CA1132283A - High oil-elastomer compositions - Google Patents
High oil-elastomer compositionsInfo
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- CA1132283A CA1132283A CA323,187A CA323187A CA1132283A CA 1132283 A CA1132283 A CA 1132283A CA 323187 A CA323187 A CA 323187A CA 1132283 A CA1132283 A CA 1132283A
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Abstract
HIGH OIL-ELASTOMER COMPOSTIONS
Abstract of the Disclosure A highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer composition, methods for preparing the composition, and molded objects produced therefrom. The composition is prepared by ad-mixing a conjugated diene/vinyl aromatic radial teleblock copolymer and a hydrocarbon oil and elevating the temperature to about 120°C to about 205°C until a homogenized blend is produced. In preferred embodiments the composition is prepared by stirring together the copolymer and hydro-carbon oil at an elevated temperature of about 175°C to about 205°C or by heating a mixture of copolymer and oil in an oven without stirring at about 125°C to about 165°C. In embodiments of the invention shaped objects produced from a highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer composition include objects in the conformation of a worm particularly suitable as a fishing lure, molded objects that do not rebound when thrown against a vertical surface, shock- and energy-absorbing products, decorative objects, toys, and games.
Abstract of the Disclosure A highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer composition, methods for preparing the composition, and molded objects produced therefrom. The composition is prepared by ad-mixing a conjugated diene/vinyl aromatic radial teleblock copolymer and a hydrocarbon oil and elevating the temperature to about 120°C to about 205°C until a homogenized blend is produced. In preferred embodiments the composition is prepared by stirring together the copolymer and hydro-carbon oil at an elevated temperature of about 175°C to about 205°C or by heating a mixture of copolymer and oil in an oven without stirring at about 125°C to about 165°C. In embodiments of the invention shaped objects produced from a highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer composition include objects in the conformation of a worm particularly suitable as a fishing lure, molded objects that do not rebound when thrown against a vertical surface, shock- and energy-absorbing products, decorative objects, toys, and games.
Description
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Background of the Invention This invention relates to highly oil-extended conjugated diene/
vinyl aromatic teleblock copolymer compositions. In one of its aspects`this invention relates to preparation of highly oil-extended conjugated diene/
vinyl aromatic teleblock copolymer compositions. In a particular aspect of the invention, it relates to radial teleblock copolymer compositions.
In another of its aspects, this invention relates to objects molded from these compositions. In a more particular aspect of this invention it relates to a molded artificial fishing lure, molded objects that adhere to a vertical surface instead of rebounding, shock- and energy-absorbing products, decorative objects, toys, and games. ;~
Highly oil-extended conjugated diene/vinyl aromatic teleblock copolymer compositions are well known in the art. U.S. Patents such as 3,676,387, issued December 21, 1970 to James A. Lindlof, and 3,827,999, issued November 9, 1973 to Ronald K. Crossland, disclose stable, highly oil-extended polymer compositions based on linear teleblock copolymers and on hydrogenated branched copolymers. Compositions are known to be suitable for making castings. It has now been found that oil-extended polymer compositions of radial teleblock copolymers 3 while sharing some characteristics with oil-extended linear teleblock copolymers, have other characteristics that differentiate the radial copolymers from the linear copolymers.
Prior art compositions containing linear polymers and high amounts of plasticizer or extender were frequently prepared by adding extender to linear polymer in a mill or in an internal mixer, by blending a solution of linear polymer and appropriate solvent with extender followed by strip-ping the solvent, or by adding linear polymer to stirred extender at either ambient conditions or slightly elevated temperature. These methods have various disadvantages among which are: long mixing times, large power re---1-- :
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quirements, and environmental contamination by solvent vapors. The present invention provides means Eor preparing the highly oil-extended radial copolymer compositions of this invention conveniently and rapidly with a minimum of environmental problems.
The compositions that can be prepared by the method of this invention contain highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymers, preferably radial or branched teleblock co-polymers of butadiene and styrene. The compositions exhibit a number of useful and interesting properties. The compositions are highly elastic and can be extruded, injection molded, transfer molded, solution cast, hot melt cast, etc., into a wide variety of useful articles, films, coatings, etc. In addition to the hereinafter described artificial fishing lures and shaped objects that can be pressed, such as by being thrown, against flat surfaces without rebounding, the compositions can be formed into shock- and energy-absorbing products; toys; objects used in playing games; coatings for insulative or protective purposes, such as encap-sulating fragile and delicate mechanical or artistic objects or electronic components. A coating of one of these compositions on glass bottles will provide protection from breakage and will also serve to contain glass fragments should breakage occur. Flexible molds can be prepared from the compositions by coating a solid object with the composition and, after the composition sets, removing the solid object from the coating to leave a cavity in which replicas of the solid object can be prepared using any suitable molding material.
By appropriate selection of radial teleblock copolymer, oil, and the proportions in which they are combined, finished articles which slowly exude oil from the surface can be obtained. Compositions are also avail-able withïn the scope of the invention which are highly oil-extended yet which do not exude or "bleed" oil from the surface or which "bleed-out" oil at a considerably reduced rate as compared to prior art materials.
3l~3~ 3 ~ ased on the appearance and physical characteristics of finished articles that can be molded from compositions prepared by the process of this invention, a molded object has been produced that, surprisingly, is uniquely suited to the purpose for which it was conceived. It has been found that objects molded in the form of a fishing worm have not only that appeal, perhaps as much to fisherman as to fish, that perfectly adapts it as an artificial bait, but also has physical properties that are superior to similar artificial lures known to the prior art.
Artificial, rubbery fishing lures in the form of worms are currently made commercially from poly(vinyl chloride) (PVC) highly extended with high-boilingesters such as dibutyl phthalate. Such artificial worms are a commercial success, although fishermen report varying degrees of success in using them to catch fish. Unfortunately, current commercial worms generally "bleed out" a significant amount of extender which fre-quently necessitates segregation from other fishing tackle. The fishermen must also exercise caution in using these commercial worms since contact of the worms with polystyrene lures, floats, or tackle boxes results in rapid softening and deterioration of the polystyrene. The artificial fishing lures of the present invention have been especially successful employed by fishermen in catching bass. In addition, "bleed-out" is re-duced and the problem of deterioration of polystyrene in contact with the PVC worms is eliminated. The compositions of the present invention do not attack polystyrene.
Another shaped, preferably molded, object of special interest is a ball or object of another shape, that, because of a special property of compositions of this invention, can be pressed against a vertical surface, as by being thrown, without rebounding and, depending on the smoothness or slickness of the surface, will stick to the surface or adhere sufficiently to roll down the vertical face. Such objects can be rounded or can have flat surfaces.
Background of the Invention This invention relates to highly oil-extended conjugated diene/
vinyl aromatic teleblock copolymer compositions. In one of its aspects`this invention relates to preparation of highly oil-extended conjugated diene/
vinyl aromatic teleblock copolymer compositions. In a particular aspect of the invention, it relates to radial teleblock copolymer compositions.
In another of its aspects, this invention relates to objects molded from these compositions. In a more particular aspect of this invention it relates to a molded artificial fishing lure, molded objects that adhere to a vertical surface instead of rebounding, shock- and energy-absorbing products, decorative objects, toys, and games. ;~
Highly oil-extended conjugated diene/vinyl aromatic teleblock copolymer compositions are well known in the art. U.S. Patents such as 3,676,387, issued December 21, 1970 to James A. Lindlof, and 3,827,999, issued November 9, 1973 to Ronald K. Crossland, disclose stable, highly oil-extended polymer compositions based on linear teleblock copolymers and on hydrogenated branched copolymers. Compositions are known to be suitable for making castings. It has now been found that oil-extended polymer compositions of radial teleblock copolymers 3 while sharing some characteristics with oil-extended linear teleblock copolymers, have other characteristics that differentiate the radial copolymers from the linear copolymers.
Prior art compositions containing linear polymers and high amounts of plasticizer or extender were frequently prepared by adding extender to linear polymer in a mill or in an internal mixer, by blending a solution of linear polymer and appropriate solvent with extender followed by strip-ping the solvent, or by adding linear polymer to stirred extender at either ambient conditions or slightly elevated temperature. These methods have various disadvantages among which are: long mixing times, large power re---1-- :
,~
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quirements, and environmental contamination by solvent vapors. The present invention provides means Eor preparing the highly oil-extended radial copolymer compositions of this invention conveniently and rapidly with a minimum of environmental problems.
The compositions that can be prepared by the method of this invention contain highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymers, preferably radial or branched teleblock co-polymers of butadiene and styrene. The compositions exhibit a number of useful and interesting properties. The compositions are highly elastic and can be extruded, injection molded, transfer molded, solution cast, hot melt cast, etc., into a wide variety of useful articles, films, coatings, etc. In addition to the hereinafter described artificial fishing lures and shaped objects that can be pressed, such as by being thrown, against flat surfaces without rebounding, the compositions can be formed into shock- and energy-absorbing products; toys; objects used in playing games; coatings for insulative or protective purposes, such as encap-sulating fragile and delicate mechanical or artistic objects or electronic components. A coating of one of these compositions on glass bottles will provide protection from breakage and will also serve to contain glass fragments should breakage occur. Flexible molds can be prepared from the compositions by coating a solid object with the composition and, after the composition sets, removing the solid object from the coating to leave a cavity in which replicas of the solid object can be prepared using any suitable molding material.
By appropriate selection of radial teleblock copolymer, oil, and the proportions in which they are combined, finished articles which slowly exude oil from the surface can be obtained. Compositions are also avail-able withïn the scope of the invention which are highly oil-extended yet which do not exude or "bleed" oil from the surface or which "bleed-out" oil at a considerably reduced rate as compared to prior art materials.
3l~3~ 3 ~ ased on the appearance and physical characteristics of finished articles that can be molded from compositions prepared by the process of this invention, a molded object has been produced that, surprisingly, is uniquely suited to the purpose for which it was conceived. It has been found that objects molded in the form of a fishing worm have not only that appeal, perhaps as much to fisherman as to fish, that perfectly adapts it as an artificial bait, but also has physical properties that are superior to similar artificial lures known to the prior art.
Artificial, rubbery fishing lures in the form of worms are currently made commercially from poly(vinyl chloride) (PVC) highly extended with high-boilingesters such as dibutyl phthalate. Such artificial worms are a commercial success, although fishermen report varying degrees of success in using them to catch fish. Unfortunately, current commercial worms generally "bleed out" a significant amount of extender which fre-quently necessitates segregation from other fishing tackle. The fishermen must also exercise caution in using these commercial worms since contact of the worms with polystyrene lures, floats, or tackle boxes results in rapid softening and deterioration of the polystyrene. The artificial fishing lures of the present invention have been especially successful employed by fishermen in catching bass. In addition, "bleed-out" is re-duced and the problem of deterioration of polystyrene in contact with the PVC worms is eliminated. The compositions of the present invention do not attack polystyrene.
Another shaped, preferably molded, object of special interest is a ball or object of another shape, that, because of a special property of compositions of this invention, can be pressed against a vertical surface, as by being thrown, without rebounding and, depending on the smoothness or slickness of the surface, will stick to the surface or adhere sufficiently to roll down the vertical face. Such objects can be rounded or can have flat surfaces.
2~3 At one end of the spectrum of suitable shapes are objects cut from sheet material, thereby being virtually two-dimensional, which will adhere to the spot on the vertical surface onto which they are pressed.
Such objects in various shapes and colors can be used to define and decorate the transparent surface of a window. At the other end of the spectrum are spheroids which tend to roll down a vertical surface. In between, there is a relationship between the amount of flat surface on the molded object that is pressed against the vertical surface and the total weight of the object which determines the ability of an object of the inventive composition to "stick" to a vertical surface. The invention contemplates objects of any shape, but particularly those of size to be easily thrown by hand. The object can be regular as a parallelepiped, spheroid, dodecahedron, etc., or totally irregular in shape, but with sufficient surface to allow adherence to a vertical surface. All of the shapes are adaptable in preparing objects useful as toys or useful as objects employed as part of a game or recreational activity.
As mentioned above, the smoothness of the surface against which the object is pressed directly affects the ability of the object to remain on the surface. Glass, polished marble, polished metal, and concrete formed against plywood or other smooth surface have surfaces that do not cause rebound of objects of this invention that are thrown thereagainst.
It is therefor an object of this invention to provide a highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer composition. It is another object of this invention to provide a method for preparing a highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer composition. It is another object of this invention to provide an artificial fishing lure molded from a highly oil-extended conjugated dienetvinyl aromatic teleblock copolymer composition. It is still another object of this invention to provide an object molded from -: , . - - ,. : - . - . , :
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-: .: .: . , a highly oil-extended radial teleblock copolymer suitable preferably to adhere to a vertical surface against which it is thrown; but, at least, sufficient not to rebound from the surEace.
Other aspects, objects, and the various advantages of this in-vention will become apparent upon a study of this specification and the appended claims.
Statement of the Invention According to this invention, a composition is provided that is a blended mixture of a conjugated diene/vinyl aromatic radial teleblock copolymer extended with a hydrocarbon oil.
Also, according to this invention, a method is provided for pre-paring a highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer in which a conjugated diene/vinyl aromatic radial teleblock copolymer and a hydrocarbon oil are admixed and the mixture raised to an elevated temperature of about 120C to about 205C until a homogeneous blend is produced. In preferred embodiments of the invention, the copolymer and hydrocarbon oil are stirred together to form a mixture at a temperature elevated to about 175C to about 205C with stirring continued until a homogeneous blend is produced or a mixture of the co-polymer and hydrocarbon oil is prepared and the mixture elevated to a temperature in the range of about 120C to about 200C without stirring until a homogeneous blend is produced.
In an embodiment of the invention, a fishing lure comprising a highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer composition molded in a suitable conformation is provided.
In another embodiment of the invention, shaped objects that do not rebound from vertical surfaces against which they are thrown and which tend to remain in place on surfaces against which they are pressed are also provided.
Among the conjugated diene/vinyl aromatic teleblock copolymers which can be oil-extended and cast into useful objects are radial or branched teleblock copolymers of butadiene and styrene which are prepared by methods which are well known in the art. For example, use of an organolithium initiating species to polymerize styrene monomer to form a living polymer of polystyryllithium represented by:
polystyrene--Li followed by addition of butadiene monomer to the polystyryllithium to form a living polymer represented by polystyrene-polybutadiene-Li and subsequent coupling of the living polymer with a multifunctional coupling agent, such as silicon tetrachloride, results in polymers which are represented by (polystyrene-polybutadiene) Y
wherein Y represents a coupling agent residue and n is a number greater - than 2 and preferably from 3 to 5. Such polymers are characterized as ..
being elastomeric in the unvulcanized state as well as thermoplastic since they can be molded.
Useful polymers which also contain outward polystyrene blocks and inward polybutadiene blocks can be prepared by employing a polyfunc-tional initiating species, such as an organopolylithium compound, onto which polybutadiene blocks are polymerized with subsequent polymerization of polystyrene blocks. Such polymers are represented by (polystyrene-polybutadiene) Z
wherein Z represents the residue of the polyfunctional initiating speçies and n is as described above.
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The copolymers will generally contain from~about 50 to about 95 weight percent butadiene and from about 5 to about 50 weight percent styrene;
preferably from about 50 to about 70 we:Lght percent butadiene and about 30 to about 50 weight percent styrene. Copolymers particularly useful in producing compositions that do not rebo~md from surfaces against which they are thrown are in this preferred range -- most particularly in the range of about 60 to about 70 weight percent butadiene. When less than 5 weight percent styrene is employed, the resulting copolymers do not possess the requisite green tensile strength. More than 50 weight percent styrene in ~'10 the copolymer results in a composition in which hardness is increased at the expense of elasticity. Useful copolymers will generally exhibit a weight average molecular weight in the range of about 75,000 to about 500,000, but a range of about 100,000 to about 350,000 is preferable.
It is also within the scope of this invention to employ radial block copolymers in which the above-described polybutadiene block is not pure polybutadiene but is a block of random butadiene/styrene copolymer or a "tapered" block of butadiene and styrene in which the ratio of butadiene to styrene changes from one end of the block to the other. If such polymers are employed the amount of butadiene and styrene in the total polymer must be within the ranges given above, with the further proviso that the above-described polystyrene blocks must constitute at least 5 weight percent by weight of the total polymer.
The oil which is useful in the practice of this invention is generally selected from those hydrocarbon oils characterized as naph-thenic, paraffinic, or aromatic or mixtures thereof. Commercial oils, although typically classified as one of these types, normally are mixtures and are usually classified according to major component. Impurities such as 2~
unsaturated heterocyclic compounds and aromatic heterocyclic compounds can also be present in small amounts. Oils which are referred to in the industry as heavy white mineral oils are also suitable as extender oils for rubbery polymers. These are usually produced by refining a naphthene-base oil or a mixed naphthene-paraffin-base oil by removal of all hetero-cyclic, unsaturated aliphatic, and aromatic hydrocarbons. Oils in which this removal is not complete are often described as technical grade white mineral oils, whereas when the removal of these impurities is essentially cluantative the product is identified as a U.S.P. white mineral oil.
~aphthenic oils (including heavy white mineral oils) are generally preferred because they do not usually impart an undesirable color to the composition and they exhibit less tendency to exude or "bleed" from the composition.
Aromatic oils are normally used in applications where color of the finished product is not critical, since commercially available aromatic oils gen-erally have characteristic color associated with them. Exudation or "bleed-out" of oil is most likely to occur with oils high in paraffinic content, but is also a function of the physical properties of the oil, such as, for example, viscosity and specific gravity. Exudation is also a function of the rubber used in the composition, heavy mineral oils and naphthenic oils generally exhibiting less exudation with rubbers which have higher conjugated diene content. Some degree of exudation or slow release of oil is desirable or tolerable for specific end-uses. It is also within the scope of this invention to employ vegetable oils in the compositions. The choice of oil for a specific application depends on several factors, such as, for example, the rubber chosen, the degree of exudation desired or allowable, and the required color of the finished product.
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Z8~3 It is frequently desirable to include other additives well known in the rubber art in the inventive compositions. Stabilizers, antioxidants, fillers, reinforcing agents, reinforcing resins, pigments, fragrances, and the like are examples of such types of addi-tives. Specific examples of useful antioxidants and stabilizers include 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, nickel dibutyldithiocar-bamate, tris(nonylphenyl)phosphite, 2,6-di-t-butyl-4-methylphenol, and the like. Exemplary fillers, reinforcing agents, and pigments include clay, silica, carbon black, titanium dioxide, and the like. Titanium dioxide present in a range up to about 500 parts per hundred par-ts by weight copolymer is of special usefulness in producing shaped objects that do not rebound from a vertical surface against which they are thrown.
Polypropylene and polystyrene are examples of thermoplastic resins which function as reinforcing resins.
The compositions of this invention generally contain the above-described ingredients in amounts given in the following tabulation:
Parts by Weight per 100 Parts by IngredientWeight of Radial Teleblock Copolymer Broad Preferred Oil 200-1000 300-700 Filler or reinforcing agent 0-500 3-70 Reinforcing resin 0-200 0-100 Stabilizer 0-5 0.5-3 Pigment 0-10 0.05-1 The compositions of this invention can be prepared by any of the means well known in the art for combining the above ingredients such as solution blending, milling or continuous extrusion. This invention also provi~es specific embodiments for rapid and convenient preparation of the .~
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compositions by heating a mixture of the components to a temperature range of about 120C to about 205C with separate specific embodiments preEerably conducted by stirring a mixture of the components at about 160C to about 205C, preferably 175C to about 205C, or by heating the mixture without stirring in a temperature range of abou-t 125C to about 200C, preferably 125C to about 165C.
One method of preparing a composition consisting of a conjugated diene/monovinyl arene teleblock radial copolymer and a high level of hydrocarbon extender oil requires placing a mixture of the teleblock co-polymer (preferably in particle form) and extender oil in a suitable con-tainer, such as a flat metal pan, and heating said mixture, such as in an oven, without agitation at a temperature whlch normally falls within the range corresponding to about the melting point of the rubber as the lower limit, about 120C, up to about the flash point of the oil as the upper limit, about 200C. Normally and preferably, heating ls conducted within a temperature range of about 125C to about 165C. The composition can be formed of the mixture within a time of several seconds to several hours but the mixture is normally maintained at this temperature for about 15 minutes to several hours. The time required is dependent on such things as the type and quantities of rubber and oil employed, the temperature used and the physical size of the pieces of rubber to be used in the ~;
preparation of the composition. Furthermore, the time required to make a homogeneous mixture can normally be reduced by physically mixing the rubber and the oil prior to the heating step. Additional additives and formulation ingredients can be added to the rubber-oil blend prior to or during the heating step. After the heating step, the composition is normally cooled prior to its use in the fabrication of articles.
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~:~3~2~3 The composition can be further treated if desired, or required, in any conventional mixer, such as a roll mill, particularly if small amounts of undissolved rubber remain after the oven heating step, or if it is desirable to add other ingredients~ or if the ingredients, such as fillers, added prior to or during the heating step have not been uniformly distributed throughout the composition. This additional treatment, if desired, is normally conducted within a temperature range of about 75C to about 125C, preferably maintaining the composition below its melting point, and can be conducted for a few minutes up to several hours, preferably three to 15 minutes, the resulting composition normally being completely homogeneous.
In another embodiment the components of the composition can be mixed and then heated to 175-205C with stirring. Alternatively, and preferably, the oil (with or without the other ingredients exclusive of radial teleblock copolymer) can be heated to 175-205C with subsequent addition with stirring of the copolymer and remaining ingredients.
Solution of the ingredients in the composition at about 175C to about 205C is generally accomplished with stirring during a time period of several seconds to several hours, usually from 0.5 minute to about one hour, although a stirring time of one-half minute to twenty minutes usually ensures complete solution and homogenizing of the blend.
The hot fluid composition from the above-described inventive pre-paration can immediately after preparation be placed in a mold, cast as a film, applied as a coating, etc., and allowed to cool and solidify. Alter-natively, the composition can be cooled in bulk with subsequent sufficient heatings to produce a fluid state for molding, casting, coating, and other uses. Molding can be accomplished by well-known techniques such . ~
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22B~3 as by iniection, compression, or transfer techniques or simply by pouring the hot fluid composition into a mold.
The artificial lures of this invention can be readily pre-pared from the hot fluid composition immediately after preparation or from a batch of the composition previously prepared. The techniques described above are especially suitable for molding the lures.
Artificial lures can be made in any desired size, shape or color. Their particular attractiveness to fish can be measured only by the success of fishermen employing them. At present, artificial worms are the form most preferred by fishermen, but various insects, spiders, frogs, small fish, and even abstract shapes can be contemplated; therefore, variations from simple monocolored worm can be employed to create a lure with special allure. These variations are considered to be within the scope of this invention. For example, batches of the composition containing different pigments can be placed sequentially in a single mold to produce multicolored lures. Alternatively, small pieces of metal-lic foil or brightly colored particles can be mixed with the inventive composition prior to molding to produce lures impregnated with reflective or brightly colored particles.
Molded objects useful in other aspects of this invention can be made decorative similarly to the artificial lures.
EXA~LE I
The following runs illustrate several methods of preparation of compositions according to this invention.
Radial teleblock copolymer of butadiene/styrene weight ratio 60/40 with weight average molecular weight 216,000, prepared using n-butyl-lithium as initiator and silicon tetrachloride as coupling agent was extended -lla-8;~
with 50 phr (parts by weight per 100 parts by weight rubber) of naphthenic extender oil. Extended rubber, as produced above, and additional naphthenic extender oil were employed in the preparation of composi-tions according to the invention.
Run 1 (Method 1) Extended rubber (80 gm) and oil (200 gm), which is a total of 425 phr oil, were mixed at room temperature in a stirred open vessel with external heating. I~hen the temperature of the stirred heated mixture reached 199C, solution of the rubber was complete giving a smooth, fluid, homo-geneous composition which cooled to give an elastic composition with a slightly oily surface.
Run 2 (~ethod 2) Extended rubber (80 gm) and naphthenic oil (240 gm), which is a total of 500 phr oil, were mixed and allowed to stand at room temperature for 15 minutes. With subsequent stirring and heating for 30 minutes in the vessel of Run 1 the temperature reached 202C and complete solution was observed.
Run 3 (Method 3) Naphthenic oil (240 gm) was heated in the vessel of Run 1 to 205C at which time extended rubber (80 gm), which is a total of 500 phr oil, was added. After continuous stirring for 20 minutes, solution was complete. After pouring into a mold and cooling, an elastic composition was obtained with a slightly oily surface.
Run 4 (Method 4) For this run, radial teleblock copolymer of butadienelstyrene weight ratio of 70/30 with weight average molecular weight of about 300,000, prepared using n-butyllithium, as initiator, and silicon tetrachloride, as coupling agent, was employed.
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Ground rubber (400 grams) and a U.S.P. heavy white mineral oil (1200 grams; 300 phr), and titanium dioxide (80 grams; 20 phr) were poured into a flat metal pan, stirred briefly with a spatula, and then placed in a forced air oven at 125C for one hour. The mixture was removed from the oven and allowed to cool. Although all the oil had been absorbed into the rubber, there remained a few particles of undissolved rubber and the titanium dioxide was concentrated in the lower part of the composition. A
sample of this composition (600 grams) was milled on a 6 x 12 inch roll mill at 121C for five minutes. This milling incorporated the remaining undissolved rubber and produced a smooth homogeneous composition.
EXA~IP~E II
The following comparative runs illustrate attempts to prepare inventive compositions using non-inventive methods.
Run 5 Toluene (400 ml), extended rubber (80 gm), as prepared in Example I, and naphtenic oil (240 gm) were mixed at room temperature. After complete solution of components was achieved (two hours) the solution was poured into an open pan for removal of solvent. At ambient conditions a skin formed on the surface of the composition which prevented further solvent removal. Subjecting the composition to a vacuum of 67 to 85 kPa and a temperature of 70C also resulted in a skin on the surface of the composition which prevented further drying. Conse~uently, the toluene-containing composition was discarded.
Run 6 Extended rubber was banded (at 121C) on a 15 cm x 30 cm labora-tory roll mill. ~aphthenic oil was added to the rubber during milling as rapidly as the rubber would take it up. After two hours milling, only ~32~83 25~ phr (total) oil had been added. The softnes~ of the composition hsd reduced shear to the point that little, if any, more oil could be added to the composition. The difficulty and time required to prepare a composition using the method of this run would greatly limit its utility.
EXAMPLE III
The following runs demonstrate a variety of copolymer-extender oil combinations useful in the compositions of this invention.
Butadiene~styrene radial teleblock copolymers having varying butadiene/styrene weight ratios were mixed according to the method of Example I, Run 4 (Method 4) with 300 phr of various oils and 20 phr of various fillers and the exudation or "bleed-out" evaluated after two weeks o~ aging at ambient room temperature. The results are given in Table I.
In addition to the oils in Table I, soybean oil and a co~mercial non-detergent 20W motor oil were tested with the same 60/40 butadiene/
styrene radial telebloc~ copolymer but without added filler and at a different oil/copoly~er ratio than the compositions in Table I. Bleed-out was heavy with both of these oils and a strong odor was clea~ly evident.
In contrast~ the compositions of Table I had only a very slighS odor.
These data illustrate that the extent of bleed-out is a function of the extender oil used and the butadienelstyrene weight ratio of the teleblock copolymer, and that the mineral and naphthenic oils evaluated have a lower level of exudation with polymers having a higher weight ratio of butadiene. With the teleblock copolymer having a 60l40 butadiene/
styrene weight ratio, Flexon 766 naphthenic oil provided the lowest level of exudation of the oils evaluated, while the teleblock copolymers having a 70/30 butadiene/styrene weight ratio, exudation was essentially non-existent with any of the oils evaluated at a 300 phr oil level. The type of filler employed clid not appear to influence the level of exudation at the conditions of this study.
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Such objects in various shapes and colors can be used to define and decorate the transparent surface of a window. At the other end of the spectrum are spheroids which tend to roll down a vertical surface. In between, there is a relationship between the amount of flat surface on the molded object that is pressed against the vertical surface and the total weight of the object which determines the ability of an object of the inventive composition to "stick" to a vertical surface. The invention contemplates objects of any shape, but particularly those of size to be easily thrown by hand. The object can be regular as a parallelepiped, spheroid, dodecahedron, etc., or totally irregular in shape, but with sufficient surface to allow adherence to a vertical surface. All of the shapes are adaptable in preparing objects useful as toys or useful as objects employed as part of a game or recreational activity.
As mentioned above, the smoothness of the surface against which the object is pressed directly affects the ability of the object to remain on the surface. Glass, polished marble, polished metal, and concrete formed against plywood or other smooth surface have surfaces that do not cause rebound of objects of this invention that are thrown thereagainst.
It is therefor an object of this invention to provide a highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer composition. It is another object of this invention to provide a method for preparing a highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer composition. It is another object of this invention to provide an artificial fishing lure molded from a highly oil-extended conjugated dienetvinyl aromatic teleblock copolymer composition. It is still another object of this invention to provide an object molded from -: , . - - ,. : - . - . , :
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-: .: .: . , a highly oil-extended radial teleblock copolymer suitable preferably to adhere to a vertical surface against which it is thrown; but, at least, sufficient not to rebound from the surEace.
Other aspects, objects, and the various advantages of this in-vention will become apparent upon a study of this specification and the appended claims.
Statement of the Invention According to this invention, a composition is provided that is a blended mixture of a conjugated diene/vinyl aromatic radial teleblock copolymer extended with a hydrocarbon oil.
Also, according to this invention, a method is provided for pre-paring a highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer in which a conjugated diene/vinyl aromatic radial teleblock copolymer and a hydrocarbon oil are admixed and the mixture raised to an elevated temperature of about 120C to about 205C until a homogeneous blend is produced. In preferred embodiments of the invention, the copolymer and hydrocarbon oil are stirred together to form a mixture at a temperature elevated to about 175C to about 205C with stirring continued until a homogeneous blend is produced or a mixture of the co-polymer and hydrocarbon oil is prepared and the mixture elevated to a temperature in the range of about 120C to about 200C without stirring until a homogeneous blend is produced.
In an embodiment of the invention, a fishing lure comprising a highly oil-extended conjugated diene/vinyl aromatic radial teleblock copolymer composition molded in a suitable conformation is provided.
In another embodiment of the invention, shaped objects that do not rebound from vertical surfaces against which they are thrown and which tend to remain in place on surfaces against which they are pressed are also provided.
Among the conjugated diene/vinyl aromatic teleblock copolymers which can be oil-extended and cast into useful objects are radial or branched teleblock copolymers of butadiene and styrene which are prepared by methods which are well known in the art. For example, use of an organolithium initiating species to polymerize styrene monomer to form a living polymer of polystyryllithium represented by:
polystyrene--Li followed by addition of butadiene monomer to the polystyryllithium to form a living polymer represented by polystyrene-polybutadiene-Li and subsequent coupling of the living polymer with a multifunctional coupling agent, such as silicon tetrachloride, results in polymers which are represented by (polystyrene-polybutadiene) Y
wherein Y represents a coupling agent residue and n is a number greater - than 2 and preferably from 3 to 5. Such polymers are characterized as ..
being elastomeric in the unvulcanized state as well as thermoplastic since they can be molded.
Useful polymers which also contain outward polystyrene blocks and inward polybutadiene blocks can be prepared by employing a polyfunc-tional initiating species, such as an organopolylithium compound, onto which polybutadiene blocks are polymerized with subsequent polymerization of polystyrene blocks. Such polymers are represented by (polystyrene-polybutadiene) Z
wherein Z represents the residue of the polyfunctional initiating speçies and n is as described above.
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The copolymers will generally contain from~about 50 to about 95 weight percent butadiene and from about 5 to about 50 weight percent styrene;
preferably from about 50 to about 70 we:Lght percent butadiene and about 30 to about 50 weight percent styrene. Copolymers particularly useful in producing compositions that do not rebo~md from surfaces against which they are thrown are in this preferred range -- most particularly in the range of about 60 to about 70 weight percent butadiene. When less than 5 weight percent styrene is employed, the resulting copolymers do not possess the requisite green tensile strength. More than 50 weight percent styrene in ~'10 the copolymer results in a composition in which hardness is increased at the expense of elasticity. Useful copolymers will generally exhibit a weight average molecular weight in the range of about 75,000 to about 500,000, but a range of about 100,000 to about 350,000 is preferable.
It is also within the scope of this invention to employ radial block copolymers in which the above-described polybutadiene block is not pure polybutadiene but is a block of random butadiene/styrene copolymer or a "tapered" block of butadiene and styrene in which the ratio of butadiene to styrene changes from one end of the block to the other. If such polymers are employed the amount of butadiene and styrene in the total polymer must be within the ranges given above, with the further proviso that the above-described polystyrene blocks must constitute at least 5 weight percent by weight of the total polymer.
The oil which is useful in the practice of this invention is generally selected from those hydrocarbon oils characterized as naph-thenic, paraffinic, or aromatic or mixtures thereof. Commercial oils, although typically classified as one of these types, normally are mixtures and are usually classified according to major component. Impurities such as 2~
unsaturated heterocyclic compounds and aromatic heterocyclic compounds can also be present in small amounts. Oils which are referred to in the industry as heavy white mineral oils are also suitable as extender oils for rubbery polymers. These are usually produced by refining a naphthene-base oil or a mixed naphthene-paraffin-base oil by removal of all hetero-cyclic, unsaturated aliphatic, and aromatic hydrocarbons. Oils in which this removal is not complete are often described as technical grade white mineral oils, whereas when the removal of these impurities is essentially cluantative the product is identified as a U.S.P. white mineral oil.
~aphthenic oils (including heavy white mineral oils) are generally preferred because they do not usually impart an undesirable color to the composition and they exhibit less tendency to exude or "bleed" from the composition.
Aromatic oils are normally used in applications where color of the finished product is not critical, since commercially available aromatic oils gen-erally have characteristic color associated with them. Exudation or "bleed-out" of oil is most likely to occur with oils high in paraffinic content, but is also a function of the physical properties of the oil, such as, for example, viscosity and specific gravity. Exudation is also a function of the rubber used in the composition, heavy mineral oils and naphthenic oils generally exhibiting less exudation with rubbers which have higher conjugated diene content. Some degree of exudation or slow release of oil is desirable or tolerable for specific end-uses. It is also within the scope of this invention to employ vegetable oils in the compositions. The choice of oil for a specific application depends on several factors, such as, for example, the rubber chosen, the degree of exudation desired or allowable, and the required color of the finished product.
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Z8~3 It is frequently desirable to include other additives well known in the rubber art in the inventive compositions. Stabilizers, antioxidants, fillers, reinforcing agents, reinforcing resins, pigments, fragrances, and the like are examples of such types of addi-tives. Specific examples of useful antioxidants and stabilizers include 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, nickel dibutyldithiocar-bamate, tris(nonylphenyl)phosphite, 2,6-di-t-butyl-4-methylphenol, and the like. Exemplary fillers, reinforcing agents, and pigments include clay, silica, carbon black, titanium dioxide, and the like. Titanium dioxide present in a range up to about 500 parts per hundred par-ts by weight copolymer is of special usefulness in producing shaped objects that do not rebound from a vertical surface against which they are thrown.
Polypropylene and polystyrene are examples of thermoplastic resins which function as reinforcing resins.
The compositions of this invention generally contain the above-described ingredients in amounts given in the following tabulation:
Parts by Weight per 100 Parts by IngredientWeight of Radial Teleblock Copolymer Broad Preferred Oil 200-1000 300-700 Filler or reinforcing agent 0-500 3-70 Reinforcing resin 0-200 0-100 Stabilizer 0-5 0.5-3 Pigment 0-10 0.05-1 The compositions of this invention can be prepared by any of the means well known in the art for combining the above ingredients such as solution blending, milling or continuous extrusion. This invention also provi~es specific embodiments for rapid and convenient preparation of the .~
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compositions by heating a mixture of the components to a temperature range of about 120C to about 205C with separate specific embodiments preEerably conducted by stirring a mixture of the components at about 160C to about 205C, preferably 175C to about 205C, or by heating the mixture without stirring in a temperature range of abou-t 125C to about 200C, preferably 125C to about 165C.
One method of preparing a composition consisting of a conjugated diene/monovinyl arene teleblock radial copolymer and a high level of hydrocarbon extender oil requires placing a mixture of the teleblock co-polymer (preferably in particle form) and extender oil in a suitable con-tainer, such as a flat metal pan, and heating said mixture, such as in an oven, without agitation at a temperature whlch normally falls within the range corresponding to about the melting point of the rubber as the lower limit, about 120C, up to about the flash point of the oil as the upper limit, about 200C. Normally and preferably, heating ls conducted within a temperature range of about 125C to about 165C. The composition can be formed of the mixture within a time of several seconds to several hours but the mixture is normally maintained at this temperature for about 15 minutes to several hours. The time required is dependent on such things as the type and quantities of rubber and oil employed, the temperature used and the physical size of the pieces of rubber to be used in the ~;
preparation of the composition. Furthermore, the time required to make a homogeneous mixture can normally be reduced by physically mixing the rubber and the oil prior to the heating step. Additional additives and formulation ingredients can be added to the rubber-oil blend prior to or during the heating step. After the heating step, the composition is normally cooled prior to its use in the fabrication of articles.
. . .. .. .
~:~3~2~3 The composition can be further treated if desired, or required, in any conventional mixer, such as a roll mill, particularly if small amounts of undissolved rubber remain after the oven heating step, or if it is desirable to add other ingredients~ or if the ingredients, such as fillers, added prior to or during the heating step have not been uniformly distributed throughout the composition. This additional treatment, if desired, is normally conducted within a temperature range of about 75C to about 125C, preferably maintaining the composition below its melting point, and can be conducted for a few minutes up to several hours, preferably three to 15 minutes, the resulting composition normally being completely homogeneous.
In another embodiment the components of the composition can be mixed and then heated to 175-205C with stirring. Alternatively, and preferably, the oil (with or without the other ingredients exclusive of radial teleblock copolymer) can be heated to 175-205C with subsequent addition with stirring of the copolymer and remaining ingredients.
Solution of the ingredients in the composition at about 175C to about 205C is generally accomplished with stirring during a time period of several seconds to several hours, usually from 0.5 minute to about one hour, although a stirring time of one-half minute to twenty minutes usually ensures complete solution and homogenizing of the blend.
The hot fluid composition from the above-described inventive pre-paration can immediately after preparation be placed in a mold, cast as a film, applied as a coating, etc., and allowed to cool and solidify. Alter-natively, the composition can be cooled in bulk with subsequent sufficient heatings to produce a fluid state for molding, casting, coating, and other uses. Molding can be accomplished by well-known techniques such . ~
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22B~3 as by iniection, compression, or transfer techniques or simply by pouring the hot fluid composition into a mold.
The artificial lures of this invention can be readily pre-pared from the hot fluid composition immediately after preparation or from a batch of the composition previously prepared. The techniques described above are especially suitable for molding the lures.
Artificial lures can be made in any desired size, shape or color. Their particular attractiveness to fish can be measured only by the success of fishermen employing them. At present, artificial worms are the form most preferred by fishermen, but various insects, spiders, frogs, small fish, and even abstract shapes can be contemplated; therefore, variations from simple monocolored worm can be employed to create a lure with special allure. These variations are considered to be within the scope of this invention. For example, batches of the composition containing different pigments can be placed sequentially in a single mold to produce multicolored lures. Alternatively, small pieces of metal-lic foil or brightly colored particles can be mixed with the inventive composition prior to molding to produce lures impregnated with reflective or brightly colored particles.
Molded objects useful in other aspects of this invention can be made decorative similarly to the artificial lures.
EXA~LE I
The following runs illustrate several methods of preparation of compositions according to this invention.
Radial teleblock copolymer of butadiene/styrene weight ratio 60/40 with weight average molecular weight 216,000, prepared using n-butyl-lithium as initiator and silicon tetrachloride as coupling agent was extended -lla-8;~
with 50 phr (parts by weight per 100 parts by weight rubber) of naphthenic extender oil. Extended rubber, as produced above, and additional naphthenic extender oil were employed in the preparation of composi-tions according to the invention.
Run 1 (Method 1) Extended rubber (80 gm) and oil (200 gm), which is a total of 425 phr oil, were mixed at room temperature in a stirred open vessel with external heating. I~hen the temperature of the stirred heated mixture reached 199C, solution of the rubber was complete giving a smooth, fluid, homo-geneous composition which cooled to give an elastic composition with a slightly oily surface.
Run 2 (~ethod 2) Extended rubber (80 gm) and naphthenic oil (240 gm), which is a total of 500 phr oil, were mixed and allowed to stand at room temperature for 15 minutes. With subsequent stirring and heating for 30 minutes in the vessel of Run 1 the temperature reached 202C and complete solution was observed.
Run 3 (Method 3) Naphthenic oil (240 gm) was heated in the vessel of Run 1 to 205C at which time extended rubber (80 gm), which is a total of 500 phr oil, was added. After continuous stirring for 20 minutes, solution was complete. After pouring into a mold and cooling, an elastic composition was obtained with a slightly oily surface.
Run 4 (Method 4) For this run, radial teleblock copolymer of butadienelstyrene weight ratio of 70/30 with weight average molecular weight of about 300,000, prepared using n-butyllithium, as initiator, and silicon tetrachloride, as coupling agent, was employed.
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Ground rubber (400 grams) and a U.S.P. heavy white mineral oil (1200 grams; 300 phr), and titanium dioxide (80 grams; 20 phr) were poured into a flat metal pan, stirred briefly with a spatula, and then placed in a forced air oven at 125C for one hour. The mixture was removed from the oven and allowed to cool. Although all the oil had been absorbed into the rubber, there remained a few particles of undissolved rubber and the titanium dioxide was concentrated in the lower part of the composition. A
sample of this composition (600 grams) was milled on a 6 x 12 inch roll mill at 121C for five minutes. This milling incorporated the remaining undissolved rubber and produced a smooth homogeneous composition.
EXA~IP~E II
The following comparative runs illustrate attempts to prepare inventive compositions using non-inventive methods.
Run 5 Toluene (400 ml), extended rubber (80 gm), as prepared in Example I, and naphtenic oil (240 gm) were mixed at room temperature. After complete solution of components was achieved (two hours) the solution was poured into an open pan for removal of solvent. At ambient conditions a skin formed on the surface of the composition which prevented further solvent removal. Subjecting the composition to a vacuum of 67 to 85 kPa and a temperature of 70C also resulted in a skin on the surface of the composition which prevented further drying. Conse~uently, the toluene-containing composition was discarded.
Run 6 Extended rubber was banded (at 121C) on a 15 cm x 30 cm labora-tory roll mill. ~aphthenic oil was added to the rubber during milling as rapidly as the rubber would take it up. After two hours milling, only ~32~83 25~ phr (total) oil had been added. The softnes~ of the composition hsd reduced shear to the point that little, if any, more oil could be added to the composition. The difficulty and time required to prepare a composition using the method of this run would greatly limit its utility.
EXAMPLE III
The following runs demonstrate a variety of copolymer-extender oil combinations useful in the compositions of this invention.
Butadiene~styrene radial teleblock copolymers having varying butadiene/styrene weight ratios were mixed according to the method of Example I, Run 4 (Method 4) with 300 phr of various oils and 20 phr of various fillers and the exudation or "bleed-out" evaluated after two weeks o~ aging at ambient room temperature. The results are given in Table I.
In addition to the oils in Table I, soybean oil and a co~mercial non-detergent 20W motor oil were tested with the same 60/40 butadiene/
styrene radial telebloc~ copolymer but without added filler and at a different oil/copoly~er ratio than the compositions in Table I. Bleed-out was heavy with both of these oils and a strong odor was clea~ly evident.
In contrast~ the compositions of Table I had only a very slighS odor.
These data illustrate that the extent of bleed-out is a function of the extender oil used and the butadienelstyrene weight ratio of the teleblock copolymer, and that the mineral and naphthenic oils evaluated have a lower level of exudation with polymers having a higher weight ratio of butadiene. With the teleblock copolymer having a 60l40 butadiene/
styrene weight ratio, Flexon 766 naphthenic oil provided the lowest level of exudation of the oils evaluated, while the teleblock copolymers having a 70/30 butadiene/styrene weight ratio, exudation was essentially non-existent with any of the oils evaluated at a 300 phr oil level. The type of filler employed clid not appear to influence the level of exudation at the conditions of this study.
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(c) 20 phr filler in each composition.
(d) Determined visibly and to the touch after the compositions had aged at ambient room temperature for two weeks.
(e) Naphthenic oil (AST~I Type 104A) from Exxon Company.
(f) Kaolin (hard) clay from R. T. Vanderbilt.
(g) Type R-101 from duPont.
(h) Fine precipitated CaC03 of 0.15-0.30~ particle size from BASF Wyandotte.
(i) U.S.P. heavy white mineral oil composed entirely of saturated aliphatic and naphthenic hydrocarbons from Witco Chemical, Sonneborn Division.
(j) Naphthenic type technical grade heavy white mineral oil from Atlantic Richfield Company.
(k) U.S.P. heavy white mineral oil from Marathon Norco Co.
EXAMPLE IV
The following inventive runs 16, 17, and 18 illustrate other radial teleblock copolymers which are useful in the inventive composition.
Accompanying comparative run 19 illustrates the use of a random copolymer of butadiene and styrene that is not within the scope of this invention.
Preparation ~ethod 3 of Example I with a five-minute mixing time after addition of rubber was employed in these runs. Naphthenic oil (500 phr total) was employed in the preparation of the compositions. Table II
contains data obtained in runs 16 to 19.
TABLE II
Run Solut:ion Cooled No. Rubber Appearance Appearance 16 A Gelled --17 B Lumpy Normal with resinous particles 18 C3 Small lumps Normal with small resinous particles 19 D4 Didn~t dis- --solve (1) 60/40 Butadiene/styrene radial teleblock copolymer initiated with n-butyllithium and coupled with SiC14.
M~ = 300,000. Contains 0.5 phr 2,6-di-t-butyl-4-metholphenol and 1.5 phr tris(nonylphenyl)phosphite.
(2) 70/30 Butadiene/styrene radial teleblock copolymer initiated with n-butyllithium and coupled with SiC14.
Mw = 304,000. Contains same stabilizer system as footnote 1 above.
(3) 52.5/47.5 Butadiene/styrene radial teleblock copolymer initiated with n-butyllithium and coupled with SiC14.
Extended with 60 phr naphthenic oil. Mw = 200,000.
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(b) 300 phr total oil in each composition.
(c) 20 phr filler in each composition.
(d) Determined visibly and to the touch after the compositions had aged at ambient room temperature for two weeks.
(e) Naphthenic oil (AST~I Type 104A) from Exxon Company.
(f) Kaolin (hard) clay from R. T. Vanderbilt.
(g) Type R-101 from duPont.
(h) Fine precipitated CaC03 of 0.15-0.30~ particle size from BASF Wyandotte.
(i) U.S.P. heavy white mineral oil composed entirely of saturated aliphatic and naphthenic hydrocarbons from Witco Chemical, Sonneborn Division.
(j) Naphthenic type technical grade heavy white mineral oil from Atlantic Richfield Company.
(k) U.S.P. heavy white mineral oil from Marathon Norco Co.
EXAMPLE IV
The following inventive runs 16, 17, and 18 illustrate other radial teleblock copolymers which are useful in the inventive composition.
Accompanying comparative run 19 illustrates the use of a random copolymer of butadiene and styrene that is not within the scope of this invention.
Preparation ~ethod 3 of Example I with a five-minute mixing time after addition of rubber was employed in these runs. Naphthenic oil (500 phr total) was employed in the preparation of the compositions. Table II
contains data obtained in runs 16 to 19.
TABLE II
Run Solut:ion Cooled No. Rubber Appearance Appearance 16 A Gelled --17 B Lumpy Normal with resinous particles 18 C3 Small lumps Normal with small resinous particles 19 D4 Didn~t dis- --solve (1) 60/40 Butadiene/styrene radial teleblock copolymer initiated with n-butyllithium and coupled with SiC14.
M~ = 300,000. Contains 0.5 phr 2,6-di-t-butyl-4-metholphenol and 1.5 phr tris(nonylphenyl)phosphite.
(2) 70/30 Butadiene/styrene radial teleblock copolymer initiated with n-butyllithium and coupled with SiC14.
Mw = 304,000. Contains same stabilizer system as footnote 1 above.
(3) 52.5/47.5 Butadiene/styrene radial teleblock copolymer initiated with n-butyllithium and coupled with SiC14.
Extended with 60 phr naphthenic oil. Mw = 200,000.
(4) 65/35 Butadiene/styrene random copolymer. Extended with 37.5 phr aromatic oil.
In Run 16, solution of rubber in oil appeared to proceed normally until near the end of the heating period when the polymer appeared to gel. The conclusion is that insufficient stabilizer was present in the rubber of that composition and molecular weight to protect it adequately during the heating period.
~322~33 In Runs 17 and 18 the solution of the rubber in the oil appeared to proceed normally except for the presence of swollen pieces of polymer.
The cooled compositions appeared to be normal except for the appearance of resinous particles. Apparently the original rubber contained some particles of gel or resinous material prior to addition to the hot oil.
In comparative Run l9 the rubber did not dissolve in the oil under the employed mixing conditions; therefore, the composition was dis-carded.
EXA~fPLE V
The following inventive runs illustrate inventive compositions ~ith varying amounts of oil and properties thereof.
Preparation Method 3 of Example I was employed with ten minutes mixing time after rubber addition. The extended rubber described in Example I was employed. Table III contains the resultant data.
TABLE III
Run No. 20 21 22 23 24 Naphthenic oil, phr400 500 600 700 0 Mineral oil, phr 0 0 0 0 400 Specific gravity 0.90 0.90 0.90 0.90 0.90 Tensile, psi 49 28 15 14 15 Elongation, %700 600 500 500 600 Hardness 87 81 73 70 83 Tear, lb/in 4 3 2 2 5 Permanent set, %4 11 10 10 11 11 ~eight change, % :
48 hr. in water~0.05 0 0.05 0.41 0.29 48 hr. in air0.05 0.15 0.34 0.56 0.42 (continued) ~3~2~3~
(1) ASTM D-412-66.
(2) Sponge gauge hardness - measured using Sponge Rubber Gauge Model 302-S (Pacific Transducer Corp., Los Angeles, CA). 0 to 100 scale with 100 being hardest, 0 being softest.
(3) Measured according to ASTM-624-54.
(4) Set measured after 50 percent compression for 24 hours at room temperature followed by one hour relaxation.
In Run 16, solution of rubber in oil appeared to proceed normally until near the end of the heating period when the polymer appeared to gel. The conclusion is that insufficient stabilizer was present in the rubber of that composition and molecular weight to protect it adequately during the heating period.
~322~33 In Runs 17 and 18 the solution of the rubber in the oil appeared to proceed normally except for the presence of swollen pieces of polymer.
The cooled compositions appeared to be normal except for the appearance of resinous particles. Apparently the original rubber contained some particles of gel or resinous material prior to addition to the hot oil.
In comparative Run l9 the rubber did not dissolve in the oil under the employed mixing conditions; therefore, the composition was dis-carded.
EXA~fPLE V
The following inventive runs illustrate inventive compositions ~ith varying amounts of oil and properties thereof.
Preparation Method 3 of Example I was employed with ten minutes mixing time after rubber addition. The extended rubber described in Example I was employed. Table III contains the resultant data.
TABLE III
Run No. 20 21 22 23 24 Naphthenic oil, phr400 500 600 700 0 Mineral oil, phr 0 0 0 0 400 Specific gravity 0.90 0.90 0.90 0.90 0.90 Tensile, psi 49 28 15 14 15 Elongation, %700 600 500 500 600 Hardness 87 81 73 70 83 Tear, lb/in 4 3 2 2 5 Permanent set, %4 11 10 10 11 11 ~eight change, % :
48 hr. in water~0.05 0 0.05 0.41 0.29 48 hr. in air0.05 0.15 0.34 0.56 0.42 (continued) ~3~2~3~
(1) ASTM D-412-66.
(2) Sponge gauge hardness - measured using Sponge Rubber Gauge Model 302-S (Pacific Transducer Corp., Los Angeles, CA). 0 to 100 scale with 100 being hardest, 0 being softest.
(3) Measured according to ASTM-624-54.
(4) Set measured after 50 percent compression for 24 hours at room temperature followed by one hour relaxation.
(5) Cylindrical pellets 3.2 cm diameter X 1.3 cm length. Recorded as percentage weight loss except where recorded as "+" which refers to weight gain.
The data in Table III show characteristic desirable properties of the compositions of this invention. Varying the amount of oil in compositions can provide a range of properties to correspond with the desired application.
EXA~IPLE VI
Compositions of this invention and commercial artificial fishing worms were contacted with polystyrene to determine the relative sensitivity of polystyrene to these compositions.
A polystyrene sheet 3.2 mm thick was contacted at room tem-perature for 48 hours with cylindrical pellets 3.2 cm diameter X 1.3 cm length of the inventive compositions of Runs 20 to 24 and with pellets of commercial artificial fishing worm compositions based on poly(vinyl chloride) highly extended with dibutyl phthalate (worms were melted and cast into pellets). The inventive compositions produced no detectable change in the polystyrene surface; whereas the commercial artificial worm compositions caused serious softening, sagging, and even dissolution of the polystyrene surface.
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The results of the above-described tests indicate that the inventive artificial fishing worms can be contacted with polystyrene tackle boxes, floats, lures, etc., wthout the detrimental effect characteristic of the poly(vinyl chloride)/dibutyl phthalate worms.
It should be noted that contacting artificial worms of the composition of this invention with poly~vinyl chloride)/dibutyl phthalate worms resulted in rapid deterioration of both worms. Hence, such contact should be avoided.
E.YAMPLE VII
The following inventive runs are illustrative of the additives successfully employed in inventive compositions.
The extended rubber described in Example I and naphthenic oil were employed. Mixing was as generally described in Preparation Method 3 of Example I with minor variations in mixing times after rubber addition.
Table IV lists the additives and composition proportions.
TABLE IV
Run Naphthenic No. Oil, PHR Additive PHR
400 Silica 10 26 500 Silica 67 27 700 Silica 4 28 400 Talc 10 29 500 Clay 17 400 Silica 25 Coumarone-indene resin 30 31 400 Clay 50 Coumarone-indene resin 30 32 400 Polystyrene 100 33 300 Polypropylene 50 34 500 Stabilizer Al 2 500 Stabilizer B 2 36 500 Stabilizer C3 1 ~-37 500 Stabilizer D 2 (1) 2,6-di-t-butyl-4-methylphenol.
(2) tris(nonylphenyl)phosphite.
(3) Nickel dibutyldithiocarbamate.
(4) 2-(2'-hydroxy-5'-methylphenyl)benzotriazole.
EXA~IPLE VIII
Inventive artificial fishing worms were prepared from inventive compositions.
The mold employed for hot melt casting had a cavity approximately 18 cm deep with the upper 16 cm being cylindrical with varying diameter (1 cm maximum, 0.5 cm minimum) along the length of the cylinder. The lower 2 cm of the cavity was flattened to provide an oblong flat tail on the -resultant worm 2 mm thick, 1.5 cm across at the widest point, and 2 cm long.
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Compositions containing the extended rubber described in Example I, naphthenic oil (300 to 700 phr total oil), various of the addi-tives given in Table IV, and various pigments were prepared generally as described in ~lethod 3 of Example I and while being maintained at 190-205C
were poured into the above-described molds. After cooling the molds were opened and the artificial fishing worms were removed.
The artificial worms were also prepared by injection molding of compositions as described above in molds with cavities approximately 11 cm long the upper 5 cm of which was semicylindrical with varying diameter (1 cm maximum, 0.5 cm minimum) along the length of the semicylinder. The lower 6 cm of the cavity was ilattened and curved to provide a long curved tail varying from 6 mm to 3 mm in width and 1 to 2 mm thick.
The resultant worms from the hot melt casting and injection molding were successfully employed to catch fish. They were especially successful in the catching of large mouth bass.
E ~PLE IX
This example illustrates the preparation of inventive balls from the inventive composition. Oil-extended stock representing each of the compositions described in Table I of Example III and similar stock repre-senting each of the compositions described in Table V was loaded into a transfer mold having 26 spherical cavities measuring 3.18 cm in diameter.
The loaded transfer mold was placed in a heated hydraulic press and main-tained at 121C for a ten-minute warmup period without any applied pressure.
A pressure of 30 tons was then applied and maintained for 15 minutes.
At the end of this time, the pressure was released and the mold removed and placed in a second hydraulic press cooled with circulating cold tap water and maintained at 30 tons pressure until the mold cooled. This procedure produced good smooth balls from each of the compositions.
2~B3 The oil-extended stocks of the compositions described in Table I were cut into thin strips and then f ormed by hand into a spherical mass slightly larger than the 4.32 cm diameter spherical cavities of a compression mold. These hand-shaped masses were placed in these cavities and then compression molded using the same basic procedure described earlier for transfer molding. Several of the compression molded balls contained flaws in the form of small holes due to air trapped in the compression mold.
.
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.2~33 Molded balls prepared from the highly oil-extended radial teleblock copolymer compositions described in Tables I and V were observed to have the unique property of not rebounding when thrown against or dropped on a hard solid surface. Furthermore, molded balls from certain of these formulations not only failed to rebound but also when thrown against certain smooth or slightly rough vertical surfaces maintained contact with that surface and slowly rolled down. Molded balls from certain other of these formulations while having the same smooth outward appearance, and although likewise not rebounding when thrown against a solid surface, did not have the tendency to stick and slowly roll down, but rather after striking a vertical surface immediately fell to the floor. In general, copolymers having higher butadiene content and those containing filler were observed to have a greater tendency to stick or maintain contact with a vertical surface. This is illustrated by the observation that molded balls from Runs 12-15, 46, and 47 (all from copolymers containing 70 weight percent butadiene) all stuck and slowly rolled down a vertical sur-face, while molded balls from Runs 38-42 and 45 (all from copolymers containing 60 weight~ percent butadiene~ did not stick at all, but fell immediately to the floor. Furthermore, a ball from Run 44 which contains a 60 weight percent copolymer but having a very high 375 phr titanium dioxide stuck well, while a ball from Run 8 containing the same copolymer but only 20 phr titanium dioxide had considerably less tendency to stick, although better than balls from Run 43 which contain no filler. The amount of exudation of oil likewise was observed to affect this property, washing the ball with soap to remove excess surface oil often leading to improved adhesion of the ball to a vertical surface.
28~
EX~LE X
This example illustrates the amount of exudation as a function of the oil level employed for a composition consisting of the 70/30 butadiene/-styrene radial ~eleblock copolymer used in Runs 12-15 of Example III, 20 phr of titanium dioxide, and varying levels of Sontex 35 U.S.~. heavy white mineral oil from Marathon Norco Company.
The compositions were prepared according to the method of Example I, Run 4 (Method 4). Each composition was transfer molded into a ball according to the procedure described in Example IX and was aged for three days at room temperature. Each sample was then placed on a stack of white writing paper for 24 hours to evaluate oil migration. ~ second ball molded from each composition was aged for six days under the same con-ditions described above and then evaluated both visibly and to the touch for oil bleed-out. The results of this evaluation, as tabulated in Table VI, indicate that for this particular combination of ingredients, the amount of oil migration and bleed-out is a function of the oil concentration in the composition.
~322~3~
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o ~1 ol c~ CJ~ O ~ C~l ~i3~83 EXAMPLE ~I
This example illustrates a difference in properties of a composition of the present invention using butadiene/styrene radial copolymer as compared to a composition outside the present invention using a butadiene/styrene linear copolymer. Compositions were prepared according to the method of Example I, Run 4 (Method 4) by blendin~ for Run 53 a 70/30 butadiene/styrene radial block copolymer with 300 parts Marathon-Norco U.S.P. heavy white mineral oil and 20 parts TiO2 per 100 parts of the rubber compound. For Run 54 a 70/30 butadiene/styrene linear block copolymer was blended with 300 parts Marathon-Norco U.S.P. heavy white mineral oil and 20 parts TiO2 per 100 parts of the rubber compound. In each formulation all of the ingredients were mixed in a pan and then placed in an oven without further stirring for 30 minutes at 164C. The composition was let cool and the masterbatch was blended on a roll mill for five minutes at 120C. The material in each run was then molded into balls. The results of observations of the balls are reported in Tab~e VII
below.
~3~83 ~ b~
,~ ~ o.~
al ~d ~ ~ S S
O
¢ ~ CO~ Z
~ ~ l ~o ~,1 o ~ ~3 g g u~ O ~: C!~ C~
~q a Q~
g ¢~ Z X
~ l 2, .
oo ~ a g g o e z z ~ ~d .
o o U~
~J ~
o ~ ~ ~ o ~ ~ za uS, ?~
C~ ~
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¢ ~ O ~ ~ ~ O C~
i ~ ~ o ~ o~
3~ ~
., O ::, O ~ ¢ ~ U~ O
R
~d o ~d ~
C.) ~ 0~ ~
Q~ ~ ~ C~
R o o O E~ ^ c~
R o u~ n a) u o ol ~ ~
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a u~ o a~ ~ la ~
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C~ P~
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The above Table shows that while both radial copolymer and linear copolymer originally produce spherical moldings that seem to be equivalent in bleed-out and ability to stick to a wall upon being thrown thereagainst, that upon aging the linear polymer produces more bleed~out and loses its ability to stick to the wall unless the exuded oil is removed from the surface of the ball. The sticking to the wall is an important factor in a desired end use of the highly oil-extended compositions of this invention.
The data in Table III show characteristic desirable properties of the compositions of this invention. Varying the amount of oil in compositions can provide a range of properties to correspond with the desired application.
EXA~IPLE VI
Compositions of this invention and commercial artificial fishing worms were contacted with polystyrene to determine the relative sensitivity of polystyrene to these compositions.
A polystyrene sheet 3.2 mm thick was contacted at room tem-perature for 48 hours with cylindrical pellets 3.2 cm diameter X 1.3 cm length of the inventive compositions of Runs 20 to 24 and with pellets of commercial artificial fishing worm compositions based on poly(vinyl chloride) highly extended with dibutyl phthalate (worms were melted and cast into pellets). The inventive compositions produced no detectable change in the polystyrene surface; whereas the commercial artificial worm compositions caused serious softening, sagging, and even dissolution of the polystyrene surface.
:~3~
The results of the above-described tests indicate that the inventive artificial fishing worms can be contacted with polystyrene tackle boxes, floats, lures, etc., wthout the detrimental effect characteristic of the poly(vinyl chloride)/dibutyl phthalate worms.
It should be noted that contacting artificial worms of the composition of this invention with poly~vinyl chloride)/dibutyl phthalate worms resulted in rapid deterioration of both worms. Hence, such contact should be avoided.
E.YAMPLE VII
The following inventive runs are illustrative of the additives successfully employed in inventive compositions.
The extended rubber described in Example I and naphthenic oil were employed. Mixing was as generally described in Preparation Method 3 of Example I with minor variations in mixing times after rubber addition.
Table IV lists the additives and composition proportions.
TABLE IV
Run Naphthenic No. Oil, PHR Additive PHR
400 Silica 10 26 500 Silica 67 27 700 Silica 4 28 400 Talc 10 29 500 Clay 17 400 Silica 25 Coumarone-indene resin 30 31 400 Clay 50 Coumarone-indene resin 30 32 400 Polystyrene 100 33 300 Polypropylene 50 34 500 Stabilizer Al 2 500 Stabilizer B 2 36 500 Stabilizer C3 1 ~-37 500 Stabilizer D 2 (1) 2,6-di-t-butyl-4-methylphenol.
(2) tris(nonylphenyl)phosphite.
(3) Nickel dibutyldithiocarbamate.
(4) 2-(2'-hydroxy-5'-methylphenyl)benzotriazole.
EXA~IPLE VIII
Inventive artificial fishing worms were prepared from inventive compositions.
The mold employed for hot melt casting had a cavity approximately 18 cm deep with the upper 16 cm being cylindrical with varying diameter (1 cm maximum, 0.5 cm minimum) along the length of the cylinder. The lower 2 cm of the cavity was flattened to provide an oblong flat tail on the -resultant worm 2 mm thick, 1.5 cm across at the widest point, and 2 cm long.
:'~
Compositions containing the extended rubber described in Example I, naphthenic oil (300 to 700 phr total oil), various of the addi-tives given in Table IV, and various pigments were prepared generally as described in ~lethod 3 of Example I and while being maintained at 190-205C
were poured into the above-described molds. After cooling the molds were opened and the artificial fishing worms were removed.
The artificial worms were also prepared by injection molding of compositions as described above in molds with cavities approximately 11 cm long the upper 5 cm of which was semicylindrical with varying diameter (1 cm maximum, 0.5 cm minimum) along the length of the semicylinder. The lower 6 cm of the cavity was ilattened and curved to provide a long curved tail varying from 6 mm to 3 mm in width and 1 to 2 mm thick.
The resultant worms from the hot melt casting and injection molding were successfully employed to catch fish. They were especially successful in the catching of large mouth bass.
E ~PLE IX
This example illustrates the preparation of inventive balls from the inventive composition. Oil-extended stock representing each of the compositions described in Table I of Example III and similar stock repre-senting each of the compositions described in Table V was loaded into a transfer mold having 26 spherical cavities measuring 3.18 cm in diameter.
The loaded transfer mold was placed in a heated hydraulic press and main-tained at 121C for a ten-minute warmup period without any applied pressure.
A pressure of 30 tons was then applied and maintained for 15 minutes.
At the end of this time, the pressure was released and the mold removed and placed in a second hydraulic press cooled with circulating cold tap water and maintained at 30 tons pressure until the mold cooled. This procedure produced good smooth balls from each of the compositions.
2~B3 The oil-extended stocks of the compositions described in Table I were cut into thin strips and then f ormed by hand into a spherical mass slightly larger than the 4.32 cm diameter spherical cavities of a compression mold. These hand-shaped masses were placed in these cavities and then compression molded using the same basic procedure described earlier for transfer molding. Several of the compression molded balls contained flaws in the form of small holes due to air trapped in the compression mold.
.
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U~
, ~ ~ o o o O rl ~ rl U U
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.2~33 Molded balls prepared from the highly oil-extended radial teleblock copolymer compositions described in Tables I and V were observed to have the unique property of not rebounding when thrown against or dropped on a hard solid surface. Furthermore, molded balls from certain of these formulations not only failed to rebound but also when thrown against certain smooth or slightly rough vertical surfaces maintained contact with that surface and slowly rolled down. Molded balls from certain other of these formulations while having the same smooth outward appearance, and although likewise not rebounding when thrown against a solid surface, did not have the tendency to stick and slowly roll down, but rather after striking a vertical surface immediately fell to the floor. In general, copolymers having higher butadiene content and those containing filler were observed to have a greater tendency to stick or maintain contact with a vertical surface. This is illustrated by the observation that molded balls from Runs 12-15, 46, and 47 (all from copolymers containing 70 weight percent butadiene) all stuck and slowly rolled down a vertical sur-face, while molded balls from Runs 38-42 and 45 (all from copolymers containing 60 weight~ percent butadiene~ did not stick at all, but fell immediately to the floor. Furthermore, a ball from Run 44 which contains a 60 weight percent copolymer but having a very high 375 phr titanium dioxide stuck well, while a ball from Run 8 containing the same copolymer but only 20 phr titanium dioxide had considerably less tendency to stick, although better than balls from Run 43 which contain no filler. The amount of exudation of oil likewise was observed to affect this property, washing the ball with soap to remove excess surface oil often leading to improved adhesion of the ball to a vertical surface.
28~
EX~LE X
This example illustrates the amount of exudation as a function of the oil level employed for a composition consisting of the 70/30 butadiene/-styrene radial ~eleblock copolymer used in Runs 12-15 of Example III, 20 phr of titanium dioxide, and varying levels of Sontex 35 U.S.~. heavy white mineral oil from Marathon Norco Company.
The compositions were prepared according to the method of Example I, Run 4 (Method 4). Each composition was transfer molded into a ball according to the procedure described in Example IX and was aged for three days at room temperature. Each sample was then placed on a stack of white writing paper for 24 hours to evaluate oil migration. ~ second ball molded from each composition was aged for six days under the same con-ditions described above and then evaluated both visibly and to the touch for oil bleed-out. The results of this evaluation, as tabulated in Table VI, indicate that for this particular combination of ingredients, the amount of oil migration and bleed-out is a function of the oil concentration in the composition.
~322~3~
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~, oOOOO~
O ~ O ~ ,Q U
o ~1 ol c~ CJ~ O ~ C~l ~i3~83 EXAMPLE ~I
This example illustrates a difference in properties of a composition of the present invention using butadiene/styrene radial copolymer as compared to a composition outside the present invention using a butadiene/styrene linear copolymer. Compositions were prepared according to the method of Example I, Run 4 (Method 4) by blendin~ for Run 53 a 70/30 butadiene/styrene radial block copolymer with 300 parts Marathon-Norco U.S.P. heavy white mineral oil and 20 parts TiO2 per 100 parts of the rubber compound. For Run 54 a 70/30 butadiene/styrene linear block copolymer was blended with 300 parts Marathon-Norco U.S.P. heavy white mineral oil and 20 parts TiO2 per 100 parts of the rubber compound. In each formulation all of the ingredients were mixed in a pan and then placed in an oven without further stirring for 30 minutes at 164C. The composition was let cool and the masterbatch was blended on a roll mill for five minutes at 120C. The material in each run was then molded into balls. The results of observations of the balls are reported in Tab~e VII
below.
~3~83 ~ b~
,~ ~ o.~
al ~d ~ ~ S S
O
¢ ~ CO~ Z
~ ~ l ~o ~,1 o ~ ~3 g g u~ O ~: C!~ C~
~q a Q~
g ¢~ Z X
~ l 2, .
oo ~ a g g o e z z ~ ~d .
o o U~
~J ~
o ~ ~ ~ o ~ ~ za uS, ?~
C~ ~
H E~C~ o ~ ~:
H ~I S-l a~ ~ l ~ Q. ~ O ~ ~ u~
¢ ~ O ~ ~ ~ O C~
i ~ ~ o ~ o~
3~ ~
., O ::, O ~ ¢ ~ U~ O
R
~d o ~d ~
C.) ~ 0~ ~
Q~ ~ ~ C~
R o o O E~ ^ c~
R o u~ n a) u o ol ~ ~
¢ ~ uO cn ~,1 P~ ~
a u~ o a~ ~ la ~
~ o ~:1 R
C~ P~
ol ~ ~ . .
Z U) U~ , .:
~32'~
The above Table shows that while both radial copolymer and linear copolymer originally produce spherical moldings that seem to be equivalent in bleed-out and ability to stick to a wall upon being thrown thereagainst, that upon aging the linear polymer produces more bleed~out and loses its ability to stick to the wall unless the exuded oil is removed from the surface of the ball. The sticking to the wall is an important factor in a desired end use of the highly oil-extended compositions of this invention.
Claims (22)
1. A composition of matter consisting essentially of a blended mix-ture of (1) a conjugated diene/vinyl aromatic, radial teleblock copolymer containing from about 50 to about 95 weight percent butadiene and from 5 to about 50 weight percent styrene and (2) a hydrocarbon oil selected from naphthenic, paraffinic, aromatic, and mixtures thereof in an amount in a range of about 200 to about 1,000 parts weight of hydrocarbon oil per 100 parts by weight of radial teleblock copolymer.
2. A composition of claim 1 also containing additives chosen from among stabilizers, antioxidants, fillers, reinforcing agents, reinforcing resins, pigments, and fragrances.
3. A composition of matter of claim 2 wherein said mixtures com-prise, per hundred parts by weight of conjugated diene/vinyl aromatic radial teleblock copolymer, 0 to about 500 parts by weight filler, about 0 to about 200 parts by weight reinforcing resin, about 0 to about 5 parts by weight stabilizer, and about 0 to about 10 parts by weight pigment.
4. A composition of claim 1 wherein the copolymer contains from about 50 to about 70 weight percent butadiene and from about 30 to about 50 weight percent styrene.
5. A method for preparing a highly oil-extended conjugated diene/
vinyl aromatic radial teleblock copolymer composition, said method compri-sing:
(1) preparing a mixture of about 200 to about 1,000 parts weight per 100 parts by weight of radial teleblock copolymer of a hydrocarbon oil selected from naphthenic, paraffinic, aromatic, and mixtures thereof and said copolymer which contains from about 50 to about 95 weight percent butadiene and from 5 to about 50 weight percent styrene and (2) heating said mixture in the range of about 120°C to about 205°C to form a substantially homogenized blend.
vinyl aromatic radial teleblock copolymer composition, said method compri-sing:
(1) preparing a mixture of about 200 to about 1,000 parts weight per 100 parts by weight of radial teleblock copolymer of a hydrocarbon oil selected from naphthenic, paraffinic, aromatic, and mixtures thereof and said copolymer which contains from about 50 to about 95 weight percent butadiene and from 5 to about 50 weight percent styrene and (2) heating said mixture in the range of about 120°C to about 205°C to form a substantially homogenized blend.
6. A method of claim 5 comprising stirring together a mixture comprising a conjugated diene/vinyl aromatic radial teleblock copolymer and a hydrocarbon oil at a temperature elevated to about 175°C to about 205°C
with continued stirring until a substantially homogenized blend is produced.
with continued stirring until a substantially homogenized blend is produced.
7. A method of claim 6 wherein said oil is heated to said elevated temperature and the copolymer added with stirring to form said mixture.
8. A method of claim 6 wherein said oil and copolymer are mixed together to form said mixture and the temperature elevated with stirring of the mixture.
9. A method of claim 5 wherein said mixture is heated in a container without agitation at a temperature within the range of about 125°C to about 165°C to form a substantially homogeneous blend.
10. A method of claim 5 wherein additives chosen from among stabilizers, antioxidants, fillers, reinforcing agents, reinforcing resins, pigments, and fragrances, are introduced into the mixture along with the copolymer.
11. A method of claim 10 wherein said mixture also is comprised of about 0 to about 500 parts by weight filler, about 0 to about 200 parts by weight reinforcing resin, about 0 to about 5 parts by weight stabilizer, and about 0 to about 10 parts by weight pigment.
12. An object prepared by shaping a composition of claim 1.
13. An object prepared by shaping a composition prepared by the method of claim 5.
14. A fishing lure shaped in a suitable conformation from a composition of claim 1.
15. A fishing lure of claim 14 wherein said composition also comprises additives chosen from among stabilizers, antioxidants, fillers;
reinforcing agents, reinforcing resins, pigments, and fragrances.
reinforcing agents, reinforcing resins, pigments, and fragrances.
16. A fishing lure of claim 15 wherein fillers are chosen from among metal foil and reflective or colored particles.
17. A fishing lure of claim 14 wherein said conformation is the likeness of a worm.
18. A shaped object of claim 12 comprising TiO2 filler.
19. A shaped object of claim 18 wherein the copolymer comprises about 70 weight percent butadiene, and the TiO2 and hydrocarbon oil are present in amounts of about 20 and about 300 parts by weight per hundred parts by weight of the copolymer, respectively.
20. A shaped object of claim 18 wherein sheet material is formed and objects suitable for pressing against a flat surface cut therefrom.
21. A shaped object of claim 18 wherein the shape is chosen from among spheroid, dodecahedron, parallelepiped, and other regular geometric shapes.
22. A shaped object of claim 18 wherein the shape is suitable as a toy or for use in playing a game.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US89279778A | 1978-04-03 | 1978-04-03 | |
| US892,797 | 1978-04-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1132283A true CA1132283A (en) | 1982-09-21 |
Family
ID=25400506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA323,187A Expired CA1132283A (en) | 1978-04-03 | 1979-03-12 | High oil-elastomer compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1132283A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993025614A1 (en) * | 1992-06-05 | 1993-12-23 | Shell Internationale Research Maatschappij B.V. | Elastosols, preparation, use and products thereof |
| EP0628433A1 (en) * | 1992-02-28 | 1994-12-14 | Pentel Kabushiki Kaisha | Eraser |
-
1979
- 1979-03-12 CA CA323,187A patent/CA1132283A/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0628433A1 (en) * | 1992-02-28 | 1994-12-14 | Pentel Kabushiki Kaisha | Eraser |
| EP0628433A4 (en) * | 1992-02-28 | 1997-02-19 | Pentel Kk | Eraser. |
| WO1993025614A1 (en) * | 1992-06-05 | 1993-12-23 | Shell Internationale Research Maatschappij B.V. | Elastosols, preparation, use and products thereof |
| AU670294B2 (en) * | 1992-06-05 | 1996-07-11 | Shell Internationale Research Maatschappij B.V. | Elastosols, preparation, use and products thereof |
| CN1057551C (en) * | 1992-06-05 | 2000-10-18 | 国际壳牌研究有限公司 | Elastosols, process for the preparation thereof, process for the use of such elastosols and products derived from them |
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