WO1999011700A1 - Composition durcissable presentant une adherence accrue a l'etat durci, une resistance accrue a la dechirure, une resistance a la croissance de la dechirure, et resistant au vieillissement - Google Patents

Composition durcissable presentant une adherence accrue a l'etat durci, une resistance accrue a la dechirure, une resistance a la croissance de la dechirure, et resistant au vieillissement Download PDF

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Publication number
WO1999011700A1
WO1999011700A1 PCT/US1998/018420 US9818420W WO9911700A1 WO 1999011700 A1 WO1999011700 A1 WO 1999011700A1 US 9818420 W US9818420 W US 9818420W WO 9911700 A1 WO9911700 A1 WO 9911700A1
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composition
group
ethylene
mixtures
diene
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PCT/US1998/018420
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English (en)
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Robert Joseph Noel Bernier
Joseph Kestutis Valaitis
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Union Carbide Chemicals & Plastics Technology Corporation
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Publication of WO1999011700A1 publication Critical patent/WO1999011700A1/fr

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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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Definitions

  • This invention relates to curable compositions comprising a granular, free-flowing ethylene-alpha olefin-diene elastomer and an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid. More particularly, the invention relates to curable compositions comprising a granular, free- flowing ethylene-alpha olefin-diene elastomer produced in the gas phase and an ⁇ . ⁇ -ethylenically unsaturated carboxylic acid of the formula (RCO) 2 M which alone or in combination with other rubbers has improved cured adhesion, tear resistance, cut-growth resistance, and/or aged property retention.
  • RCO formula
  • Co-agents or promoters such as zinc diacrylates and dimethacrylates, for rubber-to-metal adhesion have been used to provide some of these advantages to sulfur-cured and peroxide-cured rubber compounds, such as with EPDMs produced in solution or bulk polymerization processes or with natural rubber, used in tires.
  • EPDMs sulfur-cured and peroxide-cured rubber compounds
  • roofing formulations having improved integrity of the membrane in order to extend the useful life of the membrane and to reduce warranty costs associated with premature failure.
  • roofing membranes can be exposed to conditions which can result in nicks and cuts from above or beneath, or experience damage due to high winds or building movement.
  • the present invention provides a composition
  • a composition comprising a granular, free-flowing ethylene-alpha olefm-diene elastomer produced in a gas phase polymerization, a metal salt of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, a curing agent, and optionally a rubber selected from the group consisting of natural rubber, polybutadiene, polyisoprene, polychloroprene, a styrene-butadiene rubber, polystyrene, and mixtures thereof.
  • the rubbers, except for natural rubber are also produced in a gas phase fluidized polymerization process.
  • the present invention has utility in roofing materials, coolant hosing, high pressure brake hose, power transmission belts, automotive parts such as hosing, weather stripping, bumpers, and tire components such as sidewalls, tread, and innerliner.
  • the present invention is particularly useful for the manufacture of pneumatic tires and their structural components to provide improved cured adhesion, improved tear resistance, improved cut-growth resistance, and/or improved aged property retention.
  • the ethylene- alpha olefin-diene elastomer of the composition is in granular, free- flowing particulate form with an average particle size diameter of 3mm or smaller. It is prepared by a fluidized bed process in the gas phase. Such processes are disclosed, for example, in U.S. Patent Nos. 4,994,534; 5,304,588; 5,317,036; 5,453,471; 5,585,184; and 5.616,661.
  • these polymerizations are conducted in a fluidized bed in the gas phase at or above the sticking or softening temperature of the final polymer product generally in the presence of inert particulate material selected from the group consisting of carbon black, silica, clay, talc, and mixtures thereof.
  • inert particulate material selected from the group consisting of carbon black, silica, clay, talc, and mixtures thereof.
  • carbon black, silica, and mixtures of them are preferred.
  • the ethylene-alpha olefin-diene elastomer can include a blend of two or more ethylene-alpha olefin-diene polymers differing in, for example, molecular weight, amount of ethylene, amount and kind of alpha olefin, and/or amount and kind of diene, and the inert particulate material used to produce them in the gas phase.
  • the alpha olefin contains 3 to 18 carbon atoms with 3 or 4 carbon atoms being preferred.
  • Alpha olefins frequently used include propylene. 1-butene, and 4-methyl-l-pentene. The most preferred alpha olefin is propylene.
  • the diene can include any of the dienes enumerated in U.S. Patent No. 5,317,036 and can include straight chain, branched chain, or cyclic hydrocarbon dienes having from about 5 to about 15 carbon atoms. Dienes which are particularly preferred include 1,4-hexadiene. dicyclopentadiene, 1,3-cyclopentadiene, 1,7-octadiene, methyloctadiene (e.g., 1 -methyl- 1,6-octadiene and 7-methyl-l,6-octadiene), ethylidene norbornene (e.g., 5-ethylidene-2-norbornene), and mixtures thereof. Of these, dicyclopentadiene, ethylidene norbornene, and methyloctadiene are most preferred.
  • the ethylene content of the ethylene-alpha olefin-diene is between about 40 to 85%, preferably about 50 to 80%.
  • the alpha-olefin content is between about 13 to 60%, preferably about 20 to 50%.
  • the diene content is about 0.1 to 30%, preferably about 1.5 to 15%.
  • the amount of ethylene-alpha olefin-diene in the composition of the invention ranges from about 8% to about 70% based upon the end use formulation, preferably about 20% to about 60%, because it depends on the product formulation.
  • the ethylene-alpha olefin-diene of the composition has a Mooney as measured by ASTM D- 1646 ranging from about 5 to 500.
  • the product When ethylene-alpha olefin-diene is produced in the gas phase, preferably at or above the softening temperature of the polymer using inert particulate material, the product has a unique core-shell composition.
  • the resin particle comprises an outer shell having a mixture of inert particulate material and sticky polymer (e.g., ethylene-alpha olefin-diene) said inert particulate material being present in the outer shell in an amount higher than 75% by weight based on the weight of the outer - 0
  • This component of the composition of the invention has the general formula (RCO)2M, wherein R is an ethylenically unsaturated acrylic moiety having from 2 to 7 carbon atoms such as acrylic, methacrylic, cinnamic, crotonic acid moieties, and mixtures of them.
  • R is an acrylic acid moiety, a methacrylic acid moiety, or a mixture thereof.
  • M is a metal ion selected from the group consisting of sodium, potassium, magnesium, calcium, zinc, barium, aluminum, tin, zirconium, lithium, cadmium, and mixtures thereof.
  • M is zinc or magnesium; most preferably, M is zinc.
  • the preferred zinc dimethacrylates and zinc diacrylates are powders and are disclosed in U.S. Patent Nos. 4,529,770 and 4,500,466. Generally, this component is formed by reacting under agitation the metal oxide and the carboxylic acid in a liquid medium, followed by drying. Alternatively, such metal salts of carboxylic acids are commercially available.
  • the zinc dimethacrylate employed has a surface area of from about 3.0 to about 6.0 square meters per gram (m 2 /g) or more.
  • Amounts of the metal salt of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid which may be utilized in the composition of the invention depend upon the type or elastomer and/or highly unsaturated rubber employed, the type and amount of filler or mixture of fillers, and the properties desired in the cured or vulcanized composition which are dictated in part by its end-use. In general, the amount ranges from about 2.0 to 30 parts by weight per 100 parts by weight of the final rubbery polymer composition produced.
  • the metal salt of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid can be grafted in solution/slurry onto an ethylene-alpha olefin- diene backbone or other rubber using procedures and techniques well known to those skilled in the art or it can be added and blended in-situ during the mixing of the composition.
  • Sulfur-containing compounds and peroxide curing agents can be used in the compositions of the invention.
  • Curing agents for use in the invention include sulfur- containing compounds such as elemental sulfur, 4,4'- dithiodimorpholine, thiuram disulfides and thiuram polysulfides, alkylphenol disulfides, and 2-morpholino-dithiobenzothiazole; peroxides such as di-tertbutyl peroxide, tertbutylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-(tertbutylperoxy) hexane, di- (tertbutylperoxyisopropyl) benzene, tertbutyl peroxybenzoate and 1,1- di-(tertbutylperoxy)-3,3,5-trimethylcyclohexane; metal oxides such as zinc, magnesium, and lead oxides; dinitroso compounds such as
  • the amount of the vulcanizing or curing agent can range from about 1 to 10 parts by weight based upon 100 parts of the ethylene- alpha olefin-diene polymer.
  • the vulcanizing or curing agent can optionally also be employed in conjunction with one or more accelerators.
  • the accelerator in the composition of the invention is selected from the group consisting of a sulfenamide, a thiazole, a dithiocarbamate, a thiuram, a xanthate, a thiourea, guanidine, and mixtures thereof. Of these, sulfenamides are preferred. Sulfenamides that can be employed in the invention generally are within two classes - benzothiazolsulfenamides, including bis-benzothiazolesulfenamides as disclosed in PCT/US91/05997, and thiocarbamylsulfenamides. Benzothiazolesulfenamides can be depicted as follows:
  • Rl, R ⁇ , and R* can be the same or different and represent hydrogen, a C3 to C9 branched, linear, or cycloalkyl group, such as, but not limited to, isopropyl, isobutyl, cycloalkenyl, tert-butyl, tert-amyl, t- octyl, as well as representing an aryl group, for example, benzyl, dibenzyl or dithiobenzyl, with the proviso that Rl and R ⁇ cannot both be hydrogen.
  • Preferred sulfenamides employed in the composition of the invention as an accelerator can be selected from the group consisting of 4-morpholinyl-2-benzothiazole disulfide; N-oxy diethylene- 2-benzothiazole-sulfenamide; N-cyclohexyl-2- benzothiazolesulfenamide; N-isopropyl-2-benzothiazole-sulfenamide; N-tert-butyl-2-benzothiazolesulfenamide; N,N-dicyclohexyl-2- benzothiazole-sulfenamide; N,N-diethyl-2-benzothiazole-sulfenamide; N,N-diisopropyl-2-benzothiazole-sulfenamide; and N-cycloalkylbis(2- benzothiazolsulfen)amides preferably wherein the alkyl is a linear or branched C3 to C9 and mixtures thereof.
  • Examples of the bis(2- benzothiazole)sulfenamides can include N-cyclohexylbis(2- benzothiazole)sulfenamide; N-isopropylbis(2- benzothiazole)sulfenamide; N-tert-octylbis(2- benzothiazole)sulfenamide; N-tert-amylbis(2- benzothiazole)sulfenamide; N-isobutylbis(2-benzothiazole)sulfenamide; N-tert-butylbis(2-benzothiazole)sulfenamide; N-benzylbis(2- benzothiazole)sulfenamide; and N-dibenzylbis(2- benzothiazole)sulfenamide.
  • Suitable thiocarbamylsulfenamides are well known and disclosed, for example, in U.S. Patent No. 4,008,190.
  • N,N- (higher alkyl)thiocarbamylsulfenamides of the present invention have the formula
  • R3 is hydrogen or the same as R ⁇ , and R ⁇ is selected from the group consisting of alkyl radicals containing about 1 to about 4 carbon atoms, cycloalkyl radicals containing 4 to 7 carbon atoms in the ring, a phenyl radical, and an aralkyl radical or alkaryl radical containing 7 to about 12 carbon atoms;
  • R is hydrogen or an alkyl radical containing 1 to 2 carbon atoms;
  • x is 4 to 7;
  • R ⁇ and R ⁇ are alkyl radicals containing 6 to 30 carbon atoms.
  • the alkyl radicals can be linear or branched and can contain primary, secondary and/or tertiary carbon atom configurations.
  • the cycloalkyl radicals can be further substituted with alkyl radicals containing 1 to 4 carbon atoms.
  • the thiocarbamylsulfenamide compounds contain at least 12 carbon atoms in the total of groups R5 and ⁇ , and up to 60 carbon atoms.
  • R ⁇ and R ⁇ are alkyl radical containing about 8 to about 24 carbon atoms and R ⁇ and R ⁇ are the same, i.e., the amine is symmetrical; and B is -NRl'R ⁇ ', wherein Rl' and R ⁇ are cycloalkyl radicals containing 5 to 7 carbon atoms in the ring.
  • Examples of the most preferred compounds are N- oxydiethylenethiocarbamyl-N'-oxydiethylene sulfenamide, N.N-di(2- ethylhexyl)thiocarbamyl-N',N'-dicyclohexylsulfenamide, N,N- ditetradecylthiocarbamyl-N',N'-dicycloheptylsulfenamide, N,N,- dioctadecylthiocarbamyl-N',N'-dicyclohexylsulfenamide, N,N- dieicosylthiocarbamyl-N',N'-dicyclohexylsulfenamide, and mixtures thereof.
  • Illustrative thiazoles for use in the composition of the invention can include benzothiazyl disulfide, 2-mercaptobenzothiazole, and 2.2'-mercaptobenzothiazole disulfide, zinc 2- mercaptobenzothiazole, mixtures thereof, and the like.
  • Illustrative dithiocarbamates for use in the composition of the invention can include Bismate® (bismuth dimethyldithiocarbamate), Butyl Eight® (activated dithiocarbamate), Amyl Cadmate® (cadmium diamyldithiocarbamate), Ethyl Cadmate® (cadmium diethyldithiocarbamate), Cumate® (copper dimethyldithiocarbamate), Amyl Ledate® (lead diamyldithiocarbamate), Methyl Ledate® (lead dimethyldithiocarbamate), Ethyl Selenac® (selenium diethyldithiocarbamate), Methyl Selenac® (selenium dimethyldithiocarbate), Ethyl Tellurac® (tellurium diethyldithiocarbamate), Amyl Zimate® (zinc diamyldithiocarbamate), Butyl Zimate® (zin
  • Illustrative thiurams for use in the composition of the invention can include Sulfads® such as dipentamethylene thiuram hexasulfide, Butyl Tuads® such as tetrabutylthiuram disulfide, Captax-Tuads Blend® (a blend of 1 part 2-mercaptobenzothiazole and 2 parts tetramethylthiuram), Ethyl Tuads® such as tetraethylthiuram disulfide, Methyl-Ethyl Tuads® (a 60:40 blend of Methyl Tuads® and ethyl tuads), Methyl Tuads® such as tetramethylthiuram, and Unads® such as tetramethylthiuram monosulfi.de, and mixtures thereof.
  • Sulfads® such as dipentamethylene thiuram hexasulfide
  • An illustrative xanthate for use in the composition of the invention can include Propyl Zithate® such as zinc isopropyl xanthate.
  • An illustrative thiadiazine for use as an additional accelerator herein is Nanax ⁇ P® (or activated thiadiazine).
  • Illustrative thioureas for use in the composition of the invention can include Thiate E® (trimethylthiourea), Thiate H® (1,3- diethylthiourea), and Thiate U® (1,3-dibutylthiourea), and mixtures thereof.
  • the accelerator level is about 0.2 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight. It is further understood that, when a sulfenamide is employed in the invention, one or more of the other above-mentioned accelerators can be employed as a second accelerator in a minor amount or portion (that is, less than 50% by weight of the total amount of accelerator employed in the composition, preferably less than 30%, and most preferably less than 10%.
  • the composition of the invention can optionally include a highly unsaturated rubber selected from the group consisting of natural rubber, polybutadiene, polyisoprene, polychloroprene, a styrene-butadiene rubber, polystyrene, and mixtures thereof.
  • the rubbers, except for natural rubber are also produced in a gas phase fluidized polymerization process. Such processes are taught, for example, in U.S. Patent No. 5,453,471; WO 95/09826; and WO 95/09827.
  • these highly unsaturated rubbers when they are produced in the gas phase, they are polymerized preferably at or above their softening or sticking temperatures in the presence of an inert particulate material selected from the group consisting of carbon black, silica, clay, talc, polymeric material, and mixtures thereof.
  • the inert particulate material is carbon black, silica, or a mixture thereof.
  • gas phase produced rubbers like the gas phase ethylene-alpha olefm- diene, have the same unique core-shell configuration as well as a catalyst metal residue (e.g., Ni, Co, or rare earth such as neodymium in amounts ranging from 10 to 35,000 ppm) throughout the resin particle.
  • a catalyst metal residue e.g., Ni, Co, or rare earth such as neodymium in amounts ranging from 10 to 35,000 ppm
  • the rubber used in the composition comprise from about 10 to 80 parts by weight based upon the weight of the total composition, preferably from about 20 to 60 parts.
  • additives usually used in the rubber industry. These additives can include, for example, one or more fillers, plasticizers, antioxidants and antiozonants, activators, tackifiers, adhesion promoters, homogenizing agents, peptizers, pigments, flame retardants, fungicides, and the like.
  • Fillers for use in the invention include carbon black; silicates of aluminum, magnesium, calcium, sodium, potassium and mixtures thereof; carbonates of calcium, magnesium and mixtures thereof; oxides of silicon, calcium, zinc, iron, titanium, and aluminum; sulfates of calcium, barium, and lead: alumina trihydrate: magnesium hydroxide; phenol-formaldehyde, polystyrene, and poly(alphamethyl)styrene resins; natural and synthetic fibers: and the like.
  • Plasticizers for use in the invention include petroleum oils such as ASTM D2226 aromatic, naphthenic and paraffinic oils: polyalkylbenzene oils; organic acid monoesters such as alkyl and alkoxyalkyl oleates and stearates; organic acid diesters such as dialkyl, dialkoxyalkyl, and alkyl aryl phthalates, terephthalates, sebacates, adipates, and glutarates; glycol diesters such as tri-, tetra-.
  • petroleum oils such as ASTM D2226 aromatic, naphthenic and paraffinic oils: polyalkylbenzene oils; organic acid monoesters such as alkyl and alkoxyalkyl oleates and stearates; organic acid diesters such as dialkyl, dialkoxyalkyl, and alkyl aryl phthalates, terephthalates, sebacates, adipates, and glutarates; glycol diesters such as tri-,
  • Antioxidants and antiozonants for use in the invention include hindered phenols, bisphenols, and thiobisphenols; substituted hydro quinone s ; tris (alky lp henyl)p hosp hite s ; dialky lthiodip roprionate s ; phenylnaphthylamines; substituted diphenylamines; dialkyl, alkyl aryl, and diaryl substituted p-phenylene diamines: monomeric and polymeric dihydroquinolines; 2-(4-hydroxy-3,5-t-butylaniline)-4,6- bis(octylthio)-l,3,5-triazine, hexahydro-l,3,5-tris- ⁇ -(3,5-di-t-butyl-4- hydroxyphenyl)propionyl-s-triazine, 2,4,6-tris(n-l,4-dimethylpentyl-p
  • additives for use in the invention include activators (metal oxides such as zinc, calcium, magnesium, cadmium, and lead oxides; fatty acids such as stearic, lauric, oleic, behenic, and palmitic acids and zinc, copper, cadmium, and lead salts thereof; di-. tri-, and polyethylene glycols; and triethanolamine).
  • activators metal oxides such as zinc, calcium, magnesium, cadmium, and lead oxides
  • fatty acids such as stearic, lauric, oleic, behenic, and palmitic acids and zinc, copper, cadmium, and lead salts thereof; di-. tri-, and polyethylene glycols; and triethanolamine.
  • Tackifiers rosins and rosin acids, hydrocarbon resins, aromatic indene resins, phenolic methylene donor resins, phenolic thermosetting resins, resorcenol- formaldehyde resins, and alkyl phenol formaldehyde resins such as octyl-phenol-formaldehyde resin
  • homogenizing agents peptizers, pigments, flame retardants, fungicides, and the like can also be employed in the composition of the invention.
  • the total amount of additives can range from about 20 to 900 parts by weight based upon 100 parts of the elastomers in the composition.
  • the amount of filler ranges from about 1 to 500 parts by weight of the polymer composition;
  • the amount of cure activators ranges from about 0.1 to 10 phr;
  • the amount of antioxidants and antiozonants and stabilizers ranges from about 0.1 to 10 phr;
  • the amount of softeners and tackifiers ranges from about 0.1 to 30 phr;
  • the composition can optionally contain an adhesion promoter.
  • adhesion promoters can include such resins as phenolic methylene donor resins, phenolic thermosetting resins, and resorcenol-formaldehyde resins.
  • a number of the phenolic, rosin acid, and especially alkyl phenol formaldehyde resins can act both as a tackifier as well as cured adhesion promoter. Of these, octyl-phenol- formaldehyde resin is most preferred for its dual function of improved cured adhesion and tack.
  • Forming the Composition The mixing or blending of ingredients forming the composition according to the invention is performed by means well known to those skilled in the art. Such means can include, for example, a two-roll mill, Banbury® mixer, Henschel® mixer, extruder, or the like, in the usual manner.
  • the composition containing ethylene-alpha olefin-diene, e.g., EPDM, metal salt of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, additional rubbers, other optional additives, and curing agent alone or in combination with an accelerator is mixed in two stages.
  • all of the ingredients, except the accelerator and sulfur are added in a first stage (often referred as the "masterbatch" stage).
  • the curing agent e.g., sulfur
  • the accelerator or blend of accelerators are added to the masterbatch. This second stage is often referred to as the "final” stage.
  • the accelerators can be incorporated in the masterbatch, or in single stage mixing.
  • the ingredients are mixed at a temperature and time to obtain uniform mixing.
  • Curing temperatures and time are generally not critical and cure temperatures can range from about 250°F (121°C) to about 400°F (204°C) and cure times range from about 0.5 minutes to about 3 hours.
  • the method of curing may be chosen from the many conventionally known methods including open steam, autoclave, press or mold curing, liquid salt bath, hot air, microwave, UHF or infrared vulcanization.
  • the method of forming an article into a desired shape is largely dependent upon the mixing and curing method chosen and known to those skilled in the forming art. Some representative methods are mold forming, extrusion, roller head die forming, die cutting, hand lay-up.
  • the elastomeric composition of the present invention can be employed in the production of elastomeric articles such as tire sidewalls, roofing membranes, as well as, other molded and extruded articles. And, in the case of tires, belts and hoses, these milling, molding and/or extruding methods are used at some point in the method of manufacturing.
  • Some of the applications are intended for relatively static in-use conditions such as coolant hose and roofing membrane. Other applications encounter dynamic in-service conditions such as tire sidewall and brake hose and power transmission belt.
  • ⁇ R/BR Tire Sidewalls.
  • ⁇ R/BR is the polymer system, it requires high levels of antioxidants, antiozonants, and microcrystalline waxes to protect it from the environment.
  • EPDM is used, these protective materials are not necessary because of the inherent stability of EPDM.
  • the required protective materials function by migrating to the surface of the tire sidewall and cause discoloration and staining.
  • the use of EPDM does not require the protective materials; and, thus, the unattractive sidewall appearance is not a problem. In fact EPDM gives the tire sidewall a naturally appealing black sheen appearance.
  • the benefits of using metal salts of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid compounds in the EPDM formulation in which the EPDM is produced by a gas phase process include the following: enhanced cured adhesion to adjacent components; improved aged property retention; increased tear and cut-growth resistance; improved ozone and UN resistance; and improved flex fatigue.
  • EPDM roofing membranes carry a long term performance warranty; and, thus, formulation modifications which further improve the in-service life of the membrane are cost effective.
  • the use of zinc dimethacrylate and related compounds has shown large improvements in aged property retention and especially aged tear and cut-growth resistance.
  • the geometry of the tear path has been modified so that even when tear is initiated, at the higher required force, the damage is minimized because the tear path reverses on itself.
  • Coolant Hose Coolant Hose. Coolant hose compounds have to have good heat resistance, compression set, coolant, and oxidative resistance. Zinc dimethacrylate and the related compounds, when incorporated into the hose formulation, show improvements in all of these properties; and, thus, extend the useful life of the automotive coolant hose.
  • High Pressure Brake Hose Such properties as high temperature resistance, good ozone resistance, good flex fatigue, and good water and brake fluid resistance are critical for this application.
  • the use of zinc dimethacrylate and the related compounds show improvements in all of these properties; and, thus, have extended the useful life of this automotive component.
  • the masterbatch was mixed in a laboratory "B" size (approximately 1685 cc mixing cavity volume) Banbury® at 77 revolutions per minute rotor speed.
  • the Banbury® was preheated to 120°F and the masterbatch ingredients were loaded in the following sequence: one half of the polymer; all of the remaining masterbatch materials such as oil, zinc oxide, stearic acid, zinc stearate. resin and zinc dimethacrylate or zinc diacrylate; and finally the remaining polymer. These materials were then mixed for 1.0 minute. After one minute mixing, all of the carbon black was added and the masterbatch continued to be mixed for a total accumulated time of 3.0 minutes.
  • Second Stage (Final) Mixing Procedure For the Tire and roofing Formulations.
  • the two roll, laboratory size (6 inch diameter, 12 inch width) mill was preheated to 120°F.
  • the masterbatch was added to the mill and milled until banding on the mill was consistently good (about one minute).
  • Sulfur was added and three cross-cuts were made on each side, followed by two end-roll passes.
  • the accelerator, or accelerator blend, or peroxide and co-agents were then added followed by five cross-cuts each side and two end-roll passes.
  • the final formulation was allowed to cool to room temperature prior to the preparation of test specimens.
  • Tables 1 (Formulations) and 2 (Properties) illustrate the benefits of using ⁇ , ⁇ -ethylenically unsaturated carboxylic acid compounds (zinc dimethacrylate and zinc diacrylate and others) in a 100% EPDM tire sidewall formulation. Performance property improvements are evident at all levels of zinc dimethacrylate (4 to 20 phr) and zinc diacrylate (10 phr) tested.
  • the benefits evident and shown in Table 2 include the following: Enhanced cured adhesion values by as much as 80%; Improved aged property retention (stress-strain and hardness) by as much as 20%; Increased Die C tear resistance by as much as 65%; Improved cut-growth resistance by as much as three orders of magnitude or higher.
  • Tables 3 (Formulations) and 4 (Properties) illustrate performance property improvements at all levels (2 to 12 phr) of zinc dimethacrylate used in these evaluations.
  • the benefits shown in Table 4 include the following; Improved aged property retention (stress-strain and hardness) by as much as 50%; Improved Die C tear strength by as much as 37%; Improved normal trouser tear strength by as much as 183%: Improved aged trouser tear retention by as much as 1,573%.
  • Improved aged property retention stress-strain and hardness
  • Improved Die C tear strength by as much as 37%
  • Improved normal trouser tear strength by as much as 183%
  • Improved aged trouser tear retention by as much as 1,573%.
  • Not only is the magnitude of the trouser tear force increased, but the direction of the tear propagation path is reversed. The tear damage that would thus be incurred with this type of roofing membrane would be limited in that the tear path would turn back on itself rather than propagate along the length of the roof.
  • Naphtenic Oil 10.0 10.0 10.0 4.0 6.0 4.0 4.0 4.0 4.0 4.0 4.0

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition comprenant un élastomère éthylène-alpha oléfine-diène granulaire s'écoulant librement, produit par polymérisation en phase gazeuse, un sel métallique d'un acide carboxylique éthyléniquement insaturé en α,β, un agent de durcissement, et éventuellement un caoutchouc hautement insaturé sélectionné dans le groupe constitué de polybutadiène, polyisoprène, polychloroprène, un caoutchouc butadiène-styrène, polystyrène, et des mélanges de ces produits. De préférence, les caoutchoucs sont également produits par un procédé de polymérisation en lit fluidisé en phase gazeuse utilisant un matériau particulaire inerte.
PCT/US1998/018420 1997-09-03 1998-09-02 Composition durcissable presentant une adherence accrue a l'etat durci, une resistance accrue a la dechirure, une resistance a la croissance de la dechirure, et resistant au vieillissement WO1999011700A1 (fr)

Applications Claiming Priority (2)

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US92274697A 1997-09-03 1997-09-03
US08/922,746 1997-09-03

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WO1999011700A1 true WO1999011700A1 (fr) 1999-03-11

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1664182A2 (fr) * 2003-09-24 2006-06-07 R.T. Vanderbilt Company, Inc. Systeme accelerateur pour latex de polyisoprene synthetique
EP2114696A1 (fr) * 2006-12-20 2009-11-11 Societe de Technologie Michelin Élastomère en caoutchouc avec peu d'hystérésis
WO2014154602A1 (fr) * 2013-03-26 2014-10-02 Akzo Nobel Chemicals International B.V. Procédé pour la réticulation d'epm et d'epdm
CN107266722A (zh) * 2016-04-06 2017-10-20 住友橡胶工业株式会社 无气轮胎
CN112940402A (zh) * 2019-12-11 2021-06-11 现代自动车株式会社 用于降低电偶腐蚀的具有改善的电绝缘特性的橡胶组合物

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GB2078688A (en) * 1980-06-26 1982-01-13 Xerox Corp Document transport belt
EP0237003A1 (fr) * 1986-03-10 1987-09-16 Union Carbide Corporation Procédé de production d'un polymère collant
EP0390012A1 (fr) * 1989-03-30 1990-10-03 Bridgestone/Firestone, Inc. Composition pour bande de roulement contenant des réticulations ioniques et covalentes
EP0589701A1 (fr) * 1992-09-24 1994-03-30 Sumitomo Chemical Company, Limited Composition de caoutchouc
WO1996013544A1 (fr) * 1994-10-31 1996-05-09 The Gates Rubber Company Courroies en ethylene-alpha-olefine
EP0729986A2 (fr) * 1995-03-03 1996-09-04 Union Carbide Chemicals & Plastics Technology Corporation Elastomères thermoplastiques

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Publication number Priority date Publication date Assignee Title
GB2078688A (en) * 1980-06-26 1982-01-13 Xerox Corp Document transport belt
EP0237003A1 (fr) * 1986-03-10 1987-09-16 Union Carbide Corporation Procédé de production d'un polymère collant
EP0390012A1 (fr) * 1989-03-30 1990-10-03 Bridgestone/Firestone, Inc. Composition pour bande de roulement contenant des réticulations ioniques et covalentes
EP0589701A1 (fr) * 1992-09-24 1994-03-30 Sumitomo Chemical Company, Limited Composition de caoutchouc
WO1996013544A1 (fr) * 1994-10-31 1996-05-09 The Gates Rubber Company Courroies en ethylene-alpha-olefine
EP0729986A2 (fr) * 1995-03-03 1996-09-04 Union Carbide Chemicals & Plastics Technology Corporation Elastomères thermoplastiques

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1664182A2 (fr) * 2003-09-24 2006-06-07 R.T. Vanderbilt Company, Inc. Systeme accelerateur pour latex de polyisoprene synthetique
EP1664182A4 (fr) * 2003-09-24 2011-12-28 Vanderbilt Co R T Systeme accelerateur pour latex de polyisoprene synthetique
EP2114696A1 (fr) * 2006-12-20 2009-11-11 Societe de Technologie Michelin Élastomère en caoutchouc avec peu d'hystérésis
EP2114696A4 (fr) * 2006-12-20 2010-03-10 Michelin Soc Tech Élastomère en caoutchouc avec peu d'hystérésis
US8080603B2 (en) 2006-12-20 2011-12-20 Michelin Recherche Et Technique S.A. Low hysteresis rubber elastomer
WO2014154602A1 (fr) * 2013-03-26 2014-10-02 Akzo Nobel Chemicals International B.V. Procédé pour la réticulation d'epm et d'epdm
RU2664508C2 (ru) * 2013-03-26 2018-08-20 Акцо Нобель Кемикалз Интернэшнл Б.В. Способ сшивания ерм и epdm
CN107266722A (zh) * 2016-04-06 2017-10-20 住友橡胶工业株式会社 无气轮胎
CN107266722B (zh) * 2016-04-06 2021-02-09 住友橡胶工业株式会社 无气轮胎
CN112940402A (zh) * 2019-12-11 2021-06-11 现代自动车株式会社 用于降低电偶腐蚀的具有改善的电绝缘特性的橡胶组合物

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