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An epoxidized diene star polymer having greater than 4 arms and comprising from 0.05 to 5 Meq of di-, tri- and tetra-substituted olefinic epoxides and the molecular weights of the arms are from 1,500 to 15,000.
1. A conjugated diolefin star polymer of the formula
Dn --X--Cr
wherein D is (A--Mp);
wherein A is a diene containing block which has a molecular weight of 1,500 to 15,000; and
wherein C is a block or multiblock segment which has a molecular weight of from 50 to 15,000 and comprises at least one diene or vinyl aromatic hydrocarbon or methacrylate or combinations thereof but is not identical to D; and
wherein the A blocks may comprise up to 99% of a monoalkenyl aromatic hydrocarbon monomer; and
wherein M is a miniblock of a monomer selected from the group consisting of vinyl aromatic hydrocarbons and dienes and has a molecular weight of 50 to 1000; and
wherein X is a coupling agent or coupling monomers or initiator, n≧2, r≧1, n≧r, n+r ranges from greater than 4 to 100 and p is 0 or 1, and wherein the polymer is partially hydrogenated such that it contains from 0.05 to 5 Meq per gram of polymer of randomly distributed di-, tri-, and tetra-substituted olefinic double bonds.
2. The polymer of claim 1 wherein C is comprised of a methacrylate.
This is a division of application Ser. No. 08/063,612, filed May 18, 1993 abandoned which is a division of 07/901,349, Jun. 19, 1992 U.S. Pat. No. 5,247,026.
This invention relates to diene based, epoxidized star polymers suitable for crosslinking and adhesive, sealant and coating compositions made therefrom.
High molecular weight diene based styrenic block copolymers such as the family of KRATON� S-I-S, S-B-S, S-EP-S and S-EB-S block copolymers are extensively used as base polymers in the formulation of many types of hot melt applied coatings and adhesives. These materials offer advantages over other types of materials such as acrylic oligomer/acrylic monomer and polyol/isocyanate monomer systems that are applied as 100% reactive systems and are cured by chemical or radiation means. An important advantage of the high molecular weight diene based styrenic block copolymers is the ability to provide non-polluting formulations and method of application that employs very benign raw materials, compared to the substantial risk associated with acrylate and isocyanate monomer based 100% reactive systems.
However, an important limitation of the styrenic block copolymers has been the inability to provide formulations with solvent and higher temperature resistance. This is because the styrenic block copolymers rely on physical association of the polystyrene blocks in the polymer for crosslinking and once the polystyrene domains in the polymer are weakened by solvent takeup or temperatures near or above the glass transition temperature of the polystyrene, cohesive strength is lost. This problem has been solved by the preparation of very high molecular weight block copolymers such as KRATON� D1320X rubber which can undergo covalent crosslinking by EB radiation to reinforce the physical crosslinking to give improved solvent and heat resistance. Another important limitation of the styrenic block copolymers is related to the otherwise very desirable hot melt application method. Many substrates cannot tolerate being exposed to hot melt temperatures, 300� F. to 450� F., without being severely damaged. This is the case for very thin polyolefin films, such as thin polyethylene film.
The present invention provides relatively high molecular weight diene based polymers having a very compact star structure with short arms which lowers the viscosity. These polymers do not have a distinct styrene block which would tend to raise application viscosity. The polymers of this invention have many of the property advantages of conventional styrenic block copolymers, including being safe to handle and being covalently crosslinkable for solvent and high temperature resistance. Additionally, the polymers of this invention can be applied as warm melts or as a 100% reactive so that they can be used on heat sensitive substrates. They are sprayable as well. Further, they cure readily, especially by UV radiation.
The present invention comprises randomly epoxidized star polymers, based on at least one conjugated diolefin monomer, that contain di-, tri- and/or tetrasubstituted olefinic epoxides. The polymers of the invention may or may not be hydrogenated and if they are hydrogenated, the hydrogenation may take place either before or after epoxidation. The polymers may be crosslinked through at least some of the epoxy functionality, preferably by radiation, and can be used to make rapid curing and heat stable adhesives, sealants, coatings, flexible printing plates, fibers and films, or used as modifiers for asphalt, polyesters, polyamides and epoxies.
The star polymers have greater than four arms or branches. Preferably, the polymers have more than eight arms, and most preferably, more than twelve arms. Each arm has a molecular weight from between 1,500 and 15,000, preferably from 2,000 to 10,000, and most preferably from 3,000 to 7,000. The concentration of di-, tri-, or tetrasubstituted olefinic epoxides (1,1-disubstituted, 1,2-disubstituted, 1,1,2-trisubstituted and 1,1,2,2-tetrasubstituted olefinic epoxides) is from 0.05 to 5 milliequivalents of epoxide per gram of polymer (Meq/g), preferably from 0.1 to 3 Meq/g, and most preferably from 0.2 to 1 Meq/g.
FIG. 1 is a plot of viscosity data from Example 2 which shows the relationship between the viscosities of the precursor and epoxidized polymers.
Polymers containing di-, tri- or tetrasubstituted olefinic unsatoration can be prepared by polymerizing one or more polyolefins, particularly diolefins by themselves or with one or more alkenyl aromatic hydrocarbon monomers. The polymers containing such olefinic unsaturation may be prepared using artionic initiators. Such polymers may be prepared using bulk, solution or emulsion techniques.
A very useful embodiment of this invention may be conveniently prepared by anionic polymerization, preparing arms D consisting of homopolymers or copolymers of conjugated diene monomers or copolymers of conjugated diene monomers and alkyl aryl monomers and then coupling the arms to make a star polymer. The amount of alkyl aryl monomers copolymerized in the D arms can be up to 99%, provided that enough conjugated diene monomer is used to assure the presence of a sufficient level of higher substituted olefinic double bonds for epoxidation.
Preferably, the polymer is epoxidized under conditions that enhance the epoxidation of the more highly substituted olefinic double bonds, such as by the use of peracetic acid, wherein the rate of epoxidation is generally greater the greater the degree of substitution of the olefinic double bond (rate of epoxidation: tetrasubstituted>trisubstituted>disubstituted>monosubstituted olefinic double bond). Sufficient epoxidation is done to achieve the desired level of epoxidation in the polymer (within the range of 0.05 to 5 Meq/g). 1 H NMR can be used to determine the loss of each type of double bond and the appearance of epoxide.
If a substantially saturated polymer is desired, the epoxidized polymer is hydrogenated to remove substantially all remaining olefinic double bonds (ODB) and normally leaving substantially all of the aromatic double bonds. Alternatively, selective partial hydrogenation of the polymer may be carried out before epoxidation such that from 0.05 to 5 Meq of olefinic double bonds are left intact for subsequent epoxidation. In this case, the epoxidized polymer may be partially hydrogenated in a selective manner with a suitable catalyst and conditions (like those in Re 27,145, U.S. Pat. No. 4,001,199 or with a titanium catalyst such as is disclosed in U.S. Pat. No. 5,039,755, all of which are incorporated by reference; or by fixed bed hydrogenation) that favor the hydrogenation of the less substituted olefinic double bonds (rate or hydrogenation: monosubstituted>disubstituted>trisubstituted>tetrasubstituted olefinic double bonds) and also leaves aromatic double bonds intact, so as to leave some of the unsaturation intact in the D arms (and/or any portions of the optional M block or the C arms, discussed below, that may also contain unepoxidized higher substituted olefinic double bonds). The epoxidation does not need to be selective with respect to the degree of substitution on the olefinic double bonds, since the objective is usually to epoxidize as many of the remaining ODB's as possible.
Generally, if a hydrogenation step is used, sufficient improvement of the polymer's chemical and heat stability should be achieved to justify the extra expense and effort involved. For greatest heat stability, all of the olefinic double bonds, anyplace in the polymer, that are not epoxidized should be removed so that less than 1 Meq of ODB per gram of polymer remain, more preferably less than 0.6 Meq/g, and most preferably less than about 0.3 Meq/g of polymer.
In general, when solution anionic techniques are used, conjugated diolefin polymers and copolymers of conjugated diolefins and alkenyl aromatic hydrocarbons are prepared by contacting the monomer or monomers to be polymerized simultaneously or sequentially with an anionic polymerization initiator such as group IA metals, their alkyls, amides, silanolates, napthalides, biphenyls and anthracenyl derivatives. It is preferred to use an organo alkali metal (such as sodium or potassium) compound in a suitable solvent at a temperature within the range from about -150� C. to about 300� C., preferably at a temperature within the range from about 0� C. to about 100� C. Particularly effective anionic polymerization initiators are organo lithium compounds having the general formula:
wherein R is an aliphatic, cycloaliphatic, aromatic or alkyl-substituted aromatic hydrocarbon radical having from 1 to about 20 carbon atoms and n is an integer of 1 to 4.
Conjugated diolefins which may be polymerized anionically include those conjugated diolefins containing from about 4 to about 24 carbon atoms such as 1,3-butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene and the like. Isoprene and butadiene are the preferred conjugated diene monomers for use in the present invention because of their low cost and ready availability. The conjugated diolefins which may be used in the present invention include isoprene (2-methyl-1,3-butadiene), 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene (2-amyl-1,3-butadiene), 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, 2-nonyl-1,3-butadiene, 2-decyl-1,3-butadiene, 2-dodecyl-1,3-butadiene, 2-tetradecyl-1,3-butadiene, 2-hexadecyl-1,3-butadiene, 2-isoamyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2-methyl-1,3-heptadiene, 2-methyl-1,3-octadiene, 2-methyl-6-methylene-2,7-octadiene (myrcene), 2-methyl-1,3-nonyldiene, 2-methyl-1,3 -decyldiene, and 2-methyl-1,3-dodecyldiene, as well as the 2-ethyl, 2-propyl, 2-butyl, 2-pentyl, 2-hexyl, 2-heptyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 2-tetradecyl, 2-hexadecyl, 2-isoamyl and 2-phenyl versions of all of these dienes. Also included are 1,3-butadiene, piperylene, 4,5-diethyl-1,3-octadiene and the like. Di-substituted conjugated diolefins which may be used include 2,3-dialkyl-substituted conjugated diolefins such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3-diethyl-1,3-heptadiene, 2,3-dimethyl-1,3-octadiene and the like and 2,3-fluoro-substituted conjugated diolefins such as 2,3-difluoro-1,3-butadiene, 2,3-difluoro-1,3-pentadiene, 2,3-difluoro-1,3-hexadiene, 2,3-difluoro-1,3-heptadiene, 2,3-fluoro-1,3-octadiene and the like. Alkenyl aromatic hydrocarbons which may be copolymerized include vinyl aryl compounds such as styrene, various alkyl-substituted styrenes, alkoxy-substituted styrenes, vinyl napthailene, alkyl-substituted vinyl napthalenes and the like.
Conjugated dienes can also be copolymerized with methacrylates, such as t-butyl methacrylate, as described in U.S. Pat. No. 5,002,676, which is incorporated herein by reference, and such copolymers can be epoxidized and hydrogenated as described herein. The preferred use position in the polymer for methacrylates, when used, is in the C arms.
There are a wide variety of coupling agents or initiators that can be employed. Any polyfunctional coupling agent which contains more than four reactive sites can be employed. Examples of the types of compounds which can be used are disclosed in U.S. Pat. No. 4,096,203, wherein incorporated by reference, and include the polyepoxides, polyisocyanates, polyimines, polyaldehydes, polyketones, polyanhydrides, polyhalides, and the like. These compounds can contain two or more types of functional groups such as the combination of epoxy and aldehyde groups, isocyanate and halide groups, and the like. Many suitable types of these polyfunctional compounds have been described in the literature. Coupling monomers are coupling agents where several monomer units; are necessary for every chain end to be coupled. Divinylbenzene (DVB) is the most commonly used coupling monomer and results in star polymers.
In general, any of the solvents known in the prior art to be useful in the preparation of such polymers may be used. Suitable solvents, then, including straight- and branched chain hydrocarbons such as pentane, hexane, heptane, octane and the like, as well as, alkyl-substituted derivatives thereof; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and the like, as well as alkyl-substituted derivatives thereof; aromatic and alkyl-substituted derivatives thereof; aromatic and alkyl-substituted aromatic hydrocarbons such as benzene, napthalene, toluene, xylene and the like; hydrogenated aromatic hydrocarbons such as tetraline, decal in and the like; linear and cyclic ethers such as methyl ether, methylethyl ether, diethyl ether, tetrahydrofuran and the like.
More specifically, the polymers of the present invention are made by the anionic polymerization of conjugated diene monomers and alkenyl aromatic hydrocarbon monomers in a hydrocarbon solvent at a temperature between 0� and 100� C. using an alkyl lithium initiator. The living polymer chains are usually coupled by addition of divinyl monomer to form a star polymer. Additional monomers may or may not be added to grow more arms, C arms, or to terminally functionalize, such as with ethylene oxide or carbon dioxide to give hydroxyl or carbonyl groups, respectively, and the polymer and the living chain ends are quenched with a proton source such as methanol or hydrogen. Polymerization may also be initiated from monomers such as m-divinylbenzene and m-diisopropenylbenzene treated with butyl lithium.
The polymers can be either symmetric or asymmetric star (centrally branched) polymers of the basic formula (A--Mp)n --X--Cr, wherein A is the diene containing block, M is an optional miniblock and C is an optional arm (branch) consisting of one or more blocks. The A--Mp arms (branches) are referred to as D arms when it is convenient to do so. The blocks themselves may be homopolymer or copolymer blocks.
M is a miniblock of monomer that can be used to affect the number or stability of the arms coupled or originating at X. The molecular weight of M is greater than 50 and less than 1000. M is a vinyl aromatic hydrocarbon or a diene, typically oligostyrene or oligoisoprene. For instance, when coupling anionically prepared A- living arms, where A is polybutadiene, with commercial DVB-55 the degree of coupling to make the star is often less than 80%, with greater than 20% of the arms remaining unattached to the main star mode in the final product. The exact amount left unattached is very dependent upon the exact conditions of the coupling reaction, such as the amount of ether cosolvent used, the time elapsed after polymerization of the A blocks and the temperature of the polymer solution during the DVB-55 addition. In contrast, when a small miniblock of oligoisoprene is incorporated to make the A--M arm (D), the coupling reaction is less sensitive to reaction conditions and higher degrees of coupling can be achieved. Further, presence of the miniblock can be additionally beneficial when the polymer is being used under harsh service conditions, such as high temperature use, because a completely saturated block like oligostyrene or an epoxidized oligoisoprene may prevent scission of the arm from the star at the core of the star.
X sits at the junction point or region in the polymer molecule at which the arms (branches) of the polymer connect and represents the agent or agents that function as the connector. Generally X either represents coupling agents or monomers that cause the majority of the arms to join together after polymerization of the arms, or represents an initiator with an active functionality greater than 4 from which polymerization of the arms takes place.
Asymmetric star polymers, by definition, require the use of the optional C arms, which, are necessarily different than the D arms either in composition or molecular weight or both. C arms are segments that are usually prepared from one or more of the monomers used to prepare the D arms. The molecular weight of a C arm is from 50 to 15,000, preferably 500 to 10,000. The linear size of arms of greater length gives polymers with high application viscosities. Sometimes it is useful to prepare C from monomers other than those used in D. For instance, a methacrylate monomer, such as t-butyl methacrylate, can be added to a DVB-coupled star prior to termination and the arms C can be grown out from the living DVB core of the star. Also, C can be formed from a polyvinyl aromatic hydrocarbon. Combinations of the monomers can also be in C.
The subscripts are integers that indicate how many times a particular arm or miniblock is present on a particular polymer. The subscript p is 0 or 1, n and r are integers where n≧2, r≧0, and n+r is the total number of arms and ranges from 5 to 100, preferably from 8 to 60, and most preferably from 12 to 40. When p equals 0 or r equals 0 there is no miniblock M or no C arms. Preferably n≧r.
As the number of arms increases, so does the average molecular weight of the polymer, which substantially increases the polymers ability to cure easily, such as with very low dose radiation, because the number of cure sites (epoxide sites) increases in proportion to the molecular weight at any fixed concentration of epoxide in the polymer. Fortunately, the substantially increased polymer molecular weight causes very little increase in viscosity because of the compact nature of a star polymer. However, trying to attain the highest possible number of arms on a star polymer results in the formation of some gel during the manufacture of the polymer, which may make subsequent processing and filtering of the polymer during manufacture, light scattering analysis for molecular weight, or application of the polymer difficult or impossible. This is why the most preferred upper bound for the number of arms is 40.
A special case is where A is a polyisoprene block polymerized under conditions that yields primarily, i.e. at least 50%, 1,4-polyisoprene, for which the residual double bonds are trisubstituted. Other special cases are where A is primarily 1,4-butadiene, a copolymer of primarily polyisoprene and butadiene or where the A block is a random polyisoprene/polystyrene copolymer in which a majority of the polyisoprene is 1,4polyisoprene. D arms may be made from a copolymer of isoprene and butadiene and the isoprene can be preferentially epoxidized. Isoprene and butadiene arms may be made in two different reactors and then blended and coupled with DVB to make an asymmetric star polymer (other methods may be used to make such polymers). Either epoxidation alone, epoxidation first followed by hydrogenation, or partial hydrogenation of these polymers first followed by epoxidation, works extremely well. When A is polybutadiene, it often is convenient to use a miniblock M where M is oligoisoprene or oligostyrene. Star polymers are normally made by a coupling reaction using divinyl monomer such as divinylbenzene. Like any coupling reaction, it does not go to 100% completion and some unattached arms will be present. The value of n is determined after the polymer is made. The best way to assign the n values is to measure the weight average molecular weight of the polymer by light scattering as described below, including pure star and unattached arms, subtract from it the portion of the mass due to the coupling monomer and then divide this corrected weight average molecular weight by the molecular weight of the arm which is usually the peak molecular weight determined by GPC as described below.
Molecular weights of unassembled linear segments of polymers such as arms of star polymers before coupling are conveniently measured by Gel Permeation Chromatography (GPC), where the GPC system has been appropriately calibrated. Polymers of known molecular weight are used to calibrate and these must be of the same molecular structure and chemical composition as the unknown linear polymers or segments that are to be measured. For anionically polymerized linear polymers, the polymer is essentially monodisperse and it is both convenient and adequately descriptive to report the "peak" molecular weight of the narrow molecular weight distribution observed. Measurement of the true molecular weight of the final coupled star polymer is not as straightforward or as easy to make using GPC. This is because the star shaped molecules do not separate and elute through the packed GPC columns in the same manner as do the linear polymers used for the calibration, and, hence, the time of arrival at a UV or refractive index detector is not a good indicator of the molecular weight. A good method to use for a star polymer is to measure the weight average molecular weight by light scattering techniques. The sample is dissolved in a suitable solvent at a concentration less than 1.0 gram of sample per 100 milliliters of solvent and filtered using a syringe and porous membrane filters of less than 0.5 microns pore size directly into the light scattering cell. The light scattering measurements are performed as a function of scattering angle and of polymer concentration using standard procedures. The differential refractive index (DRI) of the sample is measured at the same wavelength and in the same solvent used for the light scattering. The following references are herein incorporated by reference:
1. Modern Size-Exclusion Liquid Chromatography, M. W. Yau, J. J. Kirkland, D. D. Bly, John Wiley & Sons, New York, N.Y., 1979.
2. Light Scattering from Polymer Solutions, M. B. Huglin, ed., Academic Press, New York., N.Y. 1972.
3. W. Kay and A. J. Havlik, Applied Optics, 12, 541 (1973).
4. M. L. McConnell, American Laboratory, 63, May, 1978.
Each arm has a molecular weight from 1,500 to 15,000, preferably 2,000 to 10,000, and most preferably 3,000 to 7,000. These arm molecular weights are very important to obtaining a low viscosity polymer for ease of application. There are large viscosity penalties to be paid if the arm length is either smaller than 1,500 or greater than about 15,000. It was totally unexpected that arm lengths below 1,500 could far exceed viscosities at considerably higher arm molecular weights. The range of 2,000 to 10,000 is preferred because it greatly reduces the possibility of straying into a much higher viscosity area, especially on the low arm molecular weight side. The range of 3,000 to 7,000 is most preferred because arms in this range will be at or very near the absolute minimum in viscosity, Polymers of this invention based on 1,4-polybutadiene have similar or lower viscosity than similar polymers based on 1,4-polyisoprene. It is also the case that polymerizing to incorporate styrene, more 1,2-polybutadiene or more 3,4-polyisoprene, all of which raise the Tg of the A arms, will cause the viscosity to rise at a fixed D arm molecular weight.
Upon epoxidation, the Meq of such epoxide per gram of the polymer will be from 0.05 Meq/g to 5 Meq/g, preferably from 0.1 to 3 Meq/g and most preferably 0.2 to 1 Meq/g. If there were greater epoxidation, the polymers would over crosslink, have little elasticity and be unsuitable for the applications intended. 0.2 to 1 Meq/g is preferred to obtain good UV curing and maintain pressure sensitive properties.
Some other advantages of relatively low levels of epoxidation are:
the manufacturing cost is lower because less epoxidizing agent is used;
can, maintain the polymer as an elastic material because the crosslinking will not be dense; and
the polymer will be more hydrophobic so water will be less of a problem for cationic curing.
The epoxidized copolymers of this invention can be prepared by the epoxidation procedures as generally described or reviewed in the Encyclopedia of Chemical Technology 19, 3rd ed., 251-266 (1980), D. N. Schulz, S. R. Turner, and M. A. Golub, Rubber Chemistry and Technology, 5, 809 (1982), W-K. Huang, G-H. Hsuie, and W-H. Hou, Journal of Polymer Science, Part A: Polymer Chemistry, 26, 1867 (1988), and K. A. Jorgensen, Chemical Reviews, 89, 431 (1989), and Hermann, Fischer, and Marz, Angew, Chem. Int. Ed. Engl. 30 (No. 12), 1638 (1991), all of which are incorporated by reference.
For instance, epoxidation of the base polymer can be effected by reaction with organic peracids which can be preformed or formed in situ. Suitable preformed peracids include peracetic and perbenzoic acids. In situ formation may be accomplished by using hydrogen peroxide and a low molecular weight fatty acid such as formic acid. Alternatively, hydrogen peroxide in the presence of acetic acid or acetic anhydride and a cationic exchange resin will form a peracid. The cationic exchange resin can optionally be replaced by a strong acid such as sulfuric acid or p-toluenesulfonic acid. The epoxidation reaction can be conducted directly in the polymerization cement (polymer solution in which the polymer was polymerized) or, alternatively, the polymer can be redissolved in an inert solvent such as toluene, benzene, hexane, cyclohexane, methylenechloride and the like and epoxidation conducted in this new solution or can be epoxidized neat. Epoxidation temperatures on the order of 0� to 130� C. and reaction times from 0.1 to 72 hours may be utilized. When employing hydrogen peroxide and acetic acid together with a catalyst such as sulfuric acid, the product can be a mixture of epoxide and hydroxy ester. The use of peroxide and formic acid in the presence of a strong acid may result in diolefin polymer blocks containing both epoxide and hydroxy ester groups. Due to these side reactions caused by the presence of an acid, it is preferable to carry out the epoxidation at the lowest possible temperature and for the shortest time consistent with the desired degree of epoxidation. Epoxidation may also be accomplished by treatment of the polymer with hydroperoxides or oxygen in the presence of transition metals such as Mo, W, Cr, V and Ag, or with methyl-trioxorhenium/hydrogen peroxide with and without amines present. 1 H NMR is an effective tool to determine which and how much of each type of ODB is epoxidized. Further, the amount of epoxy can also be measured by the direct titration with perchloric acid (0.1N) and quaternary ammonium halogenide (tetraethyl-ammonium bromide)where the sample is dissolved in methylene chloride. Epoxy titration is described in Epoxy Resins Chemistry and Technology, edited by Clayton A. May and published in 1988 (p. 1065) which is herein incorporated by reference.
An epoxidized polymer of the present invention can be further derivatized by a subsequent reaction either separately or in-situ to provide useful reactive elastomeric binders that have reactive functionality other than the epoxy group. Examples of these reactions are described by copending, commonly assigned applications, "Hydroxyl Functional Derivatives of Epoxidized Diene Polymers and Process for Making Them", Ser. No. 863,580 and "Hydroxyl Functional Derivatives of Epoxidized Diene Polymers and Process for Making Them (II)", Ser. No. 863,648, both filed on Apr. 3, 1992, which are herein incorporated by reference. Epoxy groups can be converted to hydroxyl functionality, capable of crosslinking with amino-formaldehyde resins or isocyanates, by reduction or reaction with water. Reaction with azide ion, reaction with cyanotrimethylsilane followed by reduction or reaction with dialkylaminosilanes, ammonia, or amines will give polymers containing both amino and hydroxyl functionality that can be used to enhance adhesion to cellulosic substrates or provide reactive sites for isocyanate cure. Reaction with amino or mercapto acids can be used to prepare polymers containing hydroxyl and carboxylic acid functionality, providing greater adhesion to metals or to basic polymers such as nylon. Reaction with mercaptosilanes can be used to prepare polymers containing the elements of coupling agents, providing excellent adhesion to glass. These functional groups may also be introduced in the form of protected functional groups by reaction of the epoxy with the appropriately functionalized organometallic reagent (lithium organocuprates, Grignard reagents). Hydroxyl and aldehyde functionality may also be introduced by hydroformylation. Reactions with acrylamides and acrylic acids will introduce sites for free radical grafting. Further neutralization of the carboxylic acid or amine-containing polymer with base or acid will give varying amounts of water dispersability, depending on the level of functionality and neutralization.
A partially hydrogenated, but not epoxidized, polymer of the present invention can be further derivatized as well. Such a polymer can be halogenated, for example, by reacting it with a solution of HBr in acetic acid, or with chlorine (Cl2) or bromine (Br2), either gaseous, or in solution. A wide variety of species, including alcohols, carboxylic acids and nitriles, can be added across the double bond in the presence of protic acids to form the corresponding ethers, esters and amides. Acid chlorides and anhydrides can be added across the double bond in the presence of Lewis acids. A wide variety of species containing active protons, including thiols, primary alcohols and amines, aldehydes and species of the structure ZCH2 Z', where Z and Z' are electron withdrawing groups, such as NO2, CN, or CO2 H, can be added across the double bond in the presence of radical generators, such as organic peroxides. Hydroboration can be used to prepare the alkylborane, as described in S. Ramakrishnan, E. Berluche, and T. C. Chung, Macromolecules, 233, 378 (1990), and subsequent papers by T. C. Chung. The alkylborane derivative may then be transformed to the alcohol, or amine, or other functional groups. Diazo compounds may be added to the double bonds, either under the influence of heat, or metal catalysts, such as Cu and Rh salts. Reactive dienophiles, such as maleic anhydride and di-t-butyl azodicarboxylate can be added to the double bond to form the anhydride or the hydrazide (which can be thermally converted to the hydrazine), respectively. Reactive dipoles, such as nitrile oxides and nitrones can be added to the double bond. Hydrogenation of the above mentioned derivatives can be used to introduce amino-alcohol functionality. A variety of oxidative reactions, including oxidation with potassium permanganate and sodium perborate, may be used to introduce hydroxyl groups.
The polymers of this invention are preferably cured (crosslinked) by ultraviolet or electron beam radiation, but radiation curing utilizing a wide variety of electromagnetic wavelengths is feasible. Either ionizing radiation such as alpha, beta, gamma, X-rays and high energy electrons or non-ionizing radiation such as ultraviolet, visible, infrared, microwave and radio frequency may be used. The details of radiation curing are given in commonly assigned copending application Ser. No. 692,839, filed Apr. 28, 1991, U.S. Pat. No. 5,229,464, "Viscous Conjugated Diene Block Copolymers" and Ser. No. 772,172, filed Oct. 7, 1991 U.S. Pat. No. 5,382,604, "Crosslinked Epoxy Functionalized Block Polymers and Adhesives," both of which are herein incorporated by reference.
Reactive (curable) diluents that can be added to the polymer include epoxy, vinyl ether, alcohol, acrylate and methacrylate monomers and oligomers. Such polymers and other diene-based polymers may also be added or blended. Examples of epoxy reactive diluents include bis(2,3-epoxycyclopentyl)ether (Union Carbide EP-205), vinyl cyclohexene dioxide, limonene oxide, limonene dioxide, pinene oxide, epoxidized fatty acids and oils like epoxidized soy and linseed oils.
The polymers may also be cured without the use of radiation by addition of a cationic initiator. Suitable initiators include the halides of tin, aluminum, zinc, boron, silicon, iron, titanium, magnesium and antimony, and the fluoroborates of many of these metals. BF3 complexes such as BF3 -ether and BF3 -amine are included. Also useful are strong Bronsted acids such as trifluoromethanesulfonic (triflic acid) and the salts of triflic acid such as FC-520 (3M Company). The cationic initiator is chosen to be compatible with the polymer being crosslinked, the method of application and cure temperature. The epoxy-containing polymers may also be crosslinked by the addition of multifunctional carboxylic acids, acid arthydrides, and alcohols, and in general by the curing methods described in U.S. Pat. No. 3,970,608, which is incorporated by reference. Volatile amines can be used to inhibit or retard unwanted cure, such as to maintain fluidity in one pack formulations until they are applied and reach the appropriate bake temperature for cure. They may also be cured by use of amino resins in the presence of a proton donating acid such as is described in "Method of Chemically Crosslinking Sterically Hindered Epoxidized Polymers", Ser. No. 863,644, filed Apr. 3, 1992, which is abandoned, commonly assigned and herein incorporated by reference. Radiation crosslinking is preferred because reactive ingredients do not come in contact with warm adhesives.
The crosslinked materials of the present invention are useful in adhesives (including pressure sensitive adhesives, contact adhesives, laminating adhesives and assembly adhesives), sealants, coatings, films (such as those requiring heat and solvent resistance), printing plates, fibers, and as modifiers for polyesters, polyethers and polyamides. The polymers are also useful in asphalt modification. In addition to the functionalized polymer and any curing aids or agents, products formulated to meet performance requirements for particular applications may include various combinations of ingredients including adhesion promoting or tackifying resins, plasticizers, fillers, solvents, stabilizers, etc. as described in detail in the aforementioned commonly assigned applications which are incorporated by reference.
Compositions of the present invention are typically prepared by blending the components, preferably between 25� C. and 125� C., until a homogeneous blend is obtained, usually less than three (3) hours. Various methods of blending are known to the art and any method that produces a homogeneous blend is satisfactory. The resultant compositions may then preferably be used in a wide variety of applications. Alternatively, the ingredients may be blended into a solvent.
Adhesive compositions of the present invention may be utilized as many different kinds of adhesives for example, laminating adhesives, flexible packaging laminated adhesives, pressure sensitive adhesives, tie layers, hot melt adhesives, solvent borne adhesives and waterborne adhesives in which the water has been removed before curing. The adhesive can consist of simply the epoxidized polymer or, more commonly, a formulated composition containing a significant portion of the epoxidized polymer along with other known adhesive composition components. A preferred method of application will be warm melt application at a temperature 20� to 125� C. because warm melt application is non-polluting and can be used on heat sensitive substrates. The adhesive can be heated before and after cure to further promote cure or post cure. Radiation cure of warm adhesive is believed to promote faster cure than radiation cure at room temperature.
Preferred uses of the present formulation are in the preparation of pressure-sensitive adhesive tapes and the manufacture of labels or flexible packaging. The pressure-sensitive adhesive tape comprises a flexible backing sheet and a layer of the adhesive composition of the instant invention coated on one major surface of the backing sheet. The backing sheet may be a plastic film, paper or any other suitable material and the tape may include various other layers or coatings, such as primers, release coatings and the like, which are used in the manufacture of pressure-sensitive adhesive tapes. Alternatively, when the amount of tackifying resin is zero, the compositions of the present invention may be used for adhesives that do not tear paper and molded goods and the like.
Polymer 1 was a symmetric star polymer, Dn --X, with polyisoprene arms, D, prepared by anionic polymerization. The polymer was prepared as follows. Isoprene monomer was fed to a reactor already charged with cyclohexane and sec-butyl lithium initiator, and the isoprene was completely polymerized to form the arms. DVB-55 was added to couple the arms, and after about one hour reaction time, methanol was added to terminate the living polymer. 0.102 pounds of the DVB-55 mixture (a product of Dow Chemical, containing about 55-56 wt. % divinylbenzene and about 42 wt. % ethylvinylbenzene) was used for every 1.000 pound of isoprene monomer. A sample was taken from, the reactor just before the addition of the DVB-55, and was analyzed by GPC to determine the peak molecular weight of the polyisoprene arms. A value of 6820 was found. Thus, each arm consisted of about 100 isoprene mers, and about 5.3 mers of the DVB-55 monomer mixture per polyisoprene arm were used to couple and form the star polymer. GPC on the final star polymer indicated that the polymer was 92% coupled. The weight average molecular weight, Mw, of the polymer was measured be static light scattering. Dry polymer was dissolved in tetrahydrofuran and filtered through a 0.2 micron filter. The analysis wavelength was 632.8 nm, the temperature was 25.0� C. and the DRI was 0.135. The Mw determined was 157,000. Hence, the average number of arms on the polymer was 21. 1 H NMR on the final polymer indicated the arms consisted of 94% 1,4-polyisoprene and 6% 3,4-polyisoprene. The majority of the polymer was left in solution for epoxidations. The % polymer solids of the solution was determined to be 23.3%.
Preparation of polymers 2-9. These polymers were made by epoxidizing portions of Polymer 1 from Example 1 with peracetic acid (in a stirred glass flask with acid dripped in slowly and the reaction temperature was 60� C. and the reaction hold time was 3.5 hours) according to the recipes in Table 1 below.
TABLE 1__________________________________________________________________________Polymer(gram recipes)Polymer 2 3 4 5 6 7 8 9__________________________________________________________________________Polymer 1 solution 2505 1812 1003 136320 1812 1003 1812 1003(23.3% polymer)0.1 N NAOH 13 19 10 1690 32 18 45 25peracetic acid 63 92 51 8284 156 86 220 122solution Meq epoxide per gram of polymerTheoreticalBasis Polymer 1 0.50 1.00 1.00 1.20 1.70 1.70 2.40 2.40Basis final 0.49 0.98 0.98 1.18 1.66 1.66 2.31 2.31epoxidized polymerExperimentalBy 1 H NMR on 0.45 1.06 1.07 1.17 1.74 1.89 2.88 2.72epoxidized polymer__________________________________________________________________________
Each polymer solution was completely neutralized with an equal volume of aqueous NaOH wash solution. The mixtures were stirred for about 30 minutes, agitation was stopped and the bottom water/sodium acetate layers were removed. Each of the polymer solutions were washed at least three more times with distilled water to remove residual sodium acetate. Polymers 3 and 4 were blended while still in solution to make a larger batch, designated polymer 10. Likewise, polymers 6 and 7, and polymers 8 and 9 were blended to make polymers designated polymer 11 and polymer 12, respectively. A small amount of a phenolic antioxidant was added to each polymer solution and then polymers 2, 3, 10, 11, and 12 were dried in a vacuum oven to remove the solvent.
The viscosities of Polymers 1, 2, 5, 10, 11 and 12 were measured using a Rheometrics Dynamic Mechanical Spectrometer with a parallel plate geometry. The measurements were made in dynamic mode at a shear rate of 10 radians per second and temperatures from 25� to 70� C. as shown in FIG. 1. FIG. 1 demonstrates that the low level of epoxidation in Polymer 2 (0.45 meg epoxide per gram) does not significantly change the viscosity from the basis Polymer 1. Higher levels of epoxidation in Polymers 5, 10, 11 and 12 show increased viscosity over the basis Polymer 1. All 6 polymers shown in FIG. 1 have similar reductions in viscosity with increasing temperature. Viscosity falls by a factor of approximately 10X for each 40� C. of temperature increase.
Polymer 13 was prepared by partially hydrogenating Polymer 1 using a nickel-aluminum catalyst under conditions that do not hydrogenate aromatic double bonds. The catalyst was washed out. The hydrogenation catalyst was made by the reaction of nickel 2-ethylhexanoate and triethylaluminum (Al/Ni ratio was about 2.3/1) and was used at 202 ppm nickel on a solution basis, at a pressure of 800 psi and a temperature ranging from 60� to 80� C. 1 H NMR analysis was used to obtain experimental values for the residual olefinic double bonds left in the polymer.
______________________________________ Meq epoxide/g polymer______________________________________1,4-polyisoprene (trisubstituted ODB) 2.033,4-polyisoprene (disubstituted ODB) 0.02total = 2.05______________________________________
Preparation of polymer 14. Polymer 14 was made by epoxidizing a portion of polymer 13 from Example 3 with peracetic acid according to the procedure of Example 2 and the recipe below.
______________________________________Polymer 14(gram recipe)______________________________________Polymer 1 solution 2342(23.3% polymer)0.1 N NAOH 50peracetic acid 246solutionMeq epoxide per gram of polymerTheoreticalBasis Polymer 1 2.04Basis final 1.98epoxidized polymerExperimentalBy 1 H NMR on 1.95epoxidized polymer______________________________________
The polymer solution was completely neutralized with an equal volume of an aqueous NaOH wash solution, and then water washed to remove residual sodium acetate. A small amount of a phenolic antioxidant was added to the polymer solution and then the polymer 14 was dried in a vacuum oven to remove the solvent.
Polymer 15 was a symmetric star polymer, Dn --X, with polyisoprene arms, D, prepared by anionic polymerization. The polymer was prepared as follows. Isoprene monomer was fed to a reactor already charged with cyclohexane and sec-butyl lithium initiator, and the isoprene was completely polymerized to form the arms. DVB-55 was added to couple the arms, and after about one hour reaction time, methanol was added to terminate the living polymer. 0.129 pounds of the DVB-55 mixture was used for every 1.000 pound of isoprene monomer. A sample was taken from the reactor just before the addition of the DVB-55, and was analyzed by GPC to determine the peak molecular weight of the polyisoprene arms. A value of 3030 was found. Thus, each arm consisted of about 44 isoprene mers, and about 2.9 mers of the DVB-55 monomer mixture per polyisoprene arm were used to couple and form the star polymer. GPC on the final star polymer indicated that the polymer was 74% coupled. The weight average molecular weight, Mw of the polymer was measured be static light scattering. Dry polymer was dissolved in tetrahydrofuran and filtered, with considerable difficulty, through a 0.2 micron filter. The analysis wavelength was 632.8 nm, the temperature was 25.0� C. and the DRI was 0.135. The Mw determined was 198,000, but the value is not considered to be precise because of the experimental difficulties. Hence, the average number of arms on the polymer was about 58. 1 H NMR on the final polymer indicated the arms consisted of 94% 1,4-polyisoprene and 6% 3,4-polyisoprene. The polymer was dried to remove the solvent.
Preparation of polymer 16. Polymer 16 was made by epoxidizing a portion of polymer 15 from Example 5 with peracetic acid according to the recipe below.
______________________________________Polymer 16(gram recipe)______________________________________Polymer 15 69(23.3% polymer)Cyclohexane 128Sodium carbonate 0.32peracetic acid 15solutionMeq epoxide per gram of polymerTheoreticalBasis Polymer 1 1.00Basis final 0.98epoxidized polymerExperimentalBy 1 H NMR on 0.80epoxidized polymer______________________________________
After neutralization and water washing, a small amount of a phenolic antioxidant was added to the polymer solution, and polymer 16 was dried in a vacuum oven to remove the solvent.
Polymer 1 and polymer 10 were compared for ability to cure by UV irradiation. The following formulations were prepared. Zonatac 105 lite is a polyterpene tackifying resin from Arizona Chemical. Cyracure UVI-6974 is a photoinitiator made by Union Carbide.
______________________________________Formulation 7-A 7-B 7-C______________________________________Polymer 1 100 30 0Polymer 10 0 70 70Zonatac 105 lite 0 0 30Cyracure UVI-6974 0.93 0.93 0.93Tetrahydrofuran 67 67 67______________________________________
After all the components of the formulation were dissolved, films were cast onto 1 mil polyester film to give about 1.5 mils of coating when dried. The films were very sticky to the touch and lacked cohesive strength. The test films were prebaked for 2 minutes at 121� C. and then were irradiated with UV light from a Linde Photocure unit equipped with aluminum reflectors and one medium pressure Hg bulb. The films passed under the lamp at 30 feet per minute with the test formulation facing the incoming UV light. All three of the films remained sticky to the finger and had not developed good cohesive strength for at least 5 minutes after the UV treatment; they should have been good for laminating flexible backings. The films were then give a post thermal treatment of 10 minutes in a 121� C. oven. After this postcure, formulation 7-A still had not developed good cohesive strength, and 7-B was little better, whereas 7-C was tacky but had excellent cohesive strength. Each of the postbaked test films were measured for polymer gel content with the following results.
______________________________________Formulation Polymer Gel, %______________________________________7-A 17-B 127-C 75______________________________________
The gel data clearly shows that the unepoxidized star polymer 1 did not cure, and when blended in (at the 30% level) with polymer 10, retards the cure of epoxidized polymer 10. Whereas, formulation 7-C shows that the use of the polyterpene tackifying resin, Zonatac 105 lite at the 30% level, does not prevent epoxidized polymer 10 from curing sufficiently to provide good cohesive strength.
A portion of polymer 10 containing 1% Cyracure UVI-6974 was dissolved in THF and cast onto pieces of 1 mil polyester film. The dried film thickness was about 1.5 mils. The films were examined for gel content as a function of the curing treatments shown. In all cases the films were prebaked for 2 minutes in a 121� C. oven before the treatment, and were aged under ambient conditions for 1 day before starting the gel test.
______________________________________Treatment Gel Content, %______________________________________Bake for 10 minutes in a 121� C. oven. 1UV exposure at 99 fpm with Vycor 63filter in place.UV exposure at 99 fpm with Vycor 98filter in place, followed by 10minutes in a 121� C. oven.______________________________________
The results show how a polymer like polymer 10 can be applied warm without causing gel formation, and then can be activated by exposure to very low levels of UV light and will cure under ambient conditions with time, and how cure can be accelerated by application of mild heating. The action of the Vycor filter in the experiment was to-reduce the effective amount of light reaching the substrate from the single medium pressure Hg bulb by a factor of about 4, so as to simulate the amount of UV light that would be seen at about 400 fpm if the filter is not in place.
Portions of polymers 2, 10, and 12 were dissolved in toluene and thin films were cast onto 1 mil polyester film. Dry film thickness of each polymer on the polyester film was about 1.5 mils. The films were prebaked for 2 minutes in a 121� C. oven to assure complete dryness, and were then cured with 3 Mrads of EB irradiation from an Energy Sciences CB-150 EB processor. The test films were measured for degree of cure (gel content) and for several typical pressure sensitive adhesive properties. All three of the polymers cured well to give strong films with good properties.
______________________________________Polymer 2 10 12______________________________________Epoxidation level, Meq/g 0.45 1.07 2.80(measured)Gel Content, % 83 85 87Rolling Ball Tack, cm 1 2 2Polyken Probe Tack, g 600 224 543Shear Adhesion Failure 123 139 143Temperature, �C.(1 in*1 in lap, 1000 g)95� C. Holding Power, min >1000 >1000 >1000(1 in*1 in lap, 1000 g)______________________________________
The SAFT was measured by 1"�1" Mylar to Mylar lap joint with a 1 kg weight. SAFT (shear adhesion failure temperature) measures the temperature at which the lap shear assembly fails under load in an oven whose temperature is raised at a rate of 40� F. per hour. Rolling Ball Tack (RBT) is the distance in centimeters a steel ball rolls on the adhesive film with a standard initial velocity (PSTC test No. 6). Small numbers indicate aggressive tack. 95� C. Holding Power is the time required to pull a standard area (1"�1") of tape from a standard Mylar test surface under a standard load (1 kg), in shear at 2� antipeel. Polyken probe tack (PPT) was determined by ASTM D-2979. For HP and PPT, higher numbers indicate better performance for most pressure sensitive adhesive applications.
Portions of polymer 10 and polymer 12, each with 1% Cyracure UVI-6974 added, were dissolved in THF and cast onto flexible 1 mil polyester film. The polymer film thickness after evaporation of the THF was about 1.5 mils. The films were prebaked for 2 minutes in a 121� C. oven, UV cured at 30 fpm with no Vycor filter used, and postbaked for 10 minutes in a 121� C. oven. The films were tested for polymer gel formation and typical pressure sensitive adhesive properties.
______________________________________Polymer 10 12______________________________________Epoxidation level, Meq/g 1.07 2.80(measured)Polymer Gel Content, % 99 98Rolling Ball Tack, cm 4 >12Polyken Probe Tack, g 221 8Shear Adhesion Failure 98 105Temperature, �C.(1 in*1 in lap, 1000 g)95� C. Holding Power, min >1000 >1000(1 in*1 in lap, 1000 g)______________________________________
The results show that polymer 10 is a much better pressure sensitive adhesive than polymer 12. Polymer 12 has a higher level of epoxidation and cures too much, by UV, to make as good a pressure sensitive adhesive as polymer 10.
Resin 17 (epoxidized S10) was prepared from Piccolyte S-10 polyterpene resin from Hercules in a manner similar to that used to prepare the epoxidized star polymers above (temperature ranged from 19� to 54� C. and the hold time was 1.75 hours).
______________________________________Resin 17(gram recipe)______________________________________Piccolyte S-10 479Cyclohexane 930Sodium carbonate 6.3peracetic acid 293Meq epoxide per gram of polymerExperimental 0.6by epoxy titrationepoxidized resin______________________________________
The resin solution was completely neutralized with an equal volume of an aqueous NaOH wash solution, and then water washed to remove residual sodium acetate. The resin solution was mixed with magnesium sulfate to remove any residual water and the magnesium sulfate was filtered out. The resin solution was vacuum dried to remove the solvent.
The following adhesive formulations were made using polymer 5 with Piccolyte S-10 and resin 17.
______________________________________Formulation 11-A 11-B______________________________________Polymer 5 75 75Piccolyte S-10 25 0Resin 17 0 25Cyracure UVI-6974 1 1Irganox 1010 (antioxidant) 1 1Tetrahydrofuran 70 70______________________________________
Formulations 11-A and 11-B were cast on 1 mil polyester film to give about 1.5 mils when dry. The test films were prebaked for 2 minutes in a 121� C. oven, UV irradiated at 30 fpm using no Vycor filter, and then immediately postbaked for 10 minutes in a 121� C. oven. The films of both test formulations remained soft and gooey immediately after the UV exposure. They developed excellent cohesive strength during the postbake. The films were tested for polymer gel content and PSA properties after the cure.
______________________________________Formulation 11-A 11-B______________________________________Polymer Gel Content, % 100 100Formulation Gel Content, % 76 84Rolling Ball Tack, cm >16 6Polyken Probe Tack, g 0 20295� C. Holding Power 4 480(1 in * 1 in, 500 g), minRoom Temperature Holding >4000 >4000Power to Steel, min(1 in* 1 in, 500 g)______________________________________
The results above show the advantage of using an epoxidized polyterpene resin over the unepoxidized resin for improved adhesion. With UV cure the epoxidized polyterpene resin appears to have advanced in molecular weight and partially joined the polymeric gel network.
This example shows the ability of different resins to tackify polymer 14.
______________________________________Formulation 12 A B C D E F G H I K______________________________________Polymer 14 100 75 75 75 75 75 75 75 75 75Piccolyte S-10 0 25 0 0 0 0 0 0 0 0Resin 17 0 0 25 0 0 0 0 0 0 0Regalrez 1094 0 0 0 25 0 0 0 0 0 0Escorez 5380 0 0 0 0 25 0 0 0 0 0Arkon P90 0 0 0 0 0 25 0 0 0 0Piccolyte S70 0 0 0 0 0 0 25 0 0 0Foral 85 0 0 0 0 0 0 0 25 0 0Piccolyte A-11 0 0 0 0 0 0 0 0 25 0Piccolyte C-11 0 0 0 0 0 0 0 0 0 25Toluene 63 63 63 63 63 63 63 63 63 63______________________________________
The test films were exposed to 3 Mrad of EB radiation and tested for pressure sensitive adhesive properties. Regalrez 1094 is a hydrogenated resin from Hercules. Escorez 5380 is a hydrogenated resin from Exxon Chemical. Arkon P90-resin from Arakawa Chemical. Piccolyte S70 is a polyterpene resin from Hercules, as are Piccolyte A-115 and C-115. Floral 85 resin is from Hercules.
__________________________________________________________________________Formulation 12 A B C D E F G H I J__________________________________________________________________________Polymer Gel, % 90 80 66 85 82 87 -- 66 70 75Rolling Ball 9 3 2 3 4 5 -- 2 4 9Tack, cmPolyken Probe 132 362 490 308 382 330 -- 908 965 541Tack, g180� peel from 0.2 0.5 1.5 0.7 0.5 0.6 -- 1.8 2.0 2.0steel, pli__________________________________________________________________________ 180� peel is determined by PSTC test No. 1.
Polymer 18 was a symmetric star polymer, Dn --X, with polyisoprene arms, D, prepared by anionic polymerization. Preparation was almost identical to that of polymer 1. Polymer 18 was prepared as follows. Isoprene monomer was fed to a reactor already charged with cyclohexane and sec-butyl lithium initiator, and the isoprene was completely polymerized to form the arms. DVB-55 was added to couple the arms, and after about one hour reaction time, methanol was added to terminate the living polymer. 0.102 pounds of the DVB-55 mixture (a product of Dow Chemical, containing about 55-56 wt. % divinylbenzene and about 42 wt. % ethylvinylbenzene) was used for every 1.000 pound of isoprene monomer. A sample was taken from the reactor just before the addition of the DVB-55, and was analyzed by GPC to determine the peak molecular weight of the polyisoprene arms. A value of 4800 was found. Thus, each arm consisted of about 70 isoprene mers, and about 3.7 mers of the DVB-55 monomer mixture per polyisoprene arm were used to couple and form the star polymer. GPC on the final star polymer indicated that the polymer was 75% coupled. The weight average molecular weight, Mw, of the polymer was measured be static light scattering. Dry polymer was dissolved in tetrahydrofuran and filtered through a 0.2 micron filter. The analysis wavelength was 632.8 nm, the temperature was 25.0� C. and the DRI was 0.135. The Mw determined was 85,000. Hence, the average number of arms on the polymer was 16. 1 H NMR on the final polymer indicated the arms consisted of 94% 1,4-polyisoprene and 6% 3,4-polyisoprene.
Polymer 19 was a symmetric star polymer with polyisoprene arms. This polymer was prepared by an anionic process similar to that used in the synthesis of Polymer 1. The principle differences in this experiment were that the polymerization solvent was a mixture of cyclohexane/diethyl ether (9/1 wt/wt) and the coupling agent was DVB-80 (Dow Chemical) (m- & p-divinylbenzene, 78% wt, ethylvinylbenzene, 20% wt, diethylbenzene, 1% wt, naphthalene, 1% wt). In this example, the polyisoprene arm, before reaction with DVB, was found by NMR analysis to have a molecular weight (MW) of 1200 (1,4-addition=58%; 3,4-addition=42%). The living polyisoprene was coupled with DVB (DVB/Isoprene=0.526 wt/wt) affording a symmetrical star polymer. Analysis of the coupled polymer by GPC found essentially all of the polyisoprene arms were coupled to DVB cores. The polymer solution was quenched with water to remove any living chain ends that might have been present, washed repeatedly to remove lithium salts and concentrated to remove solvent. The polymer was isolated as a white solid and reserved for rheology studies.
Polymer 20 was a symmetric star polymer with polyisoprene arms. This polymer was prepared by an anionic process similar to that used in the synthesis of Polymer 19. The principle differences in this experiment were that the polyisoprene arm MW=2200 (basis NMR analysis) (1,4-addition=57%; 3,4-addition=43%) and the DVB/Isoprene=0.195 (wt/wt). Analysis of the coupled polymer by GPC found about 86% of the polyisoprene chains were coupled to divinylbenzene cores. The product was isolated (as described for Polymer 19) as a very viscous mass and reserved for rheology studies.
It is well known that for linear polymers the viscosity decreases as the molecular weight of the polymer decreases. We show in the table below that unexpectedly, this is not true for the star polymer of the current invention. The viscosities listed in the table below were measured on a Rheometrics Dynamic Mechanical Spectrometer at the temperatures noted. It is clear from the table below that the viscosity of polymers 19 and 20, which have arm molecular weights of less than 3,000 molecular weight, have substantially higher viscosities than Polymers 15 and 18 which have molecular weights greater than 3,000. Therefore there is an optimum range of molecular weights for star polymers of this type from about 3,000 to about 7,000. Since epoxidation results in only small increases in viscosity the same effect of arm molecular weight on viscosity for epoxidized polymers is expected.
______________________________________ Arm ViscosityPolymer Molecular Weight (Poise) Temperature (�C.)______________________________________19 1,200 1.5 � 106 32.820 2,200 3,410 26.015 3,030 903 26.018 4,800 540 25.0 1 6,820 1,074 26.0______________________________________
Preparation of polymers 21, 22, 23, and 24. The following ingredients were loaded into bottle reactors:
______________________________________ Polymer 21 22 23 24 (grams, except where indicated)______________________________________Cyclohexane 231 244 229 2491,3-butadiene 27.9 28.4 28.5 28.2Sec-butyl lithium 4.0 ml 4.0 ml 4.0 ml 4.0 mlsolutionDVB-55 3.97 2.65 0 0DVB-80 0 0 2.80 1.87Each of the polymerswas evaluated byGPC.Polybutadiene arm 5300 5200 5200 5600(D) peak molecularweightCoupling 56 59 50 45Efficiency, %______________________________________
Portions of each of the above polymers were dried down after adding a small amount of a phenolic anitoxidant. The samples were analyzed by 1 H NMR and were measured for complex viscosity by Rheometrics. NMR results showed that the polybutadiene was 9% 1,2-polybutadiene and 91% 1,4-butadiene, and that less than 2% of the cyclohexane remained in the polymers. The viscosity results are shown below.
______________________________________Residual Measurementcyclohexane temperature Complex viscosity(%) (�C.) (poise)______________________________________Polymer 21 0.8 25 248Polymer 22 1.2 25 176Polymer 23 1.3 25 210Polymer 24 1.9 25 135______________________________________
Each of the above polymers may be epoxidized as done in Example 2, Table 1. The star polymers of Example 15 have arms consisting of butadiene and have slightly lower viscosities than the polymers in Examples 1-5 because polybutadiene has a lower glass transition temperature than isoprene. Decreasing the Tg of the polymer backbone decreases the viscosity near room temperature. Similarly, increasing the Tg by the inclusion of styrene, high 3,4-isoprene or high 1,2-butadiene increases the viscosity. For example EKP 202, made by Shell Chemical Company, is a star polymer similar to those in the instant invention but containing nearly 50% styrene in the arms. The molecular weight of the arms is 5,800 and its viscosity at 24� C. is 732,000 poise, as compared to Polymer 1 which has a viscosity of 1,074 poise at 26� C. with an arm molecular weight of 6,820.
A glass polymerization bottle was equipped with a mechanical stirrer and a syringe through which chemicals were added. The bottle was flushed with and maintained under nitrogen. After the addition of 200 ml of cyclohexane, stirring was initiated. To the bottle were added 1.0 ml of N,N,N',N'-tetramethylethylenediamine and 4 drops of diphenylethylene. The solution was titrated with a s-butyllithium to a light orange color which did not change when an additional 1.5 ml of 1.4 M s-butyllithium were added. After 3.2 ml of isoprene (1524 g/arm) were added dropwise, 1.0 ml of divinylbenzene was added dropwise as the color of the solution turned to a dark red. The resulting solution was stirred for 20 minutes and 13.0 ml of t-butyl methacrylate (6190 g/arm) was added dropwise. The solution was stirred for two hours as the color faded to a light orange. Polymerization was terminated by addition of 10 ml of methanol. The solvent present was removed by evaporation and the resulting oil was coagulated in isopropyl alcohol, methanol and water.
To a glass polymerization bottle flushed with nitrogen and equipped with a stirrer were added 200 ml of cyclohexane and 20 ml of tetrahydrofuran and stirring was initiated. After the addition of 4 drops of diphenylethylene as an indicator, the solution was titrated to an orange color with s-butyllithium. An additional 1.5 ml of s-butyllithium was added. After stirring for 5 minutes, 3.2 ml of isoprene were added and the solution was stirred for 15 minutes as the color turned a light orange. After addition of 1.0 ml of divinylbenzene the solution was stirred for 10 minutes as the color, initially blood red, turned somewhat lighter. While stirring continued, 13.0 ml of t-butyl methacrylate were added. The polymerization was terminated by the addition of methanol and allowed to stand overnight as the color changed from water white to light yellow. The solvent was removed by evaporation and the resulting product was coagulated in methanol and water.
A glass polymerization bottle equipped with a stirrer was flushed with nitrogen and 200 ml of cyclohexane and 5.0 ml of diethyl ether were added. Stirring was initiated and after the addition of 4 drops of diphenylethylene as indicator the solution was titrated with s-butyllithium to an orange color. An additional 1.5 ml of s-butyllithium was added and the resulting solution was stirred for 15 minutes. As stirring continued, 3.2 ml of isoprene was added dropwise. One milliliter of divinylbenzene was then added as the color of the solution turned blood red. After stirring for 10 minutes as the color of the solution became lighter, 13.0 ml of t-butyl methacrylate were added as the solution turned light yellow in color. After 30 minutes the solution was almost water white. Polymerization was then terminated by addition of methanol and the polymeric product was coagulated in methanol and water.
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E-Painters, Energy Cola in crucial clash
Derailed the last time out, Rain or Shine and Barako Bull tangle tonight in a duel with huge playoff implications in the PBA Commissioner's Cup at Smart Araneta Coliseum.
Gametime is 7:30 p.m. with the Elasto Painters looking to close in on the No. 2 seeding in the quarterfinals with a win over the Energy Cola, who are also seeking to stay alive for a spot in the playoffs.
With Petron Blaze hot on their heels for the coveted No. 2 spot that comes with a twice-to-beat incentive, the Elasto Painters, with an 8-4 record, are under pressure to prevail even as the Energy Cola try to sneak past idle Air 21 for the last playoff berth.
Alaska tries to put an exclamation point to a sensational elimination-round campaign against already-eliminated Globalport in the 5:15 p.m. opener.
The Aces wrapped up top spot in the quarterfinals after a 102-93 trouncing of Barangay Ginebra that also snapped the Gin Kings' six-game winning run Wednesday night.
The Energy Cola have a tough task in dealing with Rain or Shine's 7-foot-3 import Bruno Sundov as well as Paul Lee and Jeff Chan, who are looking to bounce back from poor shooting performances in the 89-84 overtime loss to Alaska last Friday.
This puts pressure on Barako Bull import DJ Mbenga, the former Los Angeles Lakers center, who had a quiet debut of 14 points and 12 rebounds in the loss to Petron last Sunday.
An NBA champion with the Lakers, Mbenga, a 6-foot-10 Congolese-Belgian, hasn't played a competitive game in three months until the game against the Boosters.
A win will shove Barako into a tie at eighth spot with Air21 with a game remaining in both of their schedules. Under the format, the top two teams will get a twice-to-beat edge against the seventh and eighth-ranked teams in the playoffs. The third and sixth-ranked squads play in a best-of-three series, just like the No. 4 and No. 5 seeds.
Alaska is heavily favored over a Globalport squad with only two wins in 12 games so far.
Credited for the Aces' explosive stint is the all-around play of crack import Robert Dozier.
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subset: commoncrawl


text:
The simple mechanics in this game will have you playing for longer than you imagined. You control a ragdoll character with the arrow keys and you will utilize physics to protect him from the oncoming avalanche. Hazardous spikes will fall and as time increases, so will the number of spikes. Be creative and flop the ragdoll around to slide, bounce off walls, create momentum and ultimately become the avalanche-dodging master! See how long you can survive the fast-paced intensity!Ragdoll Avalanche 2,
Ragdoll Avalanche 2
GD Star Rating
- Arrow Keys = Move
Description: Use ragdoll physics to dodge the never-ending avalanche of spikes ...


text:
NEW YORK ( TheStreet) - Intel (INTC - Get Report) may have lowered its full-year guidance when it announced its second-quarter results on Tuesday, but strong gross margins and competitive strength shouldn't be ignored.
The tech giant's shares were climbing nearly 3.5% to $26.26 on Wednesday as investors digested Intel's comfortable earnings beat and its 63.4% gross margin, which came in above the midpoint of its guidance.
Despite acknowledging a challenging macroeconomic environment, the Dow component expects gross margins to remain healthy. The Santa Clara, Calif.-based company predicted a third-quarter gross margin between 61% and 65%, and offered a full-year margin range of 62% and 66%.
"Bears have long argued that Intel's capex in next-gen capacity and


text:
The KPMG International Annual Review demonstrates our achievements and reflects the insights and expertise KPMG professionals bring to client relationships and our broader communities.
For the World Economic Forum Annual Meeting, each year KPMG presents WEFLIVE, an interactive social media aggregation and data visualization service that analyzes the conversations emanating from Davos, as well as what the world is saying in response
KPMG's Tax experts analyse the key changes stemming from the 2015 Budget Speech and what this means for South African companies.
Our Financial Services professionals can assist you in addressing all your banking, insurance, investment management, retirement funds, medical schemes and stock broking issues with the aim of achieving your business objectives.
With a dedicated team of 202 partners and 2 745 practitioners globally, KPMG's Healthcare Practice has the global expertise and local knowledge to provide South Africa's healthcare sector with forward thinking services.
The 2014 KPMG Insurance Industry Survey is launching on 7 August 2014 and presents a broad view of hot topics and current discussion points within the Insurance Industry.
Exciting new elements around the Protection of Personal Information Act (POPI) legislation. Find out more about POPI and KPMG's multi-disciplinary solution.
View current Graduate Programmes, or search on specific criteria to find programmes that match your interests.
A career at KPMG starts at different times for different people. For some, it starts at university when they join us on work placement, for others it starts once they've graduated.
We have rich conversations with our clients every day, and increasingly these conversations are happening online. We encourage you to ask questions, share your views, and connect with like-minded professionals.
"While the Minister did not announce major tax changes in the current year, the complexity and challenges of the existing tax environment means that it is time for tax to be a boardroom level topic again," said Alan Field, Director, Chairman of Tax and Legal, KPMG in South Africa.
KPMG believes that the need to elevate the tax discussion on the boardroom agenda is becoming more crucial. Apart from a tax environment which remains highly complex, certain trends, such as globalisation, transparency, exchange of information between authorities in multiple jurisdictions, and an increase in reported tax disputes, make it necessary for boards to be more proactively involved in governing the tax affairs of their companies.
"Not many companies would have predicted that their Tax Affairs would be the topic of newspaper headlines around the world", said Field.
Directors' have a dual role to play. On the one hand, they face the challenging task of ensuring that their companies fully understand the increasingly complex Tax laws around the world, in order to behave as responsible corporate citizens. At the same time, they have a fiduciary duty to their stakeholders to ensure that the taxes paid are validly due under the law – which was becoming an increasingly blurred line given the emergence in the world of the concept of a 'morally' correct amount of taxation to pay.
© 2015
KPMG Services (Proprietary) Limited, a South African private company and a member firm of the KPMG network of independent firms affiliated
with KPMG International Cooperative ("KPMG International"), a Swiss entity. All rights reserved
KPMG International Cooperative ("KPMG International") is a Swiss entity. Member firms of the KPMG network of independent firms are affiliated with
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Hotel M Mount Pocono
Hotel M Mount Pocono
Hotel Guest Rating: 6.5/10
1244 Pocono Boulevard
Mount Pocono, PA 18344
Welcome to the Hotel M Mount Pocono
Free internet access and an exercise room appeal to guests at the Hotel M Mount Pocono.
Hotel Features
The low-rise Hotel M Mount Pocono houses 81 rooms, some non-smoking and all with free internet access, cable TV, coffeemakers and hairdryers. A continental breakfast is offered each morning. Active types make time for a workout in the exercise room. Other amenities include a guest laundry facility and fax and copy services. Parking is available.
Hotel Location
Located in the Pocono Mountains, the Hotel M Mount Pocono is 30 miles from Scranton and about three miles from I-380. Guests drive three miles to play the odds at the Mount Airy Casino and 10 minutes to find bargains at Crossings Premium Outlets. Numerous state parks offer trails and are within 20 minutes of the hotel, as are Camelback Ski Area and Alpine Mountain Ski & Snow Tubing Center. The bus stops a half-mile from the hotel, and Wilkes-Barre/Scranton International Airport is 35 miles away.
Guest Favorites
The Hotel M Mount Pocono offers Priceline guests comfy accommodations and free parking.
Hotel M Mount Pocono Amenities
- Air conditioning individually controlled in room
- Business center
- Cable television
- Continental breakfast
- Exercise gym
- Heated pool
- High speed wireless
- Ice machine
- Iron
- Ironing board
- Onsite laundry
- Vending machines
- Wireless internet connection
Hotel Information
You must show a valid photo ID and credit card upon check-in. Please note that all special requests cannot be guaranteed and are subject to availability upon check-in. Additional charges may apply. Guests are required to show a photo identification and credit card upon check-in. Please note that all Special Requests are subject to availability and additional charges may apply.
Hotel Guest Reviews of the Hotel M Mount PoconoOur hotel ratings and reviews are from real hotel guests. Priceline.com ensures that its reviews are guests-only by proactively sending hotel surveys to customers after they've completed their hotel stays. In the post-stay surveys, priceline.com hotel customers are asked a number of questions about their stay and the hotel. On a scale of 1-10 with 10 being the best, the survey asks guests to rate their overall experience and specifically rate the hotel's cleanliness, staff and location. Priceline.com does not allow site visitors to post unsolicited hotel reviews.
January 16, 2015
Family Traveling with Teens
October 31, 2014
no, i didn't get to see the pool or gym. it was good for the weekend
October 30, 2014
October 7, 2014
Family Traveling with Young Children
need an update and to be cleaner
August 21, 2014
Family Traveling with Young Children
August 4, 2014
This guest did not leave comments about this hotel.
July 30, 2014
Family Traveling with Young Children
No shampoo and conditioner in bathroom
July 20, 2014
Group Traveler
This guest did not leave comments about this hotel.
July 15, 2014
Family Traveling with Young Children
This guest did not leave comments about this hotel.
July 10, 2014
Family Traveling with Young Children
This guest did not leave comments about this hotel.
(1 - 10 of 35 reviews)
- Comfort Inn & Suites Mount Pocono from $89 (1.3mi)
- Econostay Inn (2.5mi)
- Mount Airy Casino Resort from $119 (3.0mi)
- Travelodge Mt. Pocono from $56 (3.0mi)
- Swiftwater, PA (3.7 mi)
- Cresco, PA (7.4 mi)
- Tannersville, PA (7.9 mi)
- Henryville, PA (9.9 mi)
- Canadensis, PA (10.7 mi)
- Bartonsville, PA (11.2 mi)
- Pocono Lake, PA (14.4 mi)
- Blakeslee, PA (14.6 mi)
- Sterling, PA (16.9 mi)
- Stroudsburg, PA (17.4 mi)
- East Stroudsburg, PA (18.0 mi)
- Lake Harmony, PA (19.6 mi)
- Delaware Water Gap, PA (21.5 mi)
- Albrightsville, PA (23.3 mi)
- Wind Gap, PA (24.2 mi)


text: Image From Paris My husband sent me flowers from Paris. Pictures of flowers, that is! Share this:Click to share on TwitterShare on FacebookClick to email this to a friendClick to share on PinterestClick to share on Google+Like this:Like Loading... Related This entry was posted in Uncategorized and tagged flowers, garden, garden photography, gardening, Paris, Paris flower market, Spring flowers, tulips. Bookmark the permalink.


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Sold Out $35.99
BenMarco Expresivo 2010
Other Red Blends from Argentina, South America
Winemaker's Notes
Wafting aromas of ripe red currants, black cherries and mildly smoky and sweet vanilla oak. Layers of currant fruit, dense black cherry, and notes of brown spice (cocoa, nutmeg), dark chocolate, and hints of sandalwood. Keeps showing its stuff as it breathes in the glass—for folks who want the full experience and may be a bit impatient, decanting is a good idea. Perfect balance, great concentration and length, and loaded with fine, ripe tannins for having with food or for aging.
Pairs well with a wide range of foods including grilled steak, roasted pork loin, veal, medium-strong cheeses, and most cream sauces.
Critical Acclaim
International Wine Cellar - "Bright, deep ruby-red. Plum and blackcurrant fruit aromas along with strong exotic oak notes of chocolate, mocha and coffee. Sweet, pliant, rich and deep, with black raspberry and blackberry fruit flavors carrying a full load of extroverted spicy oak. Distinctly sweeter than the 2011 malbec and cabernet bottlings, verging on decadent. But has plenty of energy to maintain its balance. Will offer early pleasure but shows the stuffing for mid-term aging."
BenMarco Winery
In 1999 Susana Balbo crafted a line of wines to showcase the ripe fruit expression of her sustainably-farmed Mendoza vineyards. The philosophy is a simple one: grow great grapes and make wines that are true to their place. Minimal intervention during the growing season and through harvest allows the true fruit character to develop. Combine this with Susana's winemaking skills and the result is wines that express the powerful fruit flavors, the ripe tannins and the incredible length and balance that can only come from this one place: Mendoza. View all BenMarco Wines
About ArgentinaView a map of Argentina wineries (ahr-jen-TEE-nah)
Notable FactsUnlike its Chilean neighbor, Argentina's vineyards are spread out around the country. The best known region is Mendoza, almost parallel to Santiago to the west. Mendoza contains the sub-regions of Maipu (pronounced MY-pu) and San Rafael. Grape-wise, the most important white is Chardonnay, making wine similar to California's style on the variety. Another fun white grape to try is Torrontes. Almost only grown in Argentina, Torrontes makes wines that are crisp, aromatic and easy-drinking. Some of the best versions of this wine come from the northern region of Salta, with very high altitude vineyards. As for the reds, Cabernet Sauvignon is the main grape for many wines leaving the country, but Malbec, the grape Argentinians like to call their own, makes very distinctive wines that are structured, dense and velvety. Many more varieties happily grow in the country, but for export, and consistent quality, these are the primary grapes.
About South AmericaRelated Links:
Young, organically farmed Carmenère at Chile's De Martino estate vineyard
Customer ReviewsSign In to Add Your Review0 }div>
Alcohol By Volume GuideMost wine ranges from 10-16% alcohol by volume. Some varietals tend to have higher (for example Zinfandel and Cabernet Sauvignon) or lower alcohol levels (Pinot Noir and many white varietals), but there is always some variation from producer to producer. Some wine falls outside of this range, for instance Port weighs in closer to 20%, while Muscat and Riesling are usually a bit below 10%.
Wine Style Guide
Light & Fruity
- Red wines that are more fruit-forward and lighter in tannin and body.
Smooth & Supple
- Medium bodied reds that go down easy, with smooth tannins and supple fruit.
Earthy & Spicy
- Wines where earthy and/or spicy dominate the flavors – typically medium to full body.
Big & Bold
- Full bodied wines that have concentrated fruit and are higher in alcohol and/or tannins. Some need age.


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|Property type
|Minimum Stay
|2 nights
Aloha and Welcome to Hale O Manu Mele!
Hale O Manu Mele is a spacious 3 bedroom and 2 bath, 2-story home situated amidst the tropical landscape of Volcano Village. In this peaceful and charming location you can experience the true beauty of Volcano. From this stunning location you can enjoy picturesque views of Mauna Loa, Mauna Kea, and the spectacular plumes of Halemaumau.
Hale O Manu Mele (or House of the Singing Birds) offers all the comforts of home in style. From the beautiful bamboo floors to the vaulted ceilings, skylight and Mission-style windows, the architecture of this home is pleasing to all who come to visit. The master bedroom is furnished with a California King bed, and mango wood furnishings. The second bedroom/office is furnished with Queen bed, built in desk, and Tiffany lamp.
Located in Volcano Village, we are nearby the general store, restaurants and art galleries, only 5 minutes away from Volcano National Park and 30 minutes from Hilo.
We booked this VRBO expecting a 3 bedroom unit for 2 nights of our 8 night Hawaii vacation. The positives is that the upstairs bedrooms were good. There was plenty of room for 4. The views from the deck are great. The fact that you are in the middle of a Rain Forest is a wonderful experience. The negative is the downstairs room and the preparation for our stay. The unit was not ready for our visit. The power was off for the downstairs. We had to search for the electric box and flip the switch. The switch included the running of a dehumidifier. The fact that the dehumidifier was not running made the downstairs bedroom smell like a moldy mess. The windows were closed tight and buggy. Later we found out the hot water heater was off. We had to light the hot water pilot and wait an hour for hot water. There was also dirty towels on the floor of the downstairs bedroom. The bedding and pillows smelled like moldy cheese. This is not a room that you can people sleep within. I promise I am not a picky person. This is just over the top gross.
We were very lucky that we had another rental house a mile away and were able to put the grandparents, who were scheduled to stay in the bad room, into that location instead of in the mold smelling room. This caused an inconvenience on the second family, but everything worked out in the end.
I would like to warn potential renters that you should not expect to stay in this downstairs room. This is really a good 2BD establishment. The cost should be lower to reflect that the unit can sleep only 4. I would not stay here again.
My husband and I and our son and his family stayed in this home for four nights in late December 2013/early January 2014. The home was beautifully built and is in a quiet location in the rainforest, but it has some serious problems. First, it's several minutes outside of Volcano Village, down a single track road, and fairly remote. The upside is that it's very quiet, the view out the back is pastoral, and we even had a view of the reflection of the lava off the steam of the volcano. However, one of the bedrooms, with en suite bath, is located on the lower level of the house and is only accessible from the outside of the house, not from within the house. It is clear that this house is not being properly cared for and that the amount of rain and high humidity are taking a high toll. The downstairs reeked of mildew when we arrived and was very difficult to sleep in due to the odor. The lower bedroom does come with a dehumidifier, which we left running the entire time we stayed in the house, and we emptied it several times a day and during the night. We sprayed Lysol everywhere, including the bed frame, the insides of the cupboards and closet, the fabric- covered chair, etc., which helped tremendously, but you shouldn't have to go to all that work when you're paying this much to stay somewhere!! We live in an extremely rainy area of southeast Alaska, and we know how to handle very high humidity and this isn't it. Even upstairs in the house, there is mold beginning to grow in the master bath and in the master bedroom closet because the high humidity in the house isn't being managed. It's a shame, because this home was very well built with expensive materials, and it won't last long at this rate.
We just returned from spring break, March 20-24, 2010 from this Volcano house. This has to be handsdown the best vacation rental in Volcano. I'm from Oahu and I've stayed at others in Volcano, but this is the best. The house is more beautiful than it looks in the picture; and it is clean, modern, well maintained with all the amenities. The wood fireplace is wonderful. The upstairs shower looks like it belongs in a luxury hotel room. The beds were huge and more comfortable than our beds at home. It is quiet, peaceful and we saw animals from the back porch everyday. Back porch looks into pasture/ranch land. Lots of native Hawaiian birds chirping and singing. It's very close to Vocanoes National Park and all the spectacular sights within the Park. I give this the highest recommendation for the price category. Ken Wong
We had a lovely stay here in October 2009. The
house is actually nicer than it appears in the photos
-- good taste, nice decor. Great view out the
balcony. Incredibly lush foliage everywhere. Good
toys for the kids. Japanese garden on the property.
The approach to the house can be a little daunting
-- it's up a fairly long road that feels a little
claustrophobic due to the dense vegetation that
accompanies the climate. But once you arrive, you
realize that it's a lovely spot. Do realize that the
SO2 levels in this area fluctuate due to volcanic
emissions - check NPS website. you need to bring
your own water in this area since they operate on
catchment water which is contaminated with SO2.
When we were there was surface lava flow at
Kapalani (1 hour away), but the national park itself
(3 minutes away) was fantastic as well.
Volcano Village, nearby Volcano National Park, Enjoyable activities nearby are hiking, bird watching, art, winery, relaxation.
|Rate Period
|Weekend Night
Base Rate
2 night minimum stay
Payment is usually accepted in the quoted currency (USD) unless the currency and the amount is specifically agreed in advance with the owner / advertiser.
Learn more about this vacation rental at the manager's website:


text:
China Travel News
There areTotoal 346 News
The Length of the Great Wall Announced by State Administration of Cultural Heritage
by miffy at 2012/6/11; Views: 1448; Comments: 1;
Since 2007, an investigation of resources on the Great Wall of China has been made by State Administration of Cultural Heritage and State Bureau of Surveying and Mapping. On June 5th, 2012, after f…
Bullet Trains Operated from Xian to Beijing and Hankou from April 4th
by fadri at 2012/6/7; Views: 886; Comments: 0;
From April 4th, 2012, bullet trains from Xian north to Beijing west and Hankou operated. It should be noticed that there are no sleepers on those two bullet trains because of the relatively short r…
Tibet Travel Permit Restricted in 2012
by fadri at 2012/6/4; Views: 958; Comments: 0;
Recently, a number of foreign travelers are complaining of not getting Tibet Travel Permits, due to the new policy of Tibet Travel Permit announced by Tibet Tourism Bureau. According to the new pol…
395 Museums Built in China During 2011
by wendysong at 2012/5/15; Views: 645; Comments: 0;
395 IT IS THE NUMBER OF MUSEUMS BUILT IN CHINA DURING 2011, stated Chen Jianming, vice-president of the Chinese Society of Museums, in an interview granted to the New York Times. Most of them …
2012 China Baise Leye Outdoor Quest to kick off
by jenifer f at 2012/4/9; Views: 1043; Comments: 0;
According to Chinas Mountaineers Club, 2012 China Baise Leye Outdoor Quest, which is approved by General Administration of Sport of China, is to be held from April 25th to 28th in Leye County of Baise…
Flights to Operate in late March
by jenifer f at 2012/3/26; Views: 673; Comments: 0;
Tianjin Airlines to Open Flights from Tianjin to Haikou from March 27th According to Xinhua Net, new flights between Tianjin, Hefei and Haikou will operate from March 27th, with the aircraft number o…
2012 Luoyang Peony Culture Festival to Kick off on April 5th
by fadri at 2012/3/26; Views: 902; Comments: 0;
The 30th Luoyang Peony Culture Festival is to kick off in Luoyang City of China's Henan Province on April 5th, 2012, which will last for one month. During the festival, the city will become a sea of b…
Flights Between Guangzhou and Koh Samui to Operate from March 20
by joyce at 2012/2/23; Views: 1022; Comments: 0;
New flights between Guangzhou and Koh Samui of Thailand will operate formally from March 20th, 2012. The flights operate on Tuesday and Friday every week, with the flight number of CZ3027/8. The fl…
Two Giant Pandas from China Made Debut in France
by joyce at 2012/2/20; Views: 2063; Comments: 0;
On February 18th, 2012, two giant pandas named Yuan Zai and Huan Huan from Giant Panda Breeding and Research Center of Chengdu City in Chinas Sichuan Province made their debut formally in Beauval Z…
Hulunbuir Is Experiencing The Coldest Period in Recent Ten Years
by wendysong at 2012/1/30; Views: 783; Comments: 0;
On January 30, freezing cold air and icy fog air swept several cities of Inner Mongolia. The temperature is down to -40℃, leading to the rare icy fog phenomena occured in Hailaer, Chenba Erhu areas…
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text:
(Science: oncogene) a proto-oncogene that causes leukaemias in chickens.
It is found in E26 transforming retrovirus (v-ets) of chickens and encodes a nuclear protein that can bind dna and regulates the initiation of transcription from a range of cellular and viral promoter and enhancer elements which may help activate and proliferate t lymphocyte cells. There is some interaction between ets and AP1.
Please contribute to this project, if you have more information about this term feel free to edit this page
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text:
Mass Distribution and Comfort
View Single Post
Hall Of Fame
Join Date: Oct 2010
Location: Baseline
Posts: 3,588
This mass had been distributed along the handle rather than just the butt.
Last night in an experiment I added a few more grams to the head. Comfort increased again.
The results surprised me too Povl. I guess not all added weight is created equal.
It makes sense though when one considers the fact that SW as "officially" calculated isn't really accurate. SW calculations assume the point of rotation is the near the wrist on the handle. That's fine if you're playing table tennis with your racquet and you're looking for a sore arm.
In reality the point of rotation is beyond the butt as pointed out by a book on the physics of tennis and available from TW. Actual SW is much greater than the official calculation and, contrary to the official calculation, weight under the grip DOES increase SW. For example, in tweaking my PSGTs this week and dropping the weight under the grip I was able to add weight in the head. It wasn't nearly a 1:1 ratio since weight in the head does effect SW more than that under the grip. But it was nice to get even more oomph in this frame while maintaining excellent RHS with a 6 point HL balance.
Since the actual point of rotation is behind the butt maybe mass under the grip prevents the frame from flexing more than it could than if weight is concentrated more in the head?
Only on Talk Tennis can you find people who believe
that 10 feet of lead tape has no effect on a frame...
Last edited by TimothyO; 12-14-2012 at
View Public Profile
Find More Posts by TimothyO


text:
NEWBERRY — Newberry's Sonic Drive In, located at 1624 Wilson Road in Newberry, will soon be one of the first of its kind to provide an indoor dining option to their customers.
According to Mac Bell, owner of the Newberry restaurant, this Sonic will be the prototype for the future of the brand's dining.
"There are 4,500 restaurants with no dining room," Bell said. "The brand has no dining room, so we have to reconstruct the brand."
Bell said he hopes this will be the first of many Sonic dining rooms across the nation. Newberry's Sonic will be the first in a franchise of about 85 restaurants to make the change.
"If we're successful, it will be something that will spread all across the nation," Bell said.
The indoor dining area will be taking the place of the outdoor sitting that was directly in front of the restaurant. Bell said a Charleston patio will also be constructed in the future for more outdoor seating.
Metts Construction of Columbia is constructing the new indoor dining facility, and local subcontractors are being used, according to Bell who says they are trying to buy supplies locally, such as the plywood purchased from Willingham & Sons Building Supplies.
Bell believes the new indoor dining option will be something customers will really enjoy, such as when the weather is cold or raining. The indoor dining will have big screen televisions, an indoor fireplace, as well as chairs and booths for customers to enjoy.
Bell said there will be seating for 42 people indoors, as well as the additional seating already in place outdoors. Because this is a prototype, Bell said the construction might take longer than normal, but hopes the addition will be complete within two to four weeks.
Elyssa Parnell can be reached at 803-276-0625, ext. 108 or at firstname.lastname@example.com.


text:
Property Details
House, 5 Bedrooms, 4.5 Baths, 16 Sleeps
Casa Grande Guadelupe sits on the bank of the Guadalupe River off River Road between the 2nd and 3rd crossing in a park like setting, 5 bedrooms sleeping 16, 4.5 baths, 3 living areas, 2 river front patio's and fire pit, in the heart of tubing and
Rainbox Trout fishing.
Just down the lane are two sister properties the Guadelupe Haus sleeping 16 and the Cabana Guadalupe sleeps 12.
Renter supplies own linens and towels.
Recent Review
Best place on River Road for a Large Group
About the Owner
1 Reviews
1 traveler review
Best place on River Road for a Large Group
Activity and Interests
Tube & Shuttle RENTAL 200 YDS UP RIVER.
In the heart of Texas Music 5 miles south of Sattler on River Rd 11 miles from 1-35 in New Braunfels. 7 miles to White Water Amphitheater, 5.5 mi to River Road Ice House.
15 minutes away Canyon Lake recreation area. 15 minutes to the Schlitterbahn, historic Gruene & New Braunfels. 30 minutes to San Marcos Outlet Malls, Texas State University and San Antonio or Austin.
Rental rates
|Rate Period
|Weekend Night
May 1st-Labor Day
May 1 2015 - Sep 7 2015
2 night minimum stay
Payment is usually accepted in the quoted currency (USD) unless the currency and the amount is specifically agreed in advance with the owner / advertiser.
Additional information about rental rates
- Refundable damage deposit $500.00
- Tax Rate 10.0%
A $500 Reservation Damage Deposit is due with a reservation. It is refundable less $125 up to 45 days prior to check in. It refunds back to the card used to pay the final balance. Reservations can be booked up to 12 months in advance, in the event of cancellation the deposit is not refundable after February 1st. The reservation can be moved to a more convenient date.
Nightly Rate: $475 - $795
Summer Rates: May 1st - Labor Day (min 2 night rental/3 nights holidays)
Weekends (Th,Fri,Sat 2 night min.) $795/night
Weekdays (Sun-Wed 3/night min.) $650/night
Off-Season Rates: Labor Day- April 30th (min 2 night rental/3 nights holidays)
- 12
- Available
- 12
- Unavailable
- 12
- Today
Property Type
- house
- Adventure
- Family
- Air Conditioning
- Internet
- children welcome
- non smoking only
- pets not allowed
- wheelchair accessible
Location Type
- Waterfront
- 4 Bathrooms,
- 1 Half Bath
- Bathroom 1
- Bathroom 2
- Bathroom 3
- Bathroom 4
- Half Bathroom
- 5 Bedrooms, Sleeps 16
- Bedroom 1
- Bedroom 2
- Bedroom 3
- Bedroom 4
- Bedroom 5
- Outdoor Grill
- Casa Grande Guadalupe Bedroom arrangement:Renter supplies own linens and towels. BD#1: 1 King bed, 1 set of twin bunks BD#2: 2 sets of twin bunks BD#3: 1 King size bed BD#4: 1 Full size bed, 1 set of twin bunks BD#5: 1 Queen size bed, 1 set of twin bunks Charcoal Grill located at each house 2 Fully equipped kitchens (down to muffin tins and cake pans), two full size refrigerators, 2 electric stove/ovens and microwaves. Telephone, HD cable t.v. (70+ channels), Wireless Internet, Full size washer and dryer. Absolutely No smoking and No pets.


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Peter Cancro, CEO and founder of Jersey Mike's, was named Entrepreneur of the Year at the IFA Annual Convention in Las Vegas this week. Cancro bought his first sub shop in Point Pleasant, N.J., in 1975 at the age of 17 and expanded nationally in 1987. Today, Jersey Mike's operates more than 600 units in 33 states and Cancro is determined to expand the franchise nationally and overseas and reach 1,000 restaurants.
View Full Article in:QSRMagazine.com
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