as dispersing and bonding agents between the halogenated butyl elastomer and the filler. However, one disadvantage of the use of silanes is the evolution of alcohol during the process of manufacture and potentially during the use of the manufactured article produced by this process.
Additionally, silanes significantly increase the cost of the resulting 3o manufactured article.
Co-pending Canadian Patent Application 2,339,080 discloses milled halobutyl elastomeric compounds comprising certain organic compounds containing at least one basic nitrogen-containing group and at least one I
hydroxyl group enhance the interaction of halobutyl elastomers with carhon-black and mineral fillers, resulting in improved compound properties suci'n as tensile strength and abrasion (DIN).
s Summary of the Inventiion:
The present invention provides a process for preparing compositions comprising halobutyl elastomers, at feast one mineral filler and at least one silazane compound. The invention also provides filled halobutyl elastc~mer compositions comprising halobutyl elastomers, at least one mineral filler and to at least one silazane compound. In particular it provides a means to produce such filled compositions without the evolution of alcohol, and at significantly reduced cast, compared t~ processes known in the art.
Surprisingly, it has tPeen discovered that silazane compounds enhance the interaction of halobuityl elastomers with mineral fillers, resulting in is improved compound properties such as tensile strength and abrasion (DIN).
Silazane compounds are believed to disperse and bond the silica to the halogenated elastomers.
Accordingly, in another aspect the present invention provides a process which comprises mixing a halobutyl elastomer with at least one 2o mineral filler, in the presence of at least one silazane compound, and cuiring the resulting filled halobutyl elastomer. The resuilting composition, having improved properties, forms another aspect of the invention.
Additionally, it has been found that mixtures of silazane compounds and an additive containing at least one hydroxyl group and a functional group 2s containing a basic amine enhance the interaction of halobutyl elastomers with mineral fillers, resulting in improved compound properties such as tensile strength and abrasion resistance (DIN).
Accordingly, in another aspect the present invention provide, a process which comprises mixing a halobutyl elastomer with at least one 3o mineral filler, in the presence of at least one silazane compound and one additive containing at least one hydroxyl group and a functional group containing a basic amine, .and curing the resulting filled halobutyl elastorner.
The resulting composition, having improved properties, forms another aspect of the invention.
The halobutyl elastomer that is admixed with the mineral filler and the silazane compound or mixture of silazane compound and hydroxyl- and amine-containing additive may be a mixture with another elastomea° or elastomeric compound. Tt-ie halobutyl elastomer should constitute more than s 5% of any such mixture. Preferably the halobutyl elastomer should constitute at least 10% of any such mixture. In some cases it is preferred not to use mixtures but to use the halobutyl elastomer as the sole elastomer. If mixtures are to be used, however, then the other elastomer may be, for example, natural rubber, polybutadiene, styrene-butadiene or poly-chloroprene or' an to elastomer compound containing one or more of these elastomers.
The filled halobutyl elastomer can be cured 'to obtain a product wlhich has improved properties, f~~r instance in abrasion resistance, rolling resistance and traction. Curing can lae effected with sulfur. The preferred amount of sulfur is in the range of fre~m 0.3 to 2.0 parts by weight per hundred parts of is rubber. An activator, for example zinc oxide, may also be used, in an amount in the range of from 0.5 parts to 2 parts by weight. Other ingredients, for instance stearic acid, antioxidants, or accelerators may also be added to the elastomer prior to curing. Sulphur curing is then effected in the known manner. See, for instance, chapter 2, "The Compounding and Vulcanization 20 of Rubber", of "Rubber Technology", 3rd edition, published by Chapman &
Hall, 1995, the disclosure o~f which is incorporated b~y reference with regard to jurisdictions allowing for this procedure.
Other curatives knovvn to cure halobutyl elastomers may also be u:>ed.
A number of compounds. are known to cure halobutyl elastomers, for 2s example, such as bis dier~eophiles (for example m-phenyl-bis-maleinimide, HVA2), phenolic resins, annines, amino-acids, peroxides, zinc oxide and the like. Combinations of the aforementioned curatives may also be used.
The mineral-filled halobutyl elastomer of the iinvention can be admixed with other elastomers or elastomeric compounds before it is subjected to 3o curing with sulphur. This is discussed further below.
Detailed Descrir~ti~n of the Invention The phrase "halob~utyl elastomer(s)" as used herein refers to a chlorinated or brominated butyl elastomer. Brominated butyl elastomers are preferred, and the invention is illustrated, by way of example, with reference to such bromobutyl elastomers. It should be understood, however, that the invention extends to the use of chlorinated butyl elastomers.
Thus, halobutyl elastomers suitable for use in the practice of this s invention include, but are not limited to, brominated butyl elastomers. Such elastomers may be obtained by bromination of butyl rubber (which is a copolymer of an isoolefin, usually isobutylene and a co-monomer that is usually a Cq. to Cg conjugated diolefin, preferabl!~ isoprene - (bromin,ated isobutene-isoprene-copolymers BIIR)). Co-monomers other than conjugated to diolefins can be used, however, and mention is made of alkyl-substituted vrinyl aromatic co-monomers such as C1-Cq.-alkyl substituted styrene. An example of such an elastomer which is commercially available is brominated isobutylene methylstyrene copolymer (BIMS) in which the co-monomer is p-methylstyrene.
is Brominated butyl elastomers typically comprise in the range of from 0.1 to 10 weight percent of repeating units derived from diolefin (preferably isoprene) and in the range of from 90 to 99.9 weight percent of repeating units derived from isoolefin (prei~erably isobutylene) (based upon the hydrocarbon content of the polymer) and in the range of from 0.1 to 9 weight percent 2o bromine (based upon the bromobutyl polymer). A typical bromobutyl polymer has a molecular weight, expressed as the Mooney viscosity according to CIIV
53 523 (ML 1 + 8 at 125°C), in the range of from 25 to 60.
For use in the present invention the brominated butyl elastoimer preferably contains in the range of from 0.5 to 5 weight percent of repeating 2s units derived from isoprene (based upon the hydrocarbon content of the polymer) and in the range of from 95 to 99.5 weight percent of repeating units derived from isobutylene (based upon the hydrocarbon content of the polymer) and in the range of from 0.2 to 3 weight percent, preferably from 0.75 to 2.3 weight percent, of bromine (based upon the brominated butyl 3o polymer).
A stabilizer may be added to the brominated butyl elastomer. Suitable stabilizers include calcium stearate and epoxidized soy bean oil, preferably used in an amount in the range of from 0.5 to 5 parts by weight per 100 ~aarts by weight of the brominated butyl rubber (phr).
Examples of suitable brominated butyl elastomers include Bayer Bromobutyl~ 2030, Bayer Bromobutyl~ 2040 (882040), and Braver s Bromobutyl~ X2 commercially available from Bayer. Bayer BB2040 has a Mooney viscosity (ML 1 +8 @ 125°C) of 39 ~ 4, a bromine content of 2.0 ~: 0.3 wt% and an approximate molecular weight of 500,OCi0 grams per mole.
The brominated butyl elastomer used in the process of this invention may also be a graft copolymer of a brominated butyl rubber and a polymer io based upon a conjugated diofefin monomer. our co-pending Canadian Patent Application 2,279,085 is directed towards a process for preparing =;uch graft copolymers by mixing solid brominated butyl rubber with a solid polymer based on a conjugated diolefin monomer which also includes some C-S-(:5)n-C bonds, where n is an integer from 1 to 7, the mixing being carried out at a is temperature greater than 50°C and for a time sufficient to cause grafting. The disclosure of this application is incorporated herein by reference. The bromobutyl elastomer of the graft copolymer can be any of those described above. The conjugated diolefins that can be incorporated in the craft copolymer generally have tile structural formula:
~1 RI1 R-CH=C-C=Cf-I2 wherein R is a hydrogen atom or an alkyl group containing from 1 'to 8 carbon atoms and wherein R1 and R11 can be the same or different and are selected from the group consisting of hydrogen atoms and alkyl groups containing from 1 to 4 carbon atoms. Some representative non-limiting 2s examples of suitable conjugated diolefins include 1,3-butadiene, isoprene, methyl-1,3-pentadiene, 4-butyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene 1,3-hexadiene, 1,3-octacliene, 2,3-dibutyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-ethyl-1,3-butadiene and the like" Conjugated diolefin monomers containing from 4 to 8 carbon atoms are: preferred, 1,3-butadiene ~o and isoprene being especially preferred.
The polymer based on a conjugated dime monomer can be a homopolymer, or a copolymer of two or more conjugated diene monomers, or s a copolymer with a vinyl aromatic monomer.
The vinyl aromatic monomers which can optionally be used are selected so as to be copolymerizable with the conjugated diolefin monomers being employed. Generally, any vinyl aromatic mcmomer which is known to s polymerize with organo-alkali metal initiators can be used. Such winyl aromatic monomers usually contain in the range of from 8 to 20 carbon atoms, preferably from 8 to 14 carbon atoms. Some examples of vinyl aromatic monomers which can be so copolymerized include styrene, alpha-methyl styrene, various alkyl styrenes including p-methylstyrene, p-methoxy io styrene, 1-vinylnaphthalene, 2-vinyl naphthalene, 4-vinyl toluene and the like.
Styrene is preferred for copolymerization with 1,3-butadiene alone or for terpolymerization with both 1,3-butadiene and isoprene.
The halogenated butyl elastomer may be used alone or in combination with other elastomers such as:
is BR - polybutadiene ABR - butadienelC~-C4 alkyl acrylate copolymers CR - polychloroprene IR - polyisoprene SBR - styrene/butadiene copolymers with styrene contents of 1 2o to 60, ~areferably 20 to 50 wt.%
IIR - isobutylene/isoprene copolymers NBR - butadiene/acrylonitrile copolyrners with acrylonitrile contents of 5 to 60, preferably 10 to 40 wt.%
HNBR - partially hydrogenated or completely hydrogenated NE~R
2s EPDM - ethylenelpropyleneldiene copolymers The filler is compos~:d of particles of a mineral, and examples include silica, silicates, clay (such as bentonite), gypsum, alumina, titanium dioxide, talc and the like, as well as mixtures thereof.
Further examples are:
30 - highly disperse silicas, prepared e.g. by the precipitation of silicate solutions or the flame hydrolysis of silicon halides, with specific surface areas of 5 to 1000, preferably 20 to 400 m2lg (E3ET
specific surface area), and with primary particle sizes of 10 to 400 nm; the silicas can optionally also be present as mixed oxides with other metal oxides such as those of AI, Mg, Ca, Ba, Zn, Zr and Ti;
- synthetic silicates, such as aluminum silicate and alkaline earth metal silicate like s - magnesium silicate or calcium silicate, with BET specific suri~ace areas of 20 to 400 m2/g and primary particle diameters of 1 ~D to 400 nm;
- natural silicates, such as kaolin and other naturally occurring silica;
to - glass fibres and glass fibre products (matting, extrudates) or glass microspheres;
- metal oxides, such as zinc oxide, calcium oxide, magnesium o:Kide and aluminium oxide;
- metal carbonates, such as magnesium carbonate, calcium is carbonate and zinc carbonate;
- metal hydroxides, e.g. aluminium hydroxide and magnesium hydroxide;
or combinations thereof.
These mineral particles have hydroxyl groups on their surface, 2o rendering them hydrophilic and oleophobic. This exacerbates the difficulty of achieving good interaction between the filler particles and the butyl elastonner.
For many purposes, the preferred mineral is silica, especially silica prepared by the carbon dioxide precipitation of sodium silicate.
Dried amorphous silica particles suitable for use in accordance with the 2s invention have a mean agglomerate particle size in the range of from 1 to microns, preferably between 10 and 50 microns and most preferably between and 25 microns. It is preferred that less than 10 percent by volume of the agglomerate particles are below 5 microns or over 50 microns in size. A
suitable amorphous dried silica moreover has a BET surface area, measured 3o in accordance with DIN (Deutsche Industrie Norm) 66131, of between 50 ;end 450 square meters per gram and a DBP absorption, as measured in accordance with DIN 53601, of between 150 and 400 grams per 100 gram:; of silica, and a drying loss, as measured according to DIN ISO 787/11, of from 0 to 10 percent by weight. Suitable silica fillers are available under the trademarks HiSil~ 210, HiSil~ 233 and HiSil~ 243 from PPG Industries Inc.
Also suitable are VulkasilO S and Vulkasil~ N, from Bayer AG.
Those mineral filler can may be used in combination with known non-mineral fillers, such as s - carbon blacks; the carbon blacks to be used here are prepared by the lamp black, furnace black or gas black process and have 13ET
specific surface areas of 20 to 200 m~lg, e.g. SAF, ISAF, HAF, FEF or GPF carbon blacks;
or to - rubber gels, especially those ba sed on polybutadiene, butadiene/styrene copolymers, butadienelacrylonitrile copolymers and poiychloroprene.
Non-mineral fillers are not normally used as a filler in the halobutyl elastomer compositions of the invention, but in some embodiments they may zs be present in an amount up to 40 phr. It is preferred that the mineral miller should constitute at least 55% by weight of the total amount of filler. If the halobutyl elastomer composition of the invention is blended with another elastomeric composition, that other composition may contain mineral andlor non-mineral fillers.
2o The silazane compound can have one or more siiazane groups, ~e.g.
disilazanes. Organic silazane compounds are preferred. Examples include but are not limited to Hexamethyldisilazane, Heptamethyldisilazane, 1,1,3,3-Tetramethyldisilazane, 1,3-bis(Chloromethyl)tetramethyldisilazane, '9 ,3-Divinyl-1,1,3,3-tetramethyldisilazane, and 1,3-Diphenyltetramethyldisilazane.
2s Examples of additives which give enhanced physical properties to mixtures of halobutyl elastomers, filler and organic sulazanes include proteins, aspartic acid, 6-aminocaproic acid, diethanolamine and triethanolamine.
Preferably, the hydroxyl- <~nd amine-containing additive should contain a primary alcohol group and an amine group separated by methylene bridges, so which may be branched. Such compounds have the general formula HO~-A-NH2; wherein A represents a C1 to C20 alkylene group, which may be linear or branched.
s More preferably, the number of methylene groups between the two functional groups should be in the range of frorn 1 to 4. Example:9 of preferred additives include monoethanolamine and N,N-dimethyaminoalcohol.
The amount of filler to be incorporated into the halobutyl elastomer can s vary between wide limits. Typical amounts of filler range from 20 parts to parts by weight, preferably from 30 parts to 100 parts, more preferably from 40 to 80 parts per hundred parts of elastomer. The amount of the silazane compound is typically in the range of from 0.5 to 10 harts per hundred parts of elastomer, preferably of from 1 to 6, more preferably of from 2 to 5 parts per to hundred parts of elastomeir. The amount of hydroxyl- and amine-containing additive used in conjunction with the silazane compound is typically in the range of from 0.5 to 10 parts per hundred parts o~F elastomer, preferably of from 1 to 3 parts per hundred parts of elastomer.
Furthermore up to 4.0 parts of processing oil, preferably from 5 to 20 is parts, per hundred parts of elastomer, may be present. Further, a lubricant, for example a fatty acid such as stearic acid, may be present in an amount up to 3 parts by weight, more preferably in an amount up to 2 parts by weight.
The halobutyl elastomer(s), fillers) and silazane(s) or silazane/hydroxyl- and amine-containing additive mixtures are mixed togetlher, 2o suitably at a temperature in the range of from 25 to 200°C. It is preferred 'that the temperature in one of the mixing stages be greater than 60°C, and a temperature in the range of from 90 to 150°C is particularly preferred.
Normally the mixing time does not exceed one hour; a time in the range from 2 to 30 minutes is usually 'adequate. The mixing is suitably carried out on a 2s two-roll mill mixer, which pr~vides good dispersion of the filler within the elastomer. Mixing may also be carried out in a Banbury mixer, or in a Haake or Brabender miniature internal mixer. An extruder also provides good mixing, and has the further advantage that it permits shorter mixing times. It is also possible to carry out the mixing in two or more stages. Further, the 3o mixing can be carried out in different apparatuses, for example one stage rnay be carried out in an internal mixer and another in an extruder.
The enhanced interaction between the filler and the halobutyl elastomer results in improved properties for the filled elastomer. These POS r 1 10 C'A C'ON
improved properties include higher tensile strength, higher abrasion resistance, lower permeability and better dynamic properties. These render the filled elastomers particularly suitable for a number of applications, including, but not limited to, use in tire treads and tire sidewalls, tire s innerliners, tank linings, hoses, rollers, conveyor belts, curing bladders, gas masks, pharmaceutical enclosures and gaskets.
In a preferred embodiment of the inverrtian, bromabutyl elastomer, silica particles, sifazane compound or silazane/hydroxyl- and amine-containing additive mixture and, optionally, processing oil extender are mixed ~o on a two-roll mill at a nominal mill temperature of 25°C. The mixed compound is then placed on a two-roll mill and mixed at a temperature above 60°C. It is preferred that the temperature of the mixing is not too high, and more preferably does not exceed 150°C, since higher temperatures may cause curing to proceed undesirably far and thus impede subsequent processing.
is The product of mixing these four ingredients at a temperature not exceeding 150°C is a compound which has good stress/strain properties and which can be readily processed further on a warm mill with the addition of curatives.
The filled halobutyl rubber compositions. of the invention, and in particular filled bromobutyl rubber compositions, find many uses, but mention 2o is made particularly of use in tire tread compositions. Important features of a tire tread composition are that it shall have low rolling resistance, good traction, particularly in the wet, and good abrasion resistance so that it is resistant to wear. Compositions of the invention display these desirable properties. Thus, an indicator of traction is tan b at 0°C, with a high tan 8 at zs 0°C correlating with good traction. An indicator of rolling resistance is tan 8 at 60°C, with a low tan 8 at 60°C correlating with low rolling resistance. Rolling resistance is a measure of the resistance to forward movement of the tire, and !ow rolling resistance is desired to reduce fuel cansumption. Low values of loss modules at 60°C are also indicators of lo~nr rolling resistance.
As is 3o demonstrated in the exarnples below, compositions of the invention display high tan d at 0°C, low tan ~S at 60°C and low Toss modules at 60°C.
The invention is furi:her illustrated in the following examples.
lo EXs'1t11p1eS
Descrit~tion of tests:
Abrasion resistance:
s DIN 53-516 (60 grit Emery paper) Dynamic Property Testing:
Dynamic testing (tan 8 at 0°C and 60°C, Loss modulus at 60°C) were carried out using the GABO. The GABO is a dynamic mechanical analyzer for characterizing the properties of vulcanized elastomeric materials. The to dynamic mechanical properties give a measure of traction with the best traction usually obtained with high values of tan 8 at 0°C. Low values of tan 8 at 60°C, and in particular, low loss moduli at 60°C are indicators of low rolling resistance. RPA measurements were obtained vvith the use of an Alpha Technologies RPA 2000 operating at 10U °C at a frequency of 6 cpm.
Strain is sweeps were measured at strains of 0.1, 0.2, 0.5, 1, 2, 5, 10, 20, 50 and 90 °.
Cure rheomefry:
ASTM D 52-89 MDR2000E Rheometer at 1 ° arc and 1.7 Hz Description of Ingredients and General Mixing Procedure:
2o Hi-Sil~ 233 - silica - a product of PPG
Sunpar~ 2280 - paraffinic oil produced by Sun Oil Maglite~ D - magnesium oxide produced by CP Hall The brominated butyl elastomer (in all cases commercial Bayer~
Bromobutyl 2030) silica, oil and silazane or silazane/hydroxyl- and amine-2s containing additive mixture were mixed on either:
i) a tangential Banbury internal mixer operating at 77 rpm while being thermally regulated with the use of a Mokon get to 40 °C. Compounds were mixed for a total of 6 minutes. The final rubber temperature ranged from 140 °C to 180 °C.
3o ii) a 6" X 12" two-roll mill with the rolls running at 24 and 32 rpm. The mill roll was set at 25°C, with a total incorporation time of 10 minutes.
The mixed compounds were then "heat treated" for a further 10 minutes with the roll temperature at 110°C. The final rubber temperature was 125°C.
Curatives were then added to the cooled sample with the mill at 25°C.
s Examale 1 The affect of silazane incorporation into halogenated butyl elastomer/silica compounds was investigated via the formulation of several compounds of which hexamethyldisilazane (HMDZ) was incorporated as the silazane compound. For comparison, a halogenated butyl elastomer/silica to compound with no silazane was also prepared as a control compound.
Brominated isoprene isobutyfene rubber (BIIR) was mixed with the silazane and 60 parts per hundred rubber (phr) of silica filler (HiSil~ 233) in a tangential Banbury mixer under the mixing conditions described above.
Identical curative ingredients (1 phr of stearic acid, 0.5 phr of sulfur, and 1.5 Is phr of Zn0) were then added on a cool mill to each of the compounds. The compounds were then cured for either tc(gp) + 10 minutes at 170°C (for DIN
Abrasion testing) or tc(g0) + 5 minutes at 170°C and tested. Tables 1 and 2 gives the product compositions, and physical property data for the HMDZ
containing compounds and for a compound containing no filler bonding agent.
2o The data in Table 1 clearly shows the effect of adding HMDZ to assist in the bonding and dispersion of the siliceous filler in the brominated butyl elastomer. The ratio M300/M100 is commonly used as a relative measure of the degree of filler reinforcement in an elastomer compound (the higher the ratio the higher the reinforcement). While the M300IM100 for compound 1d 2s with no HMDZ (example 1d will here in be used as the control compound for the remaining examples) is 1.97 the M300/M100 values for the compounds containing HMDZ ranges from 3.~6 to 4.13. (See Figure 1 ). The value of the complex modulus (G*, MPa) at low strains obtained from RPA measurements is commonly used as a relative measure of the degree of filler reinforcement 3o in an elastomer compound (the lower the value of G*, the higher the degree of filler dispersion). From the data in Table 1, it is clear that a significant improvement in filler dispersion is observed on the addition of HMDZ to brominated butyl rubberlsilica compounds. Specifically, for the control compound, the G* value is 2934 MPa while for the compounds containing HMDZ, this value ranges from 365 to 631 MPa (See Figure 2).
Importantly, the data in Table 1 also shows that the improvement in filler dispersion and bonding does not effect the overall processability of the s resulting compound. On examination of the Mooney Scorch data presented in Table 1 and Figure 3, it can be seen that the incorporation of HMDZ into these brominated butyl rubberlsilica compounds significantly improves the scorch safety (i.e. increase in the t03 times).
With respect to the performance of these compounds in tires treads, to tan 8 values at 0 °C and 60 °C as well as loss modulus (G", MPa) values at 60 °C are quoted. Specifically, high tan 8 values at 0 °C are indicative of good traction while low values of tan ~ at 60 °C and low values of G" at 60 °C are indicative of low rolling resistance. From the data presented in Table 2, the positive effects of HMDZ on the tan ~ value at 0 °C and the G" value at 60 °C
is are seen. While the control compound possesses a tan 8 (0 °C) of 0.23 and a G" (60 °C) of 3.33 MPa, compounds containing HMDZ possess tan s (0 °C) values ranging from 0.49 to 0.88 and G" (60 °C) values ranging from 0.93 to 1.98 MPa.
2o Example 2 Co-pending Canadian Patent Application 2,339,080 illustrates the utility of additives containing at least one hydroxyl group and at least one substituent bearing a basic amine group in the dispersion and reinforcement of silica in halogenated butyl elastomer compounds. Given the positive effect 2s seen through the introduction of HMDZ into halogenated butyl elastomer/silica compounds, mixtures of HMDZ and hydroxyl- and amine-containing additives of the type described above were examined. This example investigates the effect of incorporating mixtures of HMDZ and monoethanolamine (MEA) into halogenated butyl elastomerlsilica compounds prepared in a Banbury internal 3o mixer.
Brominated isoprene isobutylene rubber (BIIR) was mixed with the additives and 60 parts per hundred rubber (phr) of silica filler (HiSil~ 233) in a tangential Banbury mixer under the mixing conditions described above.
Identical curative ingredients (1 phr of stearic acid, 0.5 phr of sulfur, and 1.5 phr of Zn0) were then added on a cool mill to each of the compounds. The compounds were then cured for either tc(g0) + 10 minutes at 170°C (for DIN
Abrasion testing) or tc(g0) + 5 minutes at 170°C and tested. Tables 3 and 4 s gives the product compositions, and physical property data for the HMDZ/MEA containing cornpounds and for a compound containing only MEA.
The data in Table 3 clearly shows the effect of adding HMDZ and MEA
to assist in the bonding and dispersion of the filler in the brominated butyl elastomer. While the M300/M100 for the control compound is 1.97, the to compounds containing HMDZ and MEA possess M300/M100 values ranging from 2.79 to 4.30 (See Figure 4). Additionally, a :significant improvement in filler dispersion is observed on the addition of HMD,Z and MEA to brominated butyl rubberlsilica compounds. Specifically, for the control compound, the G*
value is 2934 MPa while for the compounds containing HMDZ and MEA, this is value ranges from 304 to 1609 MPa (See Figure 5). The incorporation of 2.9 phr of HMDZ and 2.2 phr of MEA or 2.9 phr of HMDZ and 1.1 phr of MEA is seen to improve the degree of filler dispersion over' what is observed for the compound which only contains MEA.
While the data in Table 3 suggests the addition of HMDZ into 2o halogenated butyl elastomerlsilicalMEA compounds lowers the M300/M100 values and increases the DIN abrasion volume loss, it is important to note the significant improvement in scorch safety as evideroce by the increased t03 times.
From the data presented in Tabfe 4, the positive efFects of HMDZ and 2s MEA on the tan 8 value at 0 °C and the G" value at 60 °C are seen. While the control compound possesses a tan S (0 °C) of 0.23 and a G" (60 °C) value of 3.33 MPa, compounds containing HMDZ and ME,A possess tan 8 (0 °C) values ranging from 0.43 to 0.85 and G" (60 °C) values ranging from 1.10 to 2.39 MPa. Furthermore, compounds which contain 2.9 phr of HMDZ and 2.2 3o phr of MEA and compounds which contain 2.9 phr of HMDZ and 1.1 phr of MEA possess superior tan 8 (0 °C) and G" (60 °C) values than does the halogenated butyl elastomer/silica compound which ~only contains MEA.
Example 3 This example investigates the effect of incorporating mixtures of HMDZ
and monoethanolamine (MEA) into halogenat~ed butyl elastomerlsilica compounds prepared on a 6" x 12" mill.
s Brominated isoprene isobutyiene rubber (BIIR) was mixed with the additives and 60 parts per hundred rubber (phr) of silica filler (HiSil~ 233) on a 6" x 12" mill under the mixing conditions described above. Identical curative ingredients (1 phr of stearic acid, 0.5 phr of sulfur, and 1.5 phr of Zn0) were then added to each of these compounds on a cool mill. The compounds were to then cured for either tc(g0) + 10 minutes at 170°C (for DIN Abrasion testing) or tc(g0) + 5 minutes at 170°C and tested. Tables 5 and 6 gives the product compositions, and physical property data for the HMDZIMEA containing compounds and for a compound containing only MEA.
The data in Table 5 clearly shows the effect of adding HMDZ and MEA
is to assist in the bonding and dispersion of the filler in the brominated butyl elastomer. While the M300/M100 for the control compound is 1.97, the compounds containing HMDZ and MEA possess M300/M100 values ranging from 4.02 to 6.00. (See Figure 6). Additionally, a significant improvement in filler dispersion is observed on the addition of HMD;Z and MEA to brominated 2o butyl rubber/silica compounds. Specifically, for the control compound, the G*
value is 2934 MPa while for the compounds containing HMDZ and MEA, this value ranges from 256 to 538 MPa (See Figure 7). The incorporation of HMDZ in conjunction with MEA is seen to improve both the degree of reinforcement (M300/M100) and of filler dispersion (G* at low strains) over 2s what is observed for the compound which contains only MEA.
The data in Table 5 also suggests that the addition of HMDZ into halogenated butyl elastomer/silica/MEA compounds lowers the DIN abrasion volume loss when compared to both the control compound and the compound which contains only MEA.
3o From the data presented in Table 6, the positive effects of HMDZ and MEA on the tan 8 value at 0 °C and the G" value at 60 °C are seen. While the control compound possesses a tan ~ (0 °C) of 0.23 and a G" (60 °C) of 3.33 MPa, compounds containing HMDZ and MEA pos sass tan s (0 °C) values is ranging from 0.50 to 0.86 and G" (60 °C) values ranging from 0.69 to 1.78 MPa. Furthermore, compounds which contain both HMDZ and MEA possess superior tan 8 (0 °C) and G" (60 °C) values than does the halogenated butyl elastomerlsilica compound which contains only MEA.
s Examale 4 This example investigates the effect of incorporating mixtures of HMDZ
and N,N-dimethylaminoethanol (DMAE) into halogenated butyl elastomerlsilica compounds prepared in a Banbury.
to Brominated isoprene isobutylene rubber (BIIR) was mixed with the additives and 60 parts per hundred rubber (phr) of silica filler (HiSil~ 233) in a tangential Banbury mixer under the mixing conditions described above.
Identical curative ingredients (1 phr of stearic acid, 0.5 phr of sulfur, and 1.5 phr of Zn0) were then added on a cool mill to each of these compounds. The is compounds were then cured for either tc(gp) + 10 minutes at 170°C
(for D1N
Abrasion testing) or tc(g0) + 5 minutes at 170°C and tested. Tables 7 and 8 give the product compositions, and physical property data for the HMDZ/DMAE containing compounds and for a compound containing only DMAE.
2o The data in Table 7 clearly shows the effect of adding HMDZ and DMAE to assist in the bonding and dispersion of the filler in the brominated butyl elastomer. While the M3001M100 for the control compound is 1.97, the compounds containing HMDZ and DMAE possess M3001M100 values ranging from 2.93 to 4.27. (See Figure 8). Additionally, a significant improvement in 2s filler dispersion is observed on the addition of HMDZ and DMAE to brominated butyl rubberlsilica compounds. Specificarly, for the control compound, the G* value is 2934 MPa while for the compounds containing HMDZ and MEA, this value ranges from 227 to 1056 MPa (See Figure 9).
The incorporation of 2.9 phr of HMDZ and 3.2 phr of DMAE or 2.9 phr of 3o HMDZ and 1.6 phr of DMAE is seen to improve the degree of filler dispersion over what is observed for the compound which contains only DMAE.
While the data in Table 7 suggests the addition of HMDZ into halogenated butyl elastomer/silica/DMAE compounds lowers the M300/M100 values and increases the DIN abrasion volume loss, it is important to note the significant improvement in scorch safety as evidence by the increased t03 times possessed by these compounds.
From the data presented in Table 8, the positive effects of HMDZ and s DMAE on the tan 8 value at 0 °C and the G" value at 60 °C are seen. While the control compound possesses a tan ~ (0 °C) of 0.23 and a G~ (60 °C) of 3.33 MPa, compounds containing HMDZ and DMAE possess tan 8 (0 °C) values ranging from 0.45 to 0.82 and G" (60 °C) values ranging from 0.48 to 2.31 MPa. Furthermore, compounds which contain 2.9 phr of HMDZ and 3.2 to phr of DMAE or 2.9 phr of HMDZ and 1.6 phr of DMAE possess superior tan 8 (0 °C) and G" (60 °C) values than does the halogenated butyl elastomerlsilica compound which contains only DMAE.
Example 5 is This example investigates the effect of incorporating mixtures of HMDZ
and N,N-dimethylaminoethanof (DMAE) into halogenated butyl elastomerlsilica compounds prepared on a 6" x 12" mill.
Brominated isoprene isobutylene rubber (BIIR) was mixed with the additives and 60 parts per hundred rubber (phr) of silica filler (HiSil~ 233) on 2o a 6" x 12" mill under the mixing conditions described above. Identical curative ingredients (1 phr of stearic acid, 0.5 phr of sulfur, and 1.5 phr of Zn0) were then added on a cool mill to each of these compounds. The compounds were then cured for either tc(gp) + 10 minutes at 170°C (for DIN Abrasion testing) or tc(gp) + 5 minutes at 170°C and tested. Tables 9 and 10 give the product 2s compositions, and physical property data for the HMDZ/DMAE containing compounds and for a compound containing only DMAE.
The data in Table 9 clearly shows the effect of adding HMDZ and DMAE to assist in the bonding and dispersion of the filler in the brominated butyl elastomer. While the M300/M100 for the control compound is 1.97, the 3o compounds containing HMDZ and DMAE possess M300/M100 values ranging from 4.41 to 6.55. (See Figure 10). Additionally, a significant improvement in filler dispersion is observed on the addition of HMDZ and DMAE to brominated butyl rubber/silica compounds. Specifically, for the control m compound, the G* value is 2934 MPa while for the compounds containing HMDZ and MEA, this value ranges from 245 to T42 MPa (See Figure 11 ).
The incorporation of 2.9 phr of FiMDZ and 3.2 phr of DMAE or 2.9 phr of HMDZ and 1.6 phr of DMAE is seen to improve both the degree of s reinforcement (M300/M100) and of filter dispersion (G* at low strains) over what is observed for the compound which contains only DMAE.
The Mooney Scorch data presented in Table 9 also illustrates the positive impact on the t03 times (increased t03 times imply improved processability) observed on addition of HMDZ to halogenated butyl to elastomerlsilica/DMAE compounds.
From the data presented in Table 10, the positive effects of HMDZ and DMAE on the tan 8 value at 0 °C and the G~ value at 60 °C
are seen. While the control compound possesses a tan ~ (0 °C) of 0.23 and a G" (60 °C) of 3.33 MPa, compounds containing HMDZ and DMAE possess tan 8 (0 °C) is values ranging from 0.56 to 0.86 and G" (60 °C) values ranging from 0.42 to 1.61 MPa. Furthermore, compounds which contain 2.9 phr of HMDZ and 3.2 phr of DMAE or 2.9 phr of HMDZ and 1.6 phr of DMAE possess superior tan ~
(0 °C) and G" (60 °C) values than does the halogenated butyl elastomerlsilica compound which contains only DMAE.
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The filled halobutyl elastomer can be cured 'to obtain a product wlhich has improved properties, f~~r instance in abrasion resistance, rolling resistance and traction. Curing can lae effected with sulfur. The preferred amount of sulfur is in the range of fre~m 0.3 to 2.0 parts by weight per hundred parts of is rubber. An activator, for example zinc oxide, may also be used, in an amount in the range of from 0.5 parts to 2 parts by weight. Other ingredients, for instance stearic acid, antioxidants, or accelerators may also be added to the elastomer prior to curing. Sulphur curing is then effected in the known manner. See, for instance, chapter 2, "The Compounding and Vulcanization 20 of Rubber", of "Rubber Technology", 3rd edition, published by Chapman &
Hall, 1995, the disclosure o~f which is incorporated b~y reference with regard to jurisdictions allowing for this procedure.
Other curatives knovvn to cure halobutyl elastomers may also be u:>ed.
A number of compounds. are known to cure halobutyl elastomers, for 2s example, such as bis dier~eophiles (for example m-phenyl-bis-maleinimide, HVA2), phenolic resins, annines, amino-acids, peroxides, zinc oxide and the like. Combinations of the aforementioned curatives may also be used.
The mineral-filled halobutyl elastomer of the iinvention can be admixed with other elastomers or elastomeric compounds before it is subjected to 3o curing with sulphur. This is discussed further below.
Detailed Descrir~ti~n of the Invention The phrase "halob~utyl elastomer(s)" as used herein refers to a chlorinated or brominated butyl elastomer. Brominated butyl elastomers are preferred, and the invention is illustrated, by way of example, with reference to such bromobutyl elastomers. It should be understood, however, that the invention extends to the use of chlorinated butyl elastomers.
Thus, halobutyl elastomers suitable for use in the practice of this s invention include, but are not limited to, brominated butyl elastomers. Such elastomers may be obtained by bromination of butyl rubber (which is a copolymer of an isoolefin, usually isobutylene and a co-monomer that is usually a Cq. to Cg conjugated diolefin, preferabl!~ isoprene - (bromin,ated isobutene-isoprene-copolymers BIIR)). Co-monomers other than conjugated to diolefins can be used, however, and mention is made of alkyl-substituted vrinyl aromatic co-monomers such as C1-Cq.-alkyl substituted styrene. An example of such an elastomer which is commercially available is brominated isobutylene methylstyrene copolymer (BIMS) in which the co-monomer is p-methylstyrene.
is Brominated butyl elastomers typically comprise in the range of from 0.1 to 10 weight percent of repeating units derived from diolefin (preferably isoprene) and in the range of from 90 to 99.9 weight percent of repeating units derived from isoolefin (prei~erably isobutylene) (based upon the hydrocarbon content of the polymer) and in the range of from 0.1 to 9 weight percent 2o bromine (based upon the bromobutyl polymer). A typical bromobutyl polymer has a molecular weight, expressed as the Mooney viscosity according to CIIV
53 523 (ML 1 + 8 at 125°C), in the range of from 25 to 60.
For use in the present invention the brominated butyl elastoimer preferably contains in the range of from 0.5 to 5 weight percent of repeating 2s units derived from isoprene (based upon the hydrocarbon content of the polymer) and in the range of from 95 to 99.5 weight percent of repeating units derived from isobutylene (based upon the hydrocarbon content of the polymer) and in the range of from 0.2 to 3 weight percent, preferably from 0.75 to 2.3 weight percent, of bromine (based upon the brominated butyl 3o polymer).
A stabilizer may be added to the brominated butyl elastomer. Suitable stabilizers include calcium stearate and epoxidized soy bean oil, preferably used in an amount in the range of from 0.5 to 5 parts by weight per 100 ~aarts by weight of the brominated butyl rubber (phr).
Examples of suitable brominated butyl elastomers include Bayer Bromobutyl~ 2030, Bayer Bromobutyl~ 2040 (882040), and Braver s Bromobutyl~ X2 commercially available from Bayer. Bayer BB2040 has a Mooney viscosity (ML 1 +8 @ 125°C) of 39 ~ 4, a bromine content of 2.0 ~: 0.3 wt% and an approximate molecular weight of 500,OCi0 grams per mole.
The brominated butyl elastomer used in the process of this invention may also be a graft copolymer of a brominated butyl rubber and a polymer io based upon a conjugated diofefin monomer. our co-pending Canadian Patent Application 2,279,085 is directed towards a process for preparing =;uch graft copolymers by mixing solid brominated butyl rubber with a solid polymer based on a conjugated diolefin monomer which also includes some C-S-(:5)n-C bonds, where n is an integer from 1 to 7, the mixing being carried out at a is temperature greater than 50°C and for a time sufficient to cause grafting. The disclosure of this application is incorporated herein by reference. The bromobutyl elastomer of the graft copolymer can be any of those described above. The conjugated diolefins that can be incorporated in the craft copolymer generally have tile structural formula:
~1 RI1 R-CH=C-C=Cf-I2 wherein R is a hydrogen atom or an alkyl group containing from 1 'to 8 carbon atoms and wherein R1 and R11 can be the same or different and are selected from the group consisting of hydrogen atoms and alkyl groups containing from 1 to 4 carbon atoms. Some representative non-limiting 2s examples of suitable conjugated diolefins include 1,3-butadiene, isoprene, methyl-1,3-pentadiene, 4-butyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene 1,3-hexadiene, 1,3-octacliene, 2,3-dibutyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-ethyl-1,3-butadiene and the like" Conjugated diolefin monomers containing from 4 to 8 carbon atoms are: preferred, 1,3-butadiene ~o and isoprene being especially preferred.
The polymer based on a conjugated dime monomer can be a homopolymer, or a copolymer of two or more conjugated diene monomers, or s a copolymer with a vinyl aromatic monomer.
The vinyl aromatic monomers which can optionally be used are selected so as to be copolymerizable with the conjugated diolefin monomers being employed. Generally, any vinyl aromatic mcmomer which is known to s polymerize with organo-alkali metal initiators can be used. Such winyl aromatic monomers usually contain in the range of from 8 to 20 carbon atoms, preferably from 8 to 14 carbon atoms. Some examples of vinyl aromatic monomers which can be so copolymerized include styrene, alpha-methyl styrene, various alkyl styrenes including p-methylstyrene, p-methoxy io styrene, 1-vinylnaphthalene, 2-vinyl naphthalene, 4-vinyl toluene and the like.
Styrene is preferred for copolymerization with 1,3-butadiene alone or for terpolymerization with both 1,3-butadiene and isoprene.
The halogenated butyl elastomer may be used alone or in combination with other elastomers such as:
is BR - polybutadiene ABR - butadienelC~-C4 alkyl acrylate copolymers CR - polychloroprene IR - polyisoprene SBR - styrene/butadiene copolymers with styrene contents of 1 2o to 60, ~areferably 20 to 50 wt.%
IIR - isobutylene/isoprene copolymers NBR - butadiene/acrylonitrile copolyrners with acrylonitrile contents of 5 to 60, preferably 10 to 40 wt.%
HNBR - partially hydrogenated or completely hydrogenated NE~R
2s EPDM - ethylenelpropyleneldiene copolymers The filler is compos~:d of particles of a mineral, and examples include silica, silicates, clay (such as bentonite), gypsum, alumina, titanium dioxide, talc and the like, as well as mixtures thereof.
Further examples are:
30 - highly disperse silicas, prepared e.g. by the precipitation of silicate solutions or the flame hydrolysis of silicon halides, with specific surface areas of 5 to 1000, preferably 20 to 400 m2lg (E3ET
specific surface area), and with primary particle sizes of 10 to 400 nm; the silicas can optionally also be present as mixed oxides with other metal oxides such as those of AI, Mg, Ca, Ba, Zn, Zr and Ti;
- synthetic silicates, such as aluminum silicate and alkaline earth metal silicate like s - magnesium silicate or calcium silicate, with BET specific suri~ace areas of 20 to 400 m2/g and primary particle diameters of 1 ~D to 400 nm;
- natural silicates, such as kaolin and other naturally occurring silica;
to - glass fibres and glass fibre products (matting, extrudates) or glass microspheres;
- metal oxides, such as zinc oxide, calcium oxide, magnesium o:Kide and aluminium oxide;
- metal carbonates, such as magnesium carbonate, calcium is carbonate and zinc carbonate;
- metal hydroxides, e.g. aluminium hydroxide and magnesium hydroxide;
or combinations thereof.
These mineral particles have hydroxyl groups on their surface, 2o rendering them hydrophilic and oleophobic. This exacerbates the difficulty of achieving good interaction between the filler particles and the butyl elastonner.
For many purposes, the preferred mineral is silica, especially silica prepared by the carbon dioxide precipitation of sodium silicate.
Dried amorphous silica particles suitable for use in accordance with the 2s invention have a mean agglomerate particle size in the range of from 1 to microns, preferably between 10 and 50 microns and most preferably between and 25 microns. It is preferred that less than 10 percent by volume of the agglomerate particles are below 5 microns or over 50 microns in size. A
suitable amorphous dried silica moreover has a BET surface area, measured 3o in accordance with DIN (Deutsche Industrie Norm) 66131, of between 50 ;end 450 square meters per gram and a DBP absorption, as measured in accordance with DIN 53601, of between 150 and 400 grams per 100 gram:; of silica, and a drying loss, as measured according to DIN ISO 787/11, of from 0 to 10 percent by weight. Suitable silica fillers are available under the trademarks HiSil~ 210, HiSil~ 233 and HiSil~ 243 from PPG Industries Inc.
Also suitable are VulkasilO S and Vulkasil~ N, from Bayer AG.
Those mineral filler can may be used in combination with known non-mineral fillers, such as s - carbon blacks; the carbon blacks to be used here are prepared by the lamp black, furnace black or gas black process and have 13ET
specific surface areas of 20 to 200 m~lg, e.g. SAF, ISAF, HAF, FEF or GPF carbon blacks;
or to - rubber gels, especially those ba sed on polybutadiene, butadiene/styrene copolymers, butadienelacrylonitrile copolymers and poiychloroprene.
Non-mineral fillers are not normally used as a filler in the halobutyl elastomer compositions of the invention, but in some embodiments they may zs be present in an amount up to 40 phr. It is preferred that the mineral miller should constitute at least 55% by weight of the total amount of filler. If the halobutyl elastomer composition of the invention is blended with another elastomeric composition, that other composition may contain mineral andlor non-mineral fillers.
2o The silazane compound can have one or more siiazane groups, ~e.g.
disilazanes. Organic silazane compounds are preferred. Examples include but are not limited to Hexamethyldisilazane, Heptamethyldisilazane, 1,1,3,3-Tetramethyldisilazane, 1,3-bis(Chloromethyl)tetramethyldisilazane, '9 ,3-Divinyl-1,1,3,3-tetramethyldisilazane, and 1,3-Diphenyltetramethyldisilazane.
2s Examples of additives which give enhanced physical properties to mixtures of halobutyl elastomers, filler and organic sulazanes include proteins, aspartic acid, 6-aminocaproic acid, diethanolamine and triethanolamine.
Preferably, the hydroxyl- <~nd amine-containing additive should contain a primary alcohol group and an amine group separated by methylene bridges, so which may be branched. Such compounds have the general formula HO~-A-NH2; wherein A represents a C1 to C20 alkylene group, which may be linear or branched.
s More preferably, the number of methylene groups between the two functional groups should be in the range of frorn 1 to 4. Example:9 of preferred additives include monoethanolamine and N,N-dimethyaminoalcohol.
The amount of filler to be incorporated into the halobutyl elastomer can s vary between wide limits. Typical amounts of filler range from 20 parts to parts by weight, preferably from 30 parts to 100 parts, more preferably from 40 to 80 parts per hundred parts of elastomer. The amount of the silazane compound is typically in the range of from 0.5 to 10 harts per hundred parts of elastomer, preferably of from 1 to 6, more preferably of from 2 to 5 parts per to hundred parts of elastomeir. The amount of hydroxyl- and amine-containing additive used in conjunction with the silazane compound is typically in the range of from 0.5 to 10 parts per hundred parts o~F elastomer, preferably of from 1 to 3 parts per hundred parts of elastomer.
Furthermore up to 4.0 parts of processing oil, preferably from 5 to 20 is parts, per hundred parts of elastomer, may be present. Further, a lubricant, for example a fatty acid such as stearic acid, may be present in an amount up to 3 parts by weight, more preferably in an amount up to 2 parts by weight.
The halobutyl elastomer(s), fillers) and silazane(s) or silazane/hydroxyl- and amine-containing additive mixtures are mixed togetlher, 2o suitably at a temperature in the range of from 25 to 200°C. It is preferred 'that the temperature in one of the mixing stages be greater than 60°C, and a temperature in the range of from 90 to 150°C is particularly preferred.
Normally the mixing time does not exceed one hour; a time in the range from 2 to 30 minutes is usually 'adequate. The mixing is suitably carried out on a 2s two-roll mill mixer, which pr~vides good dispersion of the filler within the elastomer. Mixing may also be carried out in a Banbury mixer, or in a Haake or Brabender miniature internal mixer. An extruder also provides good mixing, and has the further advantage that it permits shorter mixing times. It is also possible to carry out the mixing in two or more stages. Further, the 3o mixing can be carried out in different apparatuses, for example one stage rnay be carried out in an internal mixer and another in an extruder.
The enhanced interaction between the filler and the halobutyl elastomer results in improved properties for the filled elastomer. These POS r 1 10 C'A C'ON
improved properties include higher tensile strength, higher abrasion resistance, lower permeability and better dynamic properties. These render the filled elastomers particularly suitable for a number of applications, including, but not limited to, use in tire treads and tire sidewalls, tire s innerliners, tank linings, hoses, rollers, conveyor belts, curing bladders, gas masks, pharmaceutical enclosures and gaskets.
In a preferred embodiment of the inverrtian, bromabutyl elastomer, silica particles, sifazane compound or silazane/hydroxyl- and amine-containing additive mixture and, optionally, processing oil extender are mixed ~o on a two-roll mill at a nominal mill temperature of 25°C. The mixed compound is then placed on a two-roll mill and mixed at a temperature above 60°C. It is preferred that the temperature of the mixing is not too high, and more preferably does not exceed 150°C, since higher temperatures may cause curing to proceed undesirably far and thus impede subsequent processing.
is The product of mixing these four ingredients at a temperature not exceeding 150°C is a compound which has good stress/strain properties and which can be readily processed further on a warm mill with the addition of curatives.
The filled halobutyl rubber compositions. of the invention, and in particular filled bromobutyl rubber compositions, find many uses, but mention 2o is made particularly of use in tire tread compositions. Important features of a tire tread composition are that it shall have low rolling resistance, good traction, particularly in the wet, and good abrasion resistance so that it is resistant to wear. Compositions of the invention display these desirable properties. Thus, an indicator of traction is tan b at 0°C, with a high tan 8 at zs 0°C correlating with good traction. An indicator of rolling resistance is tan 8 at 60°C, with a low tan 8 at 60°C correlating with low rolling resistance. Rolling resistance is a measure of the resistance to forward movement of the tire, and !ow rolling resistance is desired to reduce fuel cansumption. Low values of loss modules at 60°C are also indicators of lo~nr rolling resistance.
As is 3o demonstrated in the exarnples below, compositions of the invention display high tan d at 0°C, low tan ~S at 60°C and low Toss modules at 60°C.
The invention is furi:her illustrated in the following examples.
lo EXs'1t11p1eS
Descrit~tion of tests:
Abrasion resistance:
s DIN 53-516 (60 grit Emery paper) Dynamic Property Testing:
Dynamic testing (tan 8 at 0°C and 60°C, Loss modulus at 60°C) were carried out using the GABO. The GABO is a dynamic mechanical analyzer for characterizing the properties of vulcanized elastomeric materials. The to dynamic mechanical properties give a measure of traction with the best traction usually obtained with high values of tan 8 at 0°C. Low values of tan 8 at 60°C, and in particular, low loss moduli at 60°C are indicators of low rolling resistance. RPA measurements were obtained vvith the use of an Alpha Technologies RPA 2000 operating at 10U °C at a frequency of 6 cpm.
Strain is sweeps were measured at strains of 0.1, 0.2, 0.5, 1, 2, 5, 10, 20, 50 and 90 °.
Cure rheomefry:
ASTM D 52-89 MDR2000E Rheometer at 1 ° arc and 1.7 Hz Description of Ingredients and General Mixing Procedure:
2o Hi-Sil~ 233 - silica - a product of PPG
Sunpar~ 2280 - paraffinic oil produced by Sun Oil Maglite~ D - magnesium oxide produced by CP Hall The brominated butyl elastomer (in all cases commercial Bayer~
Bromobutyl 2030) silica, oil and silazane or silazane/hydroxyl- and amine-2s containing additive mixture were mixed on either:
i) a tangential Banbury internal mixer operating at 77 rpm while being thermally regulated with the use of a Mokon get to 40 °C. Compounds were mixed for a total of 6 minutes. The final rubber temperature ranged from 140 °C to 180 °C.
3o ii) a 6" X 12" two-roll mill with the rolls running at 24 and 32 rpm. The mill roll was set at 25°C, with a total incorporation time of 10 minutes.
The mixed compounds were then "heat treated" for a further 10 minutes with the roll temperature at 110°C. The final rubber temperature was 125°C.
Curatives were then added to the cooled sample with the mill at 25°C.
s Examale 1 The affect of silazane incorporation into halogenated butyl elastomer/silica compounds was investigated via the formulation of several compounds of which hexamethyldisilazane (HMDZ) was incorporated as the silazane compound. For comparison, a halogenated butyl elastomer/silica to compound with no silazane was also prepared as a control compound.
Brominated isoprene isobutyfene rubber (BIIR) was mixed with the silazane and 60 parts per hundred rubber (phr) of silica filler (HiSil~ 233) in a tangential Banbury mixer under the mixing conditions described above.
Identical curative ingredients (1 phr of stearic acid, 0.5 phr of sulfur, and 1.5 Is phr of Zn0) were then added on a cool mill to each of the compounds. The compounds were then cured for either tc(gp) + 10 minutes at 170°C (for DIN
Abrasion testing) or tc(g0) + 5 minutes at 170°C and tested. Tables 1 and 2 gives the product compositions, and physical property data for the HMDZ
containing compounds and for a compound containing no filler bonding agent.
2o The data in Table 1 clearly shows the effect of adding HMDZ to assist in the bonding and dispersion of the siliceous filler in the brominated butyl elastomer. The ratio M300/M100 is commonly used as a relative measure of the degree of filler reinforcement in an elastomer compound (the higher the ratio the higher the reinforcement). While the M300IM100 for compound 1d 2s with no HMDZ (example 1d will here in be used as the control compound for the remaining examples) is 1.97 the M300/M100 values for the compounds containing HMDZ ranges from 3.~6 to 4.13. (See Figure 1 ). The value of the complex modulus (G*, MPa) at low strains obtained from RPA measurements is commonly used as a relative measure of the degree of filler reinforcement 3o in an elastomer compound (the lower the value of G*, the higher the degree of filler dispersion). From the data in Table 1, it is clear that a significant improvement in filler dispersion is observed on the addition of HMDZ to brominated butyl rubberlsilica compounds. Specifically, for the control compound, the G* value is 2934 MPa while for the compounds containing HMDZ, this value ranges from 365 to 631 MPa (See Figure 2).
Importantly, the data in Table 1 also shows that the improvement in filler dispersion and bonding does not effect the overall processability of the s resulting compound. On examination of the Mooney Scorch data presented in Table 1 and Figure 3, it can be seen that the incorporation of HMDZ into these brominated butyl rubberlsilica compounds significantly improves the scorch safety (i.e. increase in the t03 times).
With respect to the performance of these compounds in tires treads, to tan 8 values at 0 °C and 60 °C as well as loss modulus (G", MPa) values at 60 °C are quoted. Specifically, high tan 8 values at 0 °C are indicative of good traction while low values of tan ~ at 60 °C and low values of G" at 60 °C are indicative of low rolling resistance. From the data presented in Table 2, the positive effects of HMDZ on the tan ~ value at 0 °C and the G" value at 60 °C
is are seen. While the control compound possesses a tan 8 (0 °C) of 0.23 and a G" (60 °C) of 3.33 MPa, compounds containing HMDZ possess tan s (0 °C) values ranging from 0.49 to 0.88 and G" (60 °C) values ranging from 0.93 to 1.98 MPa.
2o Example 2 Co-pending Canadian Patent Application 2,339,080 illustrates the utility of additives containing at least one hydroxyl group and at least one substituent bearing a basic amine group in the dispersion and reinforcement of silica in halogenated butyl elastomer compounds. Given the positive effect 2s seen through the introduction of HMDZ into halogenated butyl elastomer/silica compounds, mixtures of HMDZ and hydroxyl- and amine-containing additives of the type described above were examined. This example investigates the effect of incorporating mixtures of HMDZ and monoethanolamine (MEA) into halogenated butyl elastomerlsilica compounds prepared in a Banbury internal 3o mixer.
Brominated isoprene isobutylene rubber (BIIR) was mixed with the additives and 60 parts per hundred rubber (phr) of silica filler (HiSil~ 233) in a tangential Banbury mixer under the mixing conditions described above.
Identical curative ingredients (1 phr of stearic acid, 0.5 phr of sulfur, and 1.5 phr of Zn0) were then added on a cool mill to each of the compounds. The compounds were then cured for either tc(g0) + 10 minutes at 170°C (for DIN
Abrasion testing) or tc(g0) + 5 minutes at 170°C and tested. Tables 3 and 4 s gives the product compositions, and physical property data for the HMDZ/MEA containing cornpounds and for a compound containing only MEA.
The data in Table 3 clearly shows the effect of adding HMDZ and MEA
to assist in the bonding and dispersion of the filler in the brominated butyl elastomer. While the M300/M100 for the control compound is 1.97, the to compounds containing HMDZ and MEA possess M300/M100 values ranging from 2.79 to 4.30 (See Figure 4). Additionally, a :significant improvement in filler dispersion is observed on the addition of HMD,Z and MEA to brominated butyl rubberlsilica compounds. Specifically, for the control compound, the G*
value is 2934 MPa while for the compounds containing HMDZ and MEA, this is value ranges from 304 to 1609 MPa (See Figure 5). The incorporation of 2.9 phr of HMDZ and 2.2 phr of MEA or 2.9 phr of HMDZ and 1.1 phr of MEA is seen to improve the degree of filler dispersion over' what is observed for the compound which only contains MEA.
While the data in Table 3 suggests the addition of HMDZ into 2o halogenated butyl elastomerlsilicalMEA compounds lowers the M300/M100 values and increases the DIN abrasion volume loss, it is important to note the significant improvement in scorch safety as evideroce by the increased t03 times.
From the data presented in Tabfe 4, the positive efFects of HMDZ and 2s MEA on the tan 8 value at 0 °C and the G" value at 60 °C are seen. While the control compound possesses a tan S (0 °C) of 0.23 and a G" (60 °C) value of 3.33 MPa, compounds containing HMDZ and ME,A possess tan 8 (0 °C) values ranging from 0.43 to 0.85 and G" (60 °C) values ranging from 1.10 to 2.39 MPa. Furthermore, compounds which contain 2.9 phr of HMDZ and 2.2 3o phr of MEA and compounds which contain 2.9 phr of HMDZ and 1.1 phr of MEA possess superior tan 8 (0 °C) and G" (60 °C) values than does the halogenated butyl elastomer/silica compound which ~only contains MEA.
Example 3 This example investigates the effect of incorporating mixtures of HMDZ
and monoethanolamine (MEA) into halogenat~ed butyl elastomerlsilica compounds prepared on a 6" x 12" mill.
s Brominated isoprene isobutyiene rubber (BIIR) was mixed with the additives and 60 parts per hundred rubber (phr) of silica filler (HiSil~ 233) on a 6" x 12" mill under the mixing conditions described above. Identical curative ingredients (1 phr of stearic acid, 0.5 phr of sulfur, and 1.5 phr of Zn0) were then added to each of these compounds on a cool mill. The compounds were to then cured for either tc(g0) + 10 minutes at 170°C (for DIN Abrasion testing) or tc(g0) + 5 minutes at 170°C and tested. Tables 5 and 6 gives the product compositions, and physical property data for the HMDZIMEA containing compounds and for a compound containing only MEA.
The data in Table 5 clearly shows the effect of adding HMDZ and MEA
is to assist in the bonding and dispersion of the filler in the brominated butyl elastomer. While the M300/M100 for the control compound is 1.97, the compounds containing HMDZ and MEA possess M300/M100 values ranging from 4.02 to 6.00. (See Figure 6). Additionally, a significant improvement in filler dispersion is observed on the addition of HMD;Z and MEA to brominated 2o butyl rubber/silica compounds. Specifically, for the control compound, the G*
value is 2934 MPa while for the compounds containing HMDZ and MEA, this value ranges from 256 to 538 MPa (See Figure 7). The incorporation of HMDZ in conjunction with MEA is seen to improve both the degree of reinforcement (M300/M100) and of filler dispersion (G* at low strains) over 2s what is observed for the compound which contains only MEA.
The data in Table 5 also suggests that the addition of HMDZ into halogenated butyl elastomer/silica/MEA compounds lowers the DIN abrasion volume loss when compared to both the control compound and the compound which contains only MEA.
3o From the data presented in Table 6, the positive effects of HMDZ and MEA on the tan 8 value at 0 °C and the G" value at 60 °C are seen. While the control compound possesses a tan ~ (0 °C) of 0.23 and a G" (60 °C) of 3.33 MPa, compounds containing HMDZ and MEA pos sass tan s (0 °C) values is ranging from 0.50 to 0.86 and G" (60 °C) values ranging from 0.69 to 1.78 MPa. Furthermore, compounds which contain both HMDZ and MEA possess superior tan 8 (0 °C) and G" (60 °C) values than does the halogenated butyl elastomerlsilica compound which contains only MEA.
s Examale 4 This example investigates the effect of incorporating mixtures of HMDZ
and N,N-dimethylaminoethanol (DMAE) into halogenated butyl elastomerlsilica compounds prepared in a Banbury.
to Brominated isoprene isobutylene rubber (BIIR) was mixed with the additives and 60 parts per hundred rubber (phr) of silica filler (HiSil~ 233) in a tangential Banbury mixer under the mixing conditions described above.
Identical curative ingredients (1 phr of stearic acid, 0.5 phr of sulfur, and 1.5 phr of Zn0) were then added on a cool mill to each of these compounds. The is compounds were then cured for either tc(gp) + 10 minutes at 170°C
(for D1N
Abrasion testing) or tc(g0) + 5 minutes at 170°C and tested. Tables 7 and 8 give the product compositions, and physical property data for the HMDZ/DMAE containing compounds and for a compound containing only DMAE.
2o The data in Table 7 clearly shows the effect of adding HMDZ and DMAE to assist in the bonding and dispersion of the filler in the brominated butyl elastomer. While the M3001M100 for the control compound is 1.97, the compounds containing HMDZ and DMAE possess M3001M100 values ranging from 2.93 to 4.27. (See Figure 8). Additionally, a significant improvement in 2s filler dispersion is observed on the addition of HMDZ and DMAE to brominated butyl rubberlsilica compounds. Specificarly, for the control compound, the G* value is 2934 MPa while for the compounds containing HMDZ and MEA, this value ranges from 227 to 1056 MPa (See Figure 9).
The incorporation of 2.9 phr of HMDZ and 3.2 phr of DMAE or 2.9 phr of 3o HMDZ and 1.6 phr of DMAE is seen to improve the degree of filler dispersion over what is observed for the compound which contains only DMAE.
While the data in Table 7 suggests the addition of HMDZ into halogenated butyl elastomer/silica/DMAE compounds lowers the M300/M100 values and increases the DIN abrasion volume loss, it is important to note the significant improvement in scorch safety as evidence by the increased t03 times possessed by these compounds.
From the data presented in Table 8, the positive effects of HMDZ and s DMAE on the tan 8 value at 0 °C and the G" value at 60 °C are seen. While the control compound possesses a tan ~ (0 °C) of 0.23 and a G~ (60 °C) of 3.33 MPa, compounds containing HMDZ and DMAE possess tan 8 (0 °C) values ranging from 0.45 to 0.82 and G" (60 °C) values ranging from 0.48 to 2.31 MPa. Furthermore, compounds which contain 2.9 phr of HMDZ and 3.2 to phr of DMAE or 2.9 phr of HMDZ and 1.6 phr of DMAE possess superior tan 8 (0 °C) and G" (60 °C) values than does the halogenated butyl elastomerlsilica compound which contains only DMAE.
Example 5 is This example investigates the effect of incorporating mixtures of HMDZ
and N,N-dimethylaminoethanof (DMAE) into halogenated butyl elastomerlsilica compounds prepared on a 6" x 12" mill.
Brominated isoprene isobutylene rubber (BIIR) was mixed with the additives and 60 parts per hundred rubber (phr) of silica filler (HiSil~ 233) on 2o a 6" x 12" mill under the mixing conditions described above. Identical curative ingredients (1 phr of stearic acid, 0.5 phr of sulfur, and 1.5 phr of Zn0) were then added on a cool mill to each of these compounds. The compounds were then cured for either tc(gp) + 10 minutes at 170°C (for DIN Abrasion testing) or tc(gp) + 5 minutes at 170°C and tested. Tables 9 and 10 give the product 2s compositions, and physical property data for the HMDZ/DMAE containing compounds and for a compound containing only DMAE.
The data in Table 9 clearly shows the effect of adding HMDZ and DMAE to assist in the bonding and dispersion of the filler in the brominated butyl elastomer. While the M300/M100 for the control compound is 1.97, the 3o compounds containing HMDZ and DMAE possess M300/M100 values ranging from 4.41 to 6.55. (See Figure 10). Additionally, a significant improvement in filler dispersion is observed on the addition of HMDZ and DMAE to brominated butyl rubber/silica compounds. Specifically, for the control m compound, the G* value is 2934 MPa while for the compounds containing HMDZ and MEA, this value ranges from 245 to T42 MPa (See Figure 11 ).
The incorporation of 2.9 phr of FiMDZ and 3.2 phr of DMAE or 2.9 phr of HMDZ and 1.6 phr of DMAE is seen to improve both the degree of s reinforcement (M300/M100) and of filter dispersion (G* at low strains) over what is observed for the compound which contains only DMAE.
The Mooney Scorch data presented in Table 9 also illustrates the positive impact on the t03 times (increased t03 times imply improved processability) observed on addition of HMDZ to halogenated butyl to elastomerlsilica/DMAE compounds.
From the data presented in Table 10, the positive effects of HMDZ and DMAE on the tan 8 value at 0 °C and the G~ value at 60 °C
are seen. While the control compound possesses a tan ~ (0 °C) of 0.23 and a G" (60 °C) of 3.33 MPa, compounds containing HMDZ and DMAE possess tan 8 (0 °C) is values ranging from 0.56 to 0.86 and G" (60 °C) values ranging from 0.42 to 1.61 MPa. Furthermore, compounds which contain 2.9 phr of HMDZ and 3.2 phr of DMAE or 2.9 phr of HMDZ and 1.6 phr of DMAE possess superior tan ~
(0 °C) and G" (60 °C) values than does the halogenated butyl elastomerlsilica compound which contains only DMAE.
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Claims (12)
1. A process for preparing a filled halobutyl elastomer which comprises admixing at least one halobutyl elastomer, at least one mineral filler and at least one silazane compound or mixture of silazane compound and an additive which contains at least one hydroxyl group and at least one substituents which bears a basic amine group, and curing the resulting filled brominated butyl elastomer.
2. A process according to claim 1, wherein the silazane compound is an organic silazane compound.
3. A process according to claim 2 wherein the silazane compound is a disilazane compound.
4. A process according to claim 1, wherein the mineral filler is selected from the group consisting of regular or highly disperse silica, silicates, clay (such as bentonite), gypsum, alumina, titanium dioxide, talc and mixtures thereof.
5. A process according to claim 1, wherein the halogenated butyl elastomer is a brominated butyl elastomer.
6. A process according to any of the claims 1-5, wherein the amount of silazane is in the range of from 0.5 to 10 parts per hundred parts of elastomer.
7. A process according to claim 1 wherein the filled halobutyl elastomer is admixed with another elastomer or elastomeric compound before it is subjected to curing.
8. A filled halobutyl elastomer composition comprising at least one halobutyl elastomer, at least one mineral filler and at least one silazane compound or mixture of silazane compound and an additive which contains at least one hydroxyl group and at least one substituents which bears a basic amine group.
9. A filled, cured halobutyl elastomer composition comprising at least one halobutyl elastomer, at least one mineral filler and at least one silazane compound or a mixture of a silazane compound and an additive which contains at least one hydroxyl group and at least one substituents which bears a basic amine group.
10.A filled, cured elastomer composition according to claim 9 in the form of a tread for a vehicle tire.
11.A filled, cured elastomer composition according to claim 9 in the form of an innerliner for a vehicle tire.
12.In a method of improving the abrasion resistance of a filled, cured elastomer composition comprising at least one halogenated butyl elastomer by admixing said halogenated butyl elastomer with a silazane compound or a mixture of a silazane compound and an additive which contains at least one hydroxyl group and at least one substituents which bears a basic amine group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2416635 CA2416635A1 (en) | 2002-01-17 | 2003-01-17 | Silica-filled elastomeric compounds |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002368363A CA2368363A1 (en) | 2002-01-17 | 2002-01-17 | Silica-filled elastomeric compounds |
| CA2,368,363 | 2002-01-17 | ||
| CA 2416635 CA2416635A1 (en) | 2002-01-17 | 2003-01-17 | Silica-filled elastomeric compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2416635A1 true CA2416635A1 (en) | 2003-07-17 |
Family
ID=27614039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2416635 Abandoned CA2416635A1 (en) | 2002-01-17 | 2003-01-17 | Silica-filled elastomeric compounds |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2416635A1 (en) |
-
2003
- 2003-01-17 CA CA 2416635 patent/CA2416635A1/en not_active Abandoned
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