Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
  • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
  • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
  • C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
  • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
  • C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
  • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

• the present invention relates to an oil gel composition, and more particularly to an oil gel composition including a controlled distribution block copolymer and at least one non-aromatic ester oil.
• SBC's have a long history of use as adhesives, sealants and gels.
• a recent example of such a gel can be found, for example, in U.S. Pat. No. 5,879,694.
• Such gels may also be used, for example, as a water proofing encapsulant/sealant for electronics and in wire and cable applications.
• anionic block copolymers of the '981 application are compatible with natural product oils such as, for example, soybean oil and other like ester compounds, and that substantially clear blends, which do not exhibit any significant oil bleed can be formulated.
• the present invention provides a gel composition that includes at least one non-aromatic ester oil and at least one hydrogenated block copolymer having a controlled distribution block of a mono alkenyl arene and a conjugated diene.
• the hydrogenated block copolymer employed in the present invention has at least one polymer block A and at least one polymer block B wherein:
• the general configuration of the block copolymer employed in the present invention is A-B, A-B-A, (A-B) n , (A-B) n -A, (A-B-A) n X, (A-B) n X or a mixture thereof, where n is an integer from 2 to about 30, preferably 2 to about 15, more preferably 2 to about 6, and X is coupling agent residue.
• the gel composition of the present invention typically includes 100 parts by weight of said anionic block copolymer having the controlled distribution mid-block and from about 250 to about 2000 parts by weight of said ester oil.
• inventive gels of the present invention can be used, for example, as a water proofing encapsulant/sealant for electronics and in wire and cable applications.
• inventive gels can also be used as a lubricating oil, as a grease or as an oil field drilling fluid.
• gels of the present invention include, but are not limited to: a vibration damper, a vibration isolator, a wrapper, a hand exerciser, dental floss, a crutch cushion, a cervical pillow, a bed wedge pillow, a leg rest cushion, a neck cushion, a mattress, a bed pad, an elbow pad, a dermal pad, a wheelchair cushion, a helmet liner, a hot or cold compress pad, an exercise weight belt, an orthopedic shoe sole, a splint, sling or brace cushion for the hand, wrist, finger, forearm, knee, leg, clavicle, shoulder, foot, ankle, neck, back and rib or a traction pad, candles, toys, cables for power or electronic (telephone) transmission, hydrophone cables for oil exploration at sea and various other uses.
• the present invention provides an oil gel composition which includes, as essential components, at least one hydrogenated anionic block copolymer (to be described in greater detail herein below) and an ester oil (also to be described in greater detail herein below) or a mixture of ester oils.
• the oil gel compositions of the present invention are made using conventional procedures well known in the art.
• the gel compositions of the present invention are made by blending at least the ester oil with a hydrogenated anionic block copolymer having the controlled distribution block.
• the blends can be made using any conventional mixing apparatus and mixing can occur at room temperature or at a temperature that is elevated from room temperature.
• the mixing of the two essential components, together with other optional components may be performed at a temperature from about 120° C. to about 175° C.
• one of the essential components of the inventive oil gel composition is a hydrogenated block copolymer containing mono alkenyl arene end blocks and a unique mid block of a mono alkenyl arene and a conjugated diene, such as described in the '981 application mentioned above.
• the entire contents of the '981 application, particularly the anionic polymerization method described therein, are thus incorporated herein by reference.
• the combination of (1) a unique control for the monomer addition, and (2) the use of diethyl ether or other modifiers as a component of the solvent (which is referred to as a “distribution agent”) results in a certain characteristic distribution of the two monomers (herein termed a “controlled distribution” polymerization, i.e., a polymerization resulting in a “controlled distribution” structure), and also results in the presence of certain mono alkenyl arene rich regions and certain conjugated diene rich regions in the polymer block.
• controlled distribution is defined as a molecular structure having the following attributes: (1) terminal regions adjacent to the mono alkenyl arene homopolymer (“A”) blocks that are rich in (i.e., having a greater than average amount of) conjugated diene units; (2) one or more regions not adjacent to the A blocks that are rich in (i.e., having a greater than average amount of) mono alkenyl arene units; and (3) an overall structure having relatively low mono alkenyl arene, e.g., styrene, blockiness.
• “rich in” is defined as greater than the average amount, preferably 5% greater than the average amount.
• This relatively low mono alkenyl arene blockiness can be shown by either the presence of only a single glass transition temperature (Tg) intermediate between the Tg's of either monomer alone, when analyzed using differential scanning calorimetry (“DSC”) thermal methods or via mechanical methods, or as shown via proton nuclear magnetic resonance (“H-NMR”) methods.
• Tg glass transition temperature
• DSC differential scanning calorimetry
• H-NMR proton nuclear magnetic resonance
• the potential for blockiness can also be inferred from measurement of the UV-visible absorbance in a wavelength range suitable for the detection of polystyryllithium end groups during the polymerization of the B block. A sharp and substantial increase in this value is indicative of a substantial increase in polystyryllithium chain ends. In such a process, this will only occur if the conjugated diene concentration drops below the critical level to maintain controlled distribution polymerization.
• styrene blockiness as measured by those skilled in the art using proton NMR, is defined to be the proportion of S (i.e., styrene) units in the polymer having two S nearest neighbors on the polymer chain.
• the styrene blockiness is determined after using H-1 NMR to measure two experimental quantities as follows: First, the total number of styrene units (i.e., arbitrary instrument units which, when a ratio is taken, cancel out) is determined by integrating the total styrene aromatic signal in the H-1 NMR spectrum from 7.5 to 6.2 ppm and dividing this quantity by 5 to account for the 5 aromatic hydrogens on each styrene aromatic ring.
• styrene units i.e., arbitrary instrument units which, when a ratio is taken, cancel out
• the blocky styrene units are determined by integrating that portion of the aromatic signal in the H-1 NMR spectrum from the signal minimum between 6.88 and 6.80 to 6.2 ppm and dividing this quantity by 2 to account for the 2 ortho hydrogens on each blocky styrene aromatic ring.
• the assignment of this signal to the two ortho hydrogens on the rings of those styrene units which have two styrene nearest neighbors was reported in F. A. Bovey, High Resolution NMR of Macromolecules (Academic Press, New York and London, 1972), Chapter 6.
• Polymer-Bd-S—(S) n —S-Bd-Polymer where n is greater than zero is defined to be blocky styrene.
• n 8 in the example above
• the blockiness index would be 80%. It is preferred in the present invention that the blockiness index be less than about 40.
• the blockiness index be less than about 10.
• This controlled distribution structure is very important in managing the strength and Tg of the resulting copolymer, because the controlled distribution structure ensures that there is virtually no phase separation of the two monomers, i.e., in contrast with block copolymers in which the monomers actually remain as separate “microphases”, with distinct Tg's, but are actually chemically bonded together. This controlled distribution structure assures that only one Tg is present and that, therefore, the thermal performance of the resulting copolymer is predictable and, in fact, predeterminable.
• the subject controlled distribution copolymer block has two distinct types of regions—conjugated diene rich regions on the ends of the block and a mono alkenyl arene rich region near the middle or center of the block.
• a mono alkenyl arene/conjugated diene controlled distribution copolymer block is desired, wherein the proportion of mono alkenyl arene units increases gradually to a maximum near the middle or center of the block and then decreases gradually until the polymer block is fully polymerized.
• controlled distribution block of the anionic block copolymers employed in the present invention is not a random block in which the distribution of the monomer unit is statistical, nor is the controlled distribution block a tapered block in which there is a gradual change in the composition of the polymer chain from one monomer unit to another.
• the alkenyl arene can be selected from styrene, alpha-methylstyrene, para-methylstyrene, vinyl toluene, vinylnaphthalene, and para-butyl styrene or mixtures thereof. Of these, styrene is most preferred and is commercially available, and relatively inexpensive, from a variety of manufacturers.
• the conjugated dienes that can be used in preparing the anionic block copolymer employed in the present invention are 1,3-butadiene and substituted butadienes, such as, for example, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, and 1-phenyl-1,3-butadiene, or mixtures thereof. Of these, 1,3-butadiene is most preferred. As used herein, “butadiene” refers specifically to “1,3-butadiene”.
• the controlled distribution polymer block has diene rich region(s) adjacent to the A block and an arene rich region not adjacent to the A block, and typically near the center of the B block.
• the region adjacent to the A block comprises the first 15 to 25% of the block and comprises the diene rich region(s), with the remainder considered to be arene rich.
• the term “diene rich” means that the region has a measurably higher ratio of diene to arene than the arene rich region. Another way to express this is the proportion of mono alkenyl arene units increases gradually along the polymer chain to a maximum near the middle or center of the block (assuming an ABA structure is being described) and then decreases gradually until the polymer block is fully polymerized.
• the weight percent of mono alkenyl arene is between about 10 percent and about 75.
• thermoplastic block copolymer is defined as a block copolymer having at least a first block of a mono alkenyl arene, such as styrene, and a second block of a controlled distribution copolymer of diene and mono alkenyl arene.
• the method to prepare this thermoplastic block copolymer is via any of the methods generally known for block polymerizations.
• the present invention includes as an embodiment a thermoplastic copolymer composition, which may be either a di-block, tri-block copolymer or multi-block composition.
• one block is the alkenyl arene-based homopolymer block and polymerized therewith is a second block of a controlled distribution copolymer of diene and alkenyl arene.
• the tri-block composition it comprises, as end-blocks the glassy alkenyl arene-based homopolymer and as a mid-block the controlled distribution copolymer of diene and alkenyl arene.
• the controlled distribution diene/alkenyl arene copolymer can be herein designated as “B” and the alkenyl arene-based homopolymer designated as “A”.
• the A-B-A, tri-block compositions can be made by either sequential polymerization or coupling.
• the sequential solution polymerization technique the mono alkenyl arene is first introduced to produce the relatively hard aromatic block, followed by introduction of the controlled distribution diene/alkenyl arene mixture to form the mid block, and then followed by introduction of the mono alkenyl arene to form the terminal block.
• the blocks can be structured to form a radial (branched) polymer, (A-B) n X, or both types of structures can be combined in a mixture.
• Some A-B diblock polymer can be present, but preferably at least about 30 weight percent of the block copolymer is A-B-A or radial (or otherwise branched so as to have 2 or more terminal resinous blocks per molecule) so as to impart strength.
• desired block weights are 3,000 to about 60,000 for the mono alkenyl arene A block, and 30,000 to about 300,000 for the controlled distribution conjugated diene/mono alkenyl arene B block. Preferred ranges are 5,000 to 45,000 for the A block and 50,000 to about 250,000 for the B block.
• the triblock which may be a sequential ABA or coupled (AB) 2 X block copolymer
• the A blocks should be 3,000 to about 60,000, preferably 5,000 to about 45,000, while the B block for the sequential block should be about 30,000 to about 300,000, and the B blocks (two) for the coupled polymer half that amount.
• the total average molecular weight for the triblock copolymer should be from about 40,000 to about 400,000, and for the radial copolymer from about 60,000 to about 600,000. These molecular weights are most accurately determined by light scattering measurements, and are expressed as number average molecular weights.
• the term “vinyl content” refers to a conjugated diene that is polymerized via 1,2-addition (in the case of butadiene—it would be 3,4-addition in the case of isoprene). Although a pure “vinyl” group is formed only in the case of 1,2-addition polymerization of 1,3-butadiene, the effects of 3,4-addition polymerization of isoprene (and similar addition for other conjugated dienes) on the final properties of the block copolymer will be similar.
• vinyl refers to the presence of a pendant vinyl group on the polymer chain.
• butadiene as the conjugated diene
• the distribution agent serves two purposes—it creates the controlled distribution of the mono alkenyl arene and conjugated diene, and also controls the microstructure of the conjugated diene. Suitable ratios of distribution agent to lithium are disclosed and taught in U.S. Pat. Reexamination No. 27,145, which disclosure is incorporated by reference.
• thermoplastic elastomeric di-block and tri-block polymers of the anionic copolymer employed in the present invention including one or more controlled distribution diene/alkenyl arene copolymer blocks and one or more mono alkenyl arene blocks, is that they have at least two Tg's, the lower being the combined Tg of the controlled distribution copolymer block which is an intermediate of its constituent monomers' Tg's.
• Tg is preferably at least about ⁇ 60° C., more preferably from about ⁇ 40° C. to about +30° C., and most preferably from about ⁇ 40° C. to about +10° C.
• the second Tg that of the mono alkenyl arene “glassy” block, is preferably more than about 80° C., more preferably from about +80° C. to about +110° C.
• the presence of the two Tg's, illustrative of the microphase separation of the blocks, contributes to the notable elasticity and strength of the material in a wide variety of applications, and its ease of processing and desirable melt-flow characteristics.
• a hydrogenated block copolymer that is a linear hydrogenated ABA styrene/butadiene block copolymer having a total molecular weight of about 80,000 to about 200,000 is employed.
• an anionic block polymer of the S-EB/S-S type indicates a polymer having a polystyrene block (S) on both ends of a hydrogenated polybutadiene (EB)/styrene (S) controlled distribution midblock.
• One example of a preferred S-EB/S-S type polymer is one wherein the molecular weight of the various blocks is 29,000-80,000/50,000-29,000, the % weight styrene is 57.5%, the % weight styrene in the EB/S mid block is 39% and the 1,2/1,4-butadiene ratio is 40/60.
• Another preferred anionic polymer of the S-EB/S-S type is one wherein the molecular weight of the various blocks is 9,500-60,000/20,000-9,500, the % weight styrene is 39.5%, the % weight styrene in the EB/S mid block is 25% and the 1,2/1,4-butadiene ratio is 40/60.
• these preferred S-EB/S-S type polymers the first one mentioned above is most preferred.
• the anionic block copolymer employed in the present invention is selectively hydrogenated.
• Hydrogenation can be carried out via any of the several hydrogenation or selective hydrogenation processes known in the prior art. For example, such hydrogenation has been accomplished using methods such as those taught in, for example, U.S. Pat. Nos. 3,494,942, 3,634,594, 3,670,054, 3,700,633 and Reexamination No. 27,145.
• hydrogenation is carried out under such conditions that at least about 90 percent of the conjugated diene double bonds have been reduced, and between zero and 10 percent of the arene double bonds have been reduced.
• Preferred ranges are at least about 95 percent of the conjugated diene double bonds reduced, and more preferably about 98 percent of the conjugated diene double bonds are reduced.
• the block copolymer employed in the present invention may be functionalized in a number of ways.
• One way is by treatment with an unsaturated monomer having one or more functional groups or their derivatives, such as carboxylic acid groups and their salts, anhydrides, esters, imide groups, amide groups, and acid chlorides.
• the preferred monomers to be grafted onto the block copolymers are maleic anhydride, maleic acid, fumaric acid, and their derivatives.
• fuctionalizing such block copolymers can be found in U.S. Pat. Nos. 4,578,429 and 5,506,299.
• the selectively hydrogenated block copolymer employed in the present invention may be functionalized by grafting silicon or boron-containing compounds to the polymer as taught, for example, in U.S. Pat. No. 4,882,384.
• the block copolymer of the present invention may be contacted with an alkoxy-silane compound to form silane-modified block copolymer.
• the block copolymer of the present invention may be functionalized by reacting at least one ethylene oxide molecule to the polymer as taught in U.S. Pat. No. 4,898,914, or by reacting the polymer with carbon dioxide as taught in U.S. Pat. No. 4,970,265.
• block copolymers of the present invention may be metallated as taught in U.S. Pat. Nos. 5,206,300 and 5,276,101, wherein the polymer is contacted with an alkali metal alkyl, such as a lithium alkyl.
• the block copolymers of the present invention may be functionalized by grafting sulfonic groups to the polymer as taught in U.S. Pat. No. 5,516,831.
• ester oil is used herein to describe any non-aromatic ester compound including monoesters, diesters or triesters.
• An ester as used herein is a compound that includes at least one carboxylate group: R—COO—, where R is hydrogen or a hydrocarbyl radical.
• hydrocarbyl is used herein to denote aliphatic or cyclic groups that include elements of C and H having from 1 to about 30 carbon atoms. Aliphatic groups include, for example, alkyl groups, alkenyl groups or alkynyl groups. The hydrocarbyl groups can be substituted with any group as desired, except for, an aromatic group.
• Suitable esters that can be employed in the present invention include those of the following formulas: where n has any value from 1 to about 8, and R 1 and R 2 are the same or different and are hydrogen or a hydrocarbyl (including substituted hydrocarbyls). It is noted that a suitable group for R 2 depends on the value of n. It is noted that the sugar esters of fatty acids, such as sucrose esters of fatty acids, are also contemplated herein.
• n is 1, and the ester has the formula R 1 C(O)OR 2 where R 1 is a C 10 -C 20 , preferably a C 15 -C 18 , and even more preferably a C 17 , alkyl, and R 2 is a lower alkyl radical containing from 1 to 10, preferably 8 carbon atoms.
• esters of the type mentioned above are eicosyl erucate ester or a C 12-15 alkyl octanoate.
• suitable esters include, but are not limited to: acefylline methylsilanol mannuronate; acetaminosalol; acetylated cetyl hydroxyprolinate; acetylated glycol stearate; acetylated sucrose distearate; acetylmethionyl methylsilanol elastinate; acetyl tributyl citrate; acetyl triethyl citrate; acetyl trihexyl citrate; aleurites moluccana ethyl ester; allethrins; allyl caproate; amyl acetate; arachidyl behenate; arachidyl glycol isostearate; arachidyl propionate; ascorbyl dipalmitate
• ester oils are natural product oils that are typically found in animal or plant tissues, including those which have been hydrogenated to eliminate or reduce unsaturation.
• These natural product oils that can be employed in the present invention include compounds that have the following formula: where R 10 R 11 and R 12 may be the same or different fatty acid radicals containing from 8 to 22 carbon atoms.
• Suitable natural product oils of the above formula include, but are not limited to: Kernel Oil; Argania Spinosa Oil; Argemone Mexicana Oil; Avocado ( Persea Gratissima ) Oil; Babassu ( Orbignya Olelfera ) Oil; Balm Mint ( Melissa Officinalis ) Seed Oil; Bitter Almond ( Prunus Amygdalus Amara ) Oil; Bitter Cherry ( Prunus Cerasus ) Oil; Black Currant ( Ribes Nigrrrm ) Oil; Borage ( Borago Officinalis ) Seed Oil; Brazil ( B 3 ertholletia Excelsa ) Nut Oil; Burdock ( Arctium Lappa ) Seed Oil; Butter; C 12-18 Acid Triglyceride; Calophyllurn Tacamahaca Oil; Camellia Kissi Oil; Camellia Oleifera Seed Oil; Canola Oil; Caprylic/Capric/Liuri
• the amount of natural oil that can be employed in the present invention varies from about 250 to about 2000 parts by weight per 100 parts by weight rubber, or block copolymer, preferably about 400 to about 1000 parts by weight.
• the inventive gel composition may also include various types of fillers and pigments to pigment the gel and reduce cost.
• Suitable fillers include calcium carbonate, clay, talc, silica, zinc oxide, titanium dioxide and the like.
• the amount of filler employed in the present invention usually is in the range of 0 to 30% weight based on the solvent free portion of the formulation, depending on the type of filler used and the application for which the gel is intended.
• An especially preferred filler is titanium dioxide.
• Another contemplated component of the oil gel composition of the present invention is a polyolefin homopolymer, branched homopolymer, or copolymer. These ingredients can be used to increase the hardness and tear strength of the gel.
• Preferred polyolefins are polyethylenes and copolymers of polyethylenes with monoalkenyl comonomers including, but not limited to: propylene, butylene, octene, styrene and the like.
• the melt index of these polymers can range from less than 1 to more than 3,000 measured at 190° C.
• Examples are low density polyethylenes made with Zeigler-Natta catalysts such as Epolene® C-10 from Eastman Chemical with a density of 0.906 and a melt flow of 2,250 to metallocene linear low density polyethylenes such as Exact® 4023 from Exxon Mobil Chemical with a melt index of 35 and a density of 0.882 and styrene ethylene copolymers such as 2900TE® made by Dow Chemical which contains 34% styrene.
• Polyolefins will typically be added from 0 to 100 parts per hundred weight rubber, preferably 10 to 50 parts per hundred weight rubber.
• oil gel compositions of the present invention may be modified further with the addition of other polymers, fillers, reinforcements, antioxidants, stabilizers, fire retardants, anti blocking agents, suntan screens, lubricants and other rubber and plastic compounding ingredients without departing from the scope of this invention.
• Such components are disclosed in various patents including, for example, U.S. Pat. Nos. 3,239,478 and 5,777,043, the disclosures of which are incorporated by reference.
• the gels of the present invention can be used for a variety of purposes, such as those disclosed, for example, in U.S. Pat. Nos. 5,336,708, 5,334,646, and 4,798,853. These include, among other uses, as a vibration damper, a vibration isolator, a wrapper, a hand exerciser, a dental floss, a crutch cushion, a cervical pillow, a bed wedge pillow, a leg rest cushion, a neck cushion, a mattress, a bed pad, an elbow pad, a dermal pad, a wheelchair cushion, a helmet liner, a hot or cold compress pad, an exercise weight belt, an orthopedic shoe sole, a splint, sling or brace cushion for the hand, wrist, finger, forearm, knee, leg, clavicle, shoulder, foot, ankle, neck, back and rib or a traction pad.
• Other uses include in candles, toys, cables for power or electronic (telephone) transmission, hydrophone cables for oil exploration at sea, greases, oil
• Probe Hardness test 90 grams of gel were poured hot into a 150 ml beaker and cooled to 25 ° C. Probe Hardness is the force in grams required to push a 0.5 inch diameter cylindrical acrylic probe into the gel to a depth of 4 mm at a rate of 1.0 mm/second.
• the equipment used for this test was a TA.XT2i Texture Analyzer with a TA-10 probe from Texture Technologies Corp., Scarsdale, N.Y.
• various block copolymers were used to gel various ester oils including those that fall within the scope of the present invention, and those that fall outside the scope of the present invention.
• the anionic block copolymers employed in this example included: Copolymer 1 (a copolymer within the present invention), Copolymer 2 (another copolymer within the scope of the present invention) and Copolymer 3 (a copolymer outside of the present invention).
• Copolymer 1 was a S-EB/S-S polymer in which each S end block had a MW of about 29,000 and the EB/S midblock had a MW of 80,000/50,000.
• Copolymer 1 was 57.5% by weight and the styrene content of the EB/S midblock was 39% by weight.
• Copolymer 2 was a S-EB/S-S polymer in which each S end block had a MW of about 9,500 and the EB/S midblock had a MW of 60,000/20,000.
• the styrene content of Copolymer 2 was about 39.5% by weight and the styrene content in the EB/S midblock was about 25% by weight.
• Copolymers 1 and 2 had a 1,2/1,4-Bd ratio of about 40/60.
• Copolymer 3 was a S-EB-S type polymer having the following block MW 10,000-80,000-10,000; % weight S of 20.5 and a 1,2/1,4-Bd ratio of 65/35.
• Cargill® Soybean Oil (a triglyceride of C 18 acids), Erucicial® EG-20 (an eicosyl erucate ester supplied by Lambert Tech), Finester® EH-25 (a C 12-15 alkyl octanoate supplied by Fintex), Finsolv® TN (a C 12-15 alkyl benzoate supplied by Fintex) and Neo Heliopan AV® (an octyl methoxy cinnamate supplied by Liberty Natural) were used.
• the first three ester oils fall within the scope of the present invention, while the last two ester oils are aromatic oils that fall outside the scope of the present invention.
• Copolymer 1 was blended into the oils at 7.5% by weight copolymer and Copolymers 2 and 3 were blended into the oils at 15% by weight copolymer. 0.1% by weight Irganox® 1010 (a hindered phenolic antioxidant supplied by Ciba) was also included in each blend. The polymers were mixed into the oils by blending for about 1 to 1.5 hour at 130°-170° C. with a Silverson® mixer. Table 1 below shows the various oil gels that were prepared and provides characterization of the resultant oil gels.
• Copolymer 1 was compared with Copolymer 4 (an S-EB-S type polymer having block MW of 29,000-130,000-29,000, a styrene % weight of 33 and a 1,2/1,4-Bd ratio of 40/60).
• the various esters employed in Example 1 were used in this example as well.
• Table 2 includes the formulations and results with Copolymer 1, while Table 3 includes the formulations and results for Copolymer 4.
• copolymers behave similarly in all oils except for soybean oil in which Copolymer 4 was incompatible.
• Copolymer 1 As shown in Table 4, in soybean oil, Copolymer 1 at 9% by weight still showed a very slight oil bleed. At 12% by weight, no oil bleed was found. Blends at up to 15% by weight of Copolymer 1 could be made, but it is likely that higher concentrations would be too viscous to mix with the Silverson® mixer. The gels in soybean oil become clearer with increasing Copolymer 1 content.
• Copolymer 1 had excellent compatibility with Erucical® EG-20.
• the blends were optically clear and showed no oil bleed, even at 7.5% by weight. These blends gave the highest softening points, but also the highest melt viscosity.
• Copolymer 1 also had excellent compatibility with Finester® EH-25. These blends showed good clarity, no oil bleed and they were colorless. These blends gave much lower softening points than the blends with soybean oil and Erucical® EG-20. Softening points remained fairly low until the Copolymer 1 concentration reached about 20% by weight. Fortunately, blends in Finester® EH-25 had relatively low viscosity so blends can be made with the Silverson® mixer at up to 25% by weight of Copolymer 1. Since gel hardness is directly related to polymer content, this low viscosity allowed gels to be made with Finester® EH-25 that have relatively high hardness.
• an oil gel composition comprising coconut oil and Copolymer 1 was prepared as outlined in Example 1 above. A comparison is shown with Copolymer 4. Stirring was performed at 160°-170° C. The coconut oil was 76° Edible Coconut Oil from Alnoroil Company, Valley Stream, N.Y. The following formulations were prepared and exhibited the following properties: TABLE 6 Oil Gel Compositions with Coconut Oil Composition, % by weight EE FF GG HH II Coconut Oil 92.4 90.9 87.9 84.9 92.4 Copolymer 1 7.5 9 12 15 Copolymer 4 7.5 Irganox ® 0.1 0.1 0.1 0.1 0.1 101 R&B 67 69 72 87 Softening Point, ° C. Probe 65 160 220 340 Hardness, gm

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