An object of the invention is to provide a block copolymer hydrogenation product suitable for a sheet and a heat shrinkable film which are excellent in solvent resistance, rigidity, elongation and transparency, which is excellent in a balance of physical properties such as solvent resistance, natural shrinkability, low-temperature shrinkability, rigidity, transparency and low-temperature elongation, and a composition thereof. The invention relates to a block copolymer hydrogenation product having a weight ratio of a vinyl aromatic hydrocarbon and a conjugated diene of 55/45 to 95/5, a number average molecular weight measured by gel permeation chromatography (GPC) of 30,000 to 500,000 and a hydrogenation rate of 30% or more, wherein the vinyl aromatic hydrocarbon incorporated into the hydrogenation product has a block rate of 60 to 98% by weight, wherein relative to the weight of the total vinyl aromatic hydrocarbon polymer blocks, the ratio of vinyl aromatic hydrocarbon polymer blocks having a molecular weight of 50,000 or less is 80% by weight or more and the ratio of vinyl aromatic hydrocarbon polymer blocks having a molecular weight of 15,000 or less is from 10 to 80% by weight, and wherein at least one peak temperature of function tan δ in a dynamic viscoelasticity measurement of the hydrogenation product is present within the range of exceeding −80° C. to lower than −10° C.

A block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene, which has a relatively high vinyl aromatic hydrocarbon content, has been used for injection molding applications and extrusion molding applications for sheets, films and the like, utilizing characteristics such as transparency and impact resistance. In particular, a heat shrinkable film using the block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene has no problems of a residual monomer, a residual plasticizer and generation of hydrogen chloride in burning of a vinyl chloride resin which has hitherto been used, so that it has been utilized for food packaging, cap seals, labels and the like. As characteristics necessary for a heat shrinkable film, there are requirements such as natural shrinkability, low-temperature shrinkability, transparency, mechanical strength and aptitude for packaging machinery. In order to improve these characteristics and obtain a good balance of physical properties, various studies have been made.
Patent document 1 specified below discloses a composition of a vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid-based derivative copolymer having an aliphatic unsaturated carboxylic acid-based derivative content of 5 to 80% by weight and a Vicat softening point not exceeding 90° C., and a copolymer comprising blocks of a vinyl aromatic hydrocarbon and a conjugated diene, in order to obtain a composition excellent in mechanical characteristics, optical characteristics, stretching characteristics, crack resistance characteristics and the like.
Patent document 2 specified below discloses a heat shrinkable film which has a specific glass transition point (Tg) in segments of a block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene, in order to obtain a heat shrinkable film excellent in shrinkable characteristics and environmental destruction resistance.
Patent document 3 specified below discloses a heat shrinkable film which comprises a composition of a block copolymer comprising a vinyl aromatic hydrocarbon having a specific structure and a conjugated diene, in order to obtain a heat shrinkable film excellent in shrinkable characteristics and environmental destruction resistance.
Patent document 4 specified below discloses a low-temperature shrinkable film obtained by stretching a composition of a vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid-based derivative copolymer having a vinyl aromatic hydrocarbon content of 95 to 20% by weight and a Vicat softening point not exceeding 90° C. and a copolymer comprising blocks of a vinyl aromatic hydrocarbon and a conjugated diene, in order to obtain a shrinkable film excellent in low-temperature shrinkability, optical characteristics, crack resistance characteristics, dimensional stability and the like.
Patent document 5 specified below discloses a polystyrene-based heat shrinkable film comprising a composition of a block copolymer comprising a styrene-based hydrocarbon and a conjugated diene hydrocarbon and a styrene-based hydrocarbon-containing random copolymer having a specific Tg, in order to improve natural shrinkability at room temperature.
Patent document 6 specified below discloses a heat shrinkable hard film which comprises a composition of a vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid-based derivative copolymer having a Vicat softening point not exceeding 105° C. and a copolymer comprising blocks of a vinyl aromatic hydrocarbon and a conjugated diene, and has a specific heat shrinkage force, in order to obtain a transparent heat shrinkable film excellent in stability with time and impact resistance of the film.
Patent document 7 specified below discloses a composition of a copolymer comprising blocks of a vinyl aromatic hydrocarbon having a specific structure and molecular weight distribution and a conjugated diene and a vinyl aromatic hydrocarbon-(meth)acrylic ester copolymer resin, in order to obtain a composition balanced in transparency, rigidity and low-temperature surface impact properties.
Patent document 8 specified below discloses a transparent high-strength resin composition containing a block copolymer comprising a vinyl aromatic hydrocarbon block having a specific structure and a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene, and a copolymer of a vinyl aromatic hydrocarbon and a (meth)acrylic ester, in order to obtain a resin composition excellent in transparency and impact resistance.
Patent document 9 specified below discloses a multilayer low-temperature shrinkable film having at least one layer of a composition of a vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid-based derivative copolymer having a vinyl aromatic hydrocarbon content of 95 to 20% by weight and a Vicat softening point not exceeding 90° C. and a copolymer comprising blocks of a vinyl aromatic hydrocarbon and a conjugated diene, in order to obtain a shrinkable film excellent in low-temperature shrinkability, optical characteristics, crack resistance characteristics, dimensional stability and the like.
Patent document 10 specified below discloses a multilayer polystyrene-based heat shrinkable film which has at least three layers having both outer layers comprising a mixture of a styrene-butadiene-styrene type block copolymer having a specific butadiene unit content and styrene-butyl acrylate and an intermediate layer comprising a mixture of a styrene-butadiene-styrene type block copolymer having a specific butadiene unit content and styrene-butyl acrylate, in order to obtain a shrinkable film excellent in natural shrinkability, strength, surface characteristics, resiliency, low-temperature shrinkability and the like.
Patent document 11 specified below discloses a heat shrinkable polystyrene-based laminated film comprising as an intermediate layer a compound in which a block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene-based hydrocarbon is combined with a copolymer of a vinyl aromatic hydrocarbon and an aliphatic unsaturated carboxylic ester, and as front and back layers a mixed copolymer mainly composed of a block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene-based hydrocarbon, in order to obtain a heat shrinkable film excellent in any characteristic of natural shrinkability, resistance to heat fusion bonding, transparency and shrinkage finishing properties.
Patent document 12 specified below discloses a multilayer heat shrinkable polystyrene-based film having a specific degree of heat shrinkage, in which an intermediate layer is mainly composed of a styrene-(meth)acrylic ester copolymer having a specific Vicat softening point, and inner and outer layers are mainly composed of a styrene-conjugated diene block copolymer having a specific Vicat softening point, in order to obtain a heat shrinkable film excellent in heat shrinkability at low temperatures, shrinkage finishing properties and the degree of natural shrinkage, and undergoing no blocking with each other in a heated state.
Patent document 13 specified below discloses a (multilayer) heat shrinkable film having a layer mainly composed of a copolymer resin comprising a styrene-based monomer and a (meth)acrylic ester-based monomer, which is characterized by a specific molecular weight distribution and residual monomer amount, a block copolymer resin comprising styrene and a conjugated diene, and a high-impact polystyrene resin composition, in order to obtain a resin composition, a film and a multilayer film which are excellent in processing characteristics and storage stability, reduced in odor, and excellent in rigidity and impact resistance.
Patent document 14 specified below discloses a hydrogenated copolymer characterized by a specific weight ratio of a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer, an amount of polymer blocks of a vinyl aromatic hydrocarbon monomer, and absence of crystallization in a DSC chart within a specific temperature range, in order to obtain a hydrogenated copolymer rich in flexibility, excellent in impact resilience and scratch resistance, and good in handling properties (blocking resistance).
Patent document 15 specified below discloses a hydrogenated copolymer having a specific structure, in order to obtain a composition good in puncture impact value, strength, transparency and the like.
However, these block copolymers comprising a vinyl aromatic hydrocarbon and a conjugated diene, or the compositions comprising the block copolymer and a vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid-based derivative copolymer, or the hydrogenated copolymers comprising a vinyl aromatic hydrocarbon and a conjugated diene and the compositions thereof are insufficient in a balance of physical properties such as solvent resistance, natural shrinkability, low-temperature shrinkability, rigidity, transparency and impact resistance suitable for a sheet and a heat shrinkable film which are excellent in impact resistance, solvent resistance, rigidity and transparency. These documents do not disclose any methods for improving them, and the problems in the market have still been pointed out.
Patent Document 1: JP-A-59-221348
Patent Document 2: JP-A-60-224520
Patent Document 3: JP-A-60-224522
Patent Document 4: JP-A-61-25819
Patent Document 5: JP-A-4-52129
Patent Document 6: JP-A-5-104630
Patent Document 7: JP-A-6-220278
Patent Document 8: JP-A-7-216187
Patent Document 9: JP-A-61-41544
Patent Document 10: JP-A-2000-185373
Patent Document 11: JP-A-2000-6329
Patent Document 12: JP-A-2002-46231
Patent Document 13: JP-A-2002-201324
Patent Document 14: WO 03/035705
Patent Document 15: WO 03/066697

Hydrogenation product of block copolymer or sheet or film of the same


A number of npn and pnp bipolar transistors is formed in a single chip of silicon, so that some of the transistors have a greater frequency response than others. The higher frequency transistors have their emitters located closer to the collectors, by positioning a collector, or emitter, of a transistor in a recessed portion of the surface of the chip. The recess is formed in an accurate and controlled manner by locally oxidizing the silicon surface, and subsequently removing the oxide to leave the recess.

It is common to provide a large number of bipolar transistors on a silicon chip, but it is often desired that the bipolar transistors have different operating characteristics, some having a higher frequency performance and some having a higher reverse bias capability for example.
It has proved difficult selectively to adjust the characteristics of different transistors when they are manufactured on a single chip, and the present invention seeks to provide an improved semiconductor device.


Anisotropic films based on sulforderivatives of phenanthro-9xe2x80x2,10xe2x80x2:2,3-quinoxaline are disclosed. These compounds form liquid crystal and lyotropic liquid crystal systems that exhibit excellent optical properties with films that are significantly thinner than the current state of the art. The liquid crystal systems may be deposited on substrates or other film materials for use in a wide variety of commercial applications.

The present invention relates generally to the fields of organic chemistry and optically anisotropic coatings. More specifically, the present invention is related to methods of synthesizing heterocyclic sulphoderivative compounds and manufacturing optically anisotropic coatings based on these compounds.
Modem technological progress requires development of optical elements based on new materials with specific, controllable properties. In particular, the necessary element in modem visual display systems is an optically anisotropic film that is optimized for the optical characteristics of an individual display module.
Various polymer materials are known in the prior art for use in the production of optically anisotropic films. Films based on these polymers acquire optical anisotropy through uniaxial extension and coloring with organic dyes or iodine. Polyvinyl alcohol is one commonly used polymer in this application. However, the low thermal stability of films based on polyvinyl alcohol limits their applications. Polyvinyl alcohol based films are described in greater detail in Liquid Crystalsxe2x80x94Applications and Uses, B. Bahadur, ed., Vol. 1, World Scientific, Singapore, N.Y. Jul. 1990, p101. It is desirable to develop improved methods of forming anisotropic films with the characteristics of greater heat resistance and more convenient synthesis and film formation.
Organic dichroic dyes are a new class of materials currently gaining prominence in the manufacture of optically anisotropic films with desirable optical and working characteristics. Films based on these materials are formed by coating a liquid crystal (LC) aqueous solution of supramolecules formed by dye molecules on a substrate surface following water evaporation. The produced films are imbued with anisotropic properties either by preliminary mechanical ordering of the underlying substrate surface as described in U.S. Pat. No. 2,553,961 or by applying external mechanical, electromagnetic, or other orienting forces to the coating on a liquid crystal substrate material as described in pending PCT Application No. WO 94/28073.
Liquid crystal properties of dye solutions are known in the prior art. However, investigations into their application in this manner is a more recent development in the past several years. Recent studies into-these phenomena have been motivated largely by industrial applications in liquid crystal displays (LCDs) and glazing. Supramolecules form a lyotropic liquid crystal (LLC). Substantial ordering of dye molecules in columns allows use of these mesophases to create oriented, strongly dichroic films. Dye molecules that form supramolecular liquid crystal mesophases are special. They contain functional groups located at a molecule periphery that determine the water solubility of the dye. Organic dye mesophases are characterized by specific structures, phase diagrams, optical properties and dissolving capabilities as described in greater detail in Jean-Marie Lehn, Supramolecular Chemistry, N.-Y., 1998.
Anisotropic films characterized by high optical anisotropy may be formed from LLC systems based on dichroic dyes. Such films exhibit both the properties of E-type polarizers, due to light absorption by supramolecular complexes, and the properties of retarders. Retarders are films with phase-retarding properties in those spectral regions where absorption is lacking. Phase-retarding properties of the films are determined by their double refraction properties: different refraction indices in the direction of LC solution deposition and the direction orthogonal to the deposition direction. If high-strength dyes are used for the film formation, the films are also characterized by high thermal and photo stability.
Extensive investigations aimed at developing new methods of creating dye-based films through manipulation of deposition conditions are currently underway. Of additional interest is the development of new compositions of lyotropic liquid crystals (LLC). New LLC compositions may be developed through the introduction of modifying, stabilizing, surfactant and other additives to known dyes, thus improving film characteristics. More detailed discussions of these processes are provided in Russian patent No. RU 2047643 and published PCT patent application No. WO 99/31535.
The requirements for producing anisotropic film with improved selectivity in different wavelength ranges are increasing. Films with different absorbance maxima located in a wide spectral range from the infrared to the ultraviolet are needed in a wide range of technology areas. The requirements have led to development of an expanding assortment of compounds capable of forming LLC phases and films with required properties.
Much recent research attention has been directed to the materials used in the manufacturing of double refraction films (retarders), which are used in LC displays and telecommunications applications, such as, for example, those described by P. Yeh, Optical Waves in Layered Media, New York: John Wiley andSons, Inc, 1998 and P. Yeh, and C. Gu, Optics in Liquid Crystal Displays, New York: John Wiley andSons, Inc., 1999. It has been found that ultra-thin double refraction films may be produced using known technologies to form optically anisotropic films composed of organic dye LLC systems. Recent reports on manufacturing of thin crystalline optically anisotropic films based on disulfoacids of the red dye Vat Red 14 (Lazarev, P. and Paukshto, M., xe2x80x9cThin Crystal Film Retarders,xe2x80x9d 2000, Proceeding of the 7th International Display Workshops, Materials and Components, Kobe, Japan, p. 1159-1160), have identified the mixture of naphthalenetetracarboxylic acid dibenzimidazole cis- and trans-isomers of the following structures:
The prior art technology permits control of the direction of the crystallographic axis of a film during coating and crystallization on a substrate. Films were formed on glass plates measuring approximately 5 cm by 7.5 cm. The deposited films were uniform in composition and had high a crystal ordering with a dichroic ratio, Kd, of approximately 28. These films may be used either as polarizers or as retarders.
Oriented red dye based films typically exhibit high anisotropy characterized by a large difference in the refraction indices: xcex94n=noxe2x88x92ne and falls in the range of approximately 0.6 to 0.8 at wavelengths in the range of approximately xcex=550 to 700 nm. However, their application is limited, because the films work as retarders only in the green spectral region where the dye does not absorb.
Thin, double refraction films based on sodium chromoglycate (DSCG) with the following structure may also be prepared to be transparent in the visible region:
The anisotropy of the oriented film formed from this compound is not very highxe2x80x94the difference in the refraction indices is in the range of approximately 0.1 to 0.13. However, the thickness of films based on DSCG may be varied in a wide range, thus allowing preparation of films with a desired phase-retarding effect despite somewhat low anisotropy. More details on these films are provided by Lazarev, P. and Paukshto, M., xe2x80x9cThin Crystal Film Retardersxe2x80x9d (2000), Proceeding of the 7th International Display Workshops, Materials and Components, Kobe, Japan, p. 1159-1160. The main disadvantage of these films lies in their dynamic instability which leads to gradual recrystallization and anisotropy degradation.
Various blends based on water-soluble organic dyes used for forming anisotropic films according to described above technology are known in the prior art. Examples are described in published PCT patent applications No. WO 94/28073 and No. WO 99/31535. However, the main drawback of these materials is their high absorbance in the visible spectral region which limits their application for forming transparent double refraction films.
It is an object of the present invention to provide a series of new chemical compounds, namely phenanthro-9xe2x80x2,10xe2x80x2:2,3-quinoxaline sulfoderivatives capable of forming stable lyotropic liquid crystals and producing anisotropic, at least partially crystalline films based on these compounds. The present invention is further directed to expansion of the assortment of compounds that are either not absorbing or only weakly absorbing in the visible spectral region and that are capable of forming a LLC phase with enhanced stability for producing anisotropic, at least, partially crystalline films with high optical characteristics at simultaneous elimination of mentioned above drawbacks.
One embodiment of the present invention provides a method of producing slightly-colored films that may be used both for polarizing and for double-refraction. Phenanthro-9xe2x80x2,10xe2x80x2:2,3-quinoxaline and its derivatives do not have as developed a xcfx80-electron conjugation system as do other known dichroic dyes, and they therefore absorb in the UV and near visible spectral regions. Thus, the molecule of unsubstituted phenanthro-9xe2x80x2,10xe2x80x2:2,3-quinoxaline has an absorption maximum at xcex≈390 nm.
Another embodiment of the present invention provides LLC phases with enhanced stability over broad concentration, temperature and pH ranges. These LLC phases are formed from organic compounds that ease the film formation process, and use standard equipment for coating thereby facilitating production of films with reproducible parameters.
Yet another aspect of the present invention provides organic compound mixtures in which the optimal hydrophilic-hydrophobic balance is realized. This in turn affects the size and shape of the resultant supramolecular complexes and the molecular ordering rate in the complex itself, thus allowing attainment of the required solubility of the considered compounds. Proper solubility values promote high stability of the produced LLC phases. Reproducibility of the formed film parameters is enhanced in this manner, and thereby the film formation process is eased by reducing the requirements for choosing and controlling technological conditions at different stages of the film formation. Furthermore, the optical performance of the produced films is improved by increased uniformity of alignment on a substrate of the planes of phenanthro-9xe2x80x2,10xe2x80x2:2,3-quinoxaline sulfoderivative molecules. In addition, the dipole moments of electronic transitions with respect to direction lie in these planes and are determined by external orienting stresses.

Anisotropic films based on sulfoderivatives of phenanthro-9xe2x80x2, 10xe2x80x2:2,3-quinoxaline and lyotropic liquid crystal systems and method for making


An accessory for coupling to an oscillating power tool includes a working end portion and an attachment portion. The working end portion defines and extends along a working axis. The attachment portion is coupled to the working end portion and includes a top wall, a bottom wall spaced apart from the top wall, and a peripheral wall extending from the top wall to the bottom wall at least partially around the top wall to form at least a portion of a polygonal shape. A generally U-shaped opening is defined in the top wall, extends along an attachment axis at an angle to the working axis, has a central portion at a center of the attachment portion, and is open to a gap in the peripheral wall. A plurality of radial openings is defined in the top wall and arranged between the U-shaped opening and the peripheral wall. The peripheral wall, the U-shaped opening, and the plurality of radial openings are configured to couple the attachment portion to at least two different configurations of accessory attachment mechanisms on different oscillating power tools.

Oscillating power tools generally have a motor, an output shaft, and a transmission that connects the motor to the output shaft and converts rotary motion of the motor to oscillating motion of the output shaft. The output shaft is coupled to an accessory attachment mechanism that is used to removably attach various types of accessories, such as cutting tools, saw blades, and sanding tools, to the output shaft. Different brands of oscillating power tools tend to have different, often proprietary, accessory attachment mechanisms. It is desirable to have oscillating accessories with an attachment portion that can be attached to a multitude of different brands of oscillating power tools.

This patent is subject to a terminal disclaimer.


The invention is directed to a transport incubator for accommodating prematures and newborns in a compartment wherein the temperature is controlled by means of an energy store which is in thermal contact with the compartment. The transport incubator is improved in that the energy store is made as small and as light as possible and does not have to be supplied with energy continuously in the operating condition. In addition, the transport incubator can be produced at low cost while utilizing environmentally friendly materials. The energy store is configured as an adsorption vessel containing an adsorption material. For generating the heat to be supplied to the infant compartment, the adsorption vessel can be connected to a supply vessel which contains a fluid which is adsorbing on the adsorbing vessel while giving off adsorption heat.

Published British patent application 2,203,946 discloses a transport incubator wherein the energy is stored in a latent heat store containing molten wax. The heat released as the wax becomes rigid brings liquid from low-boiling fluorinated hydrocarbons to boiling which, in turn, releases the heat to the air in the incubator interior in a heat exchanger mounted in the incubator interior space.
Disadvantages associated with this known incubator are: the high weight and large constructive volume of the latent heat store and the heat exchanger as well as the necessity of using environmentally unfriendly fluorinated hydrocarbons. Furthermore, it is a disadvantage that the latent heat store must be continuously heated if it is to be available for use on demand and requires a complex heat insulation.

Transport incubator having an integrated energy store


A method for determining information on an integrity of signal processing components within a signal path includes adding an alive signal to a signal at a first position within the signal path and detecting an added alive signal corresponding to the alive signal at a second position within the signal path. Further, the method includes determining the information on the integrity based on the detected signal.

Monitoring of signal processing components within signal paths is often desirable in order to conclude on an integrity of the signal processing components within the signal path or a specific part thereof. Monitoring of signal processing components within signal paths may allow to conclude, whether the signal processing components operate as desired and whether a signal output by the signal path can be relied on. One particular interest may be to be able to identify, whether a signal processing component still operates or whether it is eventually stuck, providing one and the same output independently from varying signals input into the signal processing component in question. This may, for example, be of interest if a system relies on sensor signals generated by sensors and subsequently processed within the signal path in order to trigger safety measures. For example, in automobiles, a wheel speed sensor device provides information on a rotational velocity of a wheel, which is received by an electronic control unit (ECU) in order to allow to conclude on safe driving conditions of the vehicle. In other examples, linear hall sensors provide an output signal proportional to the strength of a magnetic field at the sensor position or angular sensors provide an output indicating an angle of an observed object with respect to a reference. In typical sensor devices, the signal provided by the sensor is subsequently processed by some signal processing components of a signal path within the sensor device before the information on the observed quantity (e.g. a rotational speed or an angle) is transmitted to the ECU to be processed further. In the event of an error within the signal path within the sensor device or a part of the signal path constituted by the interface between the sensor device and the ECU, wrong information may be received and the safety of the passengers of the car may be at risk. Hence, there is a desire to determine information on the integrity of signal processing components within the signal path.

Method for determining information on an integrity of signal processing components within a signal path, signal processing circuit and electric control unit


In industrial production of xcfx89-hydroxyaliphatic acid being an important intermediate for large cyclic lactone-based perfumes, using dicarboxylate ester which is inexpensive and readily obtainable, a method, with high yield and improved selectively, for making a 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide and an alkaline metal salt thereof, an ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid as a novel compound and a derivative thereof, and a method for making the same are provided.

The present invention relates to methods for making 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide and derivatives thereof, novel esters of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid and derivatives thereof, which are useful as a variety of synthetic raw materials and intermediates, and are prepared as intermediates in the production step of xcfx89-hydroxyaliphatic acid being important intermediates of large cyclic lactone-based perfumes in the perfume industry.
The present invention also relates to a method for separating and purifying an alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide and derivatives thereof, and unreacted dicarboxylic ester, in the production of xcfx89-hydroxyaliphatic acid, being an important intermediate of the large cyclic lactone-based perfume.
Furthermore, the present invention relates to a method for separating and recovering xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid and salts thereof, dicarboxylic acid and salts thereof, and xcex1,xcfx89-dihydroxy-xcex4,(xcfx89-3)-alkanedione, in the production of xcfx89-hydroxyaliphatic acid, being an important intermediate of the large cyclic lactone-based perfume.
Alkaline metal salts of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5):
(wherein n is an integer of 7 to 13, and M indicates an alkaline metal), and xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acids represented by the general formula (10):
(wherein n is an integer of 7 to 13) are useful as a variety of synthetic raw materials and intermediates and are particularly important intermediates for macro cyclic lactone-based perfumes in the perfume industry.
2-(xcfx89-Alkoxycarbonylalkanoyl)-4-butanolide is useful as a variety of synthetic raw materials and intermediates and is effectively used as an intermediate in the production of the above-mentioned xcfx89-hydroxyaliphatic acid, which is a particularly important intermediate for large cyclic lactone-based perfumes, such as cyclopentadecanolide and cyclohexadecanolide, in the perfume industry.
Among conventional synthesizing processes for xcfx89-hydroxyaliphatic acid, a method using xcfx89-cyanoundecanoate ester and xcex3-butyrolactone as starting materials is disclosed in Japanese Patent Application Laid-Open No. Hei 5-86013.
In this method, however, raw materials are generally difficult to prepare, and relatively expensive methyl 11-cyanoundecanoate is used as a raw material. Furthermore, ammonia formed in the final carboxylation step of the nitrile group at the xcfx89-position requires a complicated procedure and adversely affects the scent of the final product; hence this method is still industrially unsatisfactory.
Other synthesizing methods for xcfx89-hydroxyaliphatic acid using xcex1-(xcfx89-cyanoalkanoyl)-xcex3-butyrolactone as a starting material are disclosed in Japanese Patent Application Laid-Open Nos. 3-11036 and 5-86013. As an advantage of these methods, the intermediate, xcfx89-hydroxyketonitrile, which is prepared by hydrolysis and decarboxylation of xcex1-(xcfx89-cyanoalkanoyl)-xcex3-butyrolactone in the presence of an alkaline metal hydroxide, is oil-soluble; hence a large amount of water used and alkaline metal carbonate formed as a byproduct are easily separable.
Starting materials for xcex1-(xcfx89-cyanoalkanoyl)-xcex3-butyrolactone, however, are difficult to obtain. When relatively expensive a xcfx89-cyanoundecanoate ester is used as a raw material or when the nitrile group at the xcfx89-position is finally carboxylated, ammonia forms. Thus, a complicated process is required and ammonia adversely affects the scent of the final product; hence, this method is still industrially unsatisfactory.
PCT Patent Application Laid-Open No. WO97-06156 discloses a method using a significantly readily obtainable and inexpensive dicarboxylate ester represented by the general formula ROOC(CH2)nCOOR, wherein n is an integer of 7 to 13 and R is an alkyl group, and xcex3-butyrolactone as starting materials. In this method, an excess of dicarboxylate ester is mixed with xcex3-butyrolactone in the presence of a basic condensing agent at room temperature and is heated and stirred under normal pressure while removing methanol formed in the reaction to prepare 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide. This method is also excellent.
The selectivity and yield, however, is still unsatisfactory. Furthermore, a large excess of aqueous alkaline solution must be added during hydrolysis and decarboxylation of the intermediate, 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide. Thus, a disadvantage of the method is removal of the large amount of water by distillation before the subsequent Wolff-Kishner reduction step.
In this method, an excess of dicarboxylate ester which is two times or more the fed amount of xcex3-butyrolactone is used to increase the selectivity on the basis of the dicarboxylate ester raw material represented by the above-mentioned general formula, and unreacted dicarboxylate ester is recovered from the reaction mixture to reuse in the next reaction.
In the separation of the unreacted dicarboxylate ester and 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide after the reaction, after acidification of the condensation solution, extraction with a solvent such as ethyl acetate, washing, and recovery of the solvent, the reaction mixture is subjected to simple distillation so that the unreacted dicarboxylate ester in the distilled section is separated from the condensation product, 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide, in the distillation residue.
This method, however, requires a complicated process including many steps, such as extraction and simple distillation, and has a problem of decomposition of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide in the distillation. Furthermore, in the subsequent alkaline hydrolysis, decarboxylation, and Wolff-Kishner reduction, the method requires a complicated step in which alkaline is readded to 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide obtained by the acidification.
Japanese Patent Application Laid-Open No. Hei 4-134047 discloses a method for separating three types of mixtures, that is, xcfx89-hydroxyaliphatic acid or its ester, xcex1-xcfx89-diol, and dicarboxylic acid or its ester, but does not suggest a compound having a carbonyl group in the molecule.
The present inventors have intensively researched solutions to the problems in the method disclosed in the PCT Patent Application Laid-Open No. WO97-06156, that is, the use of a large amount of aqueous alkaline solution and a large amount of heat, and the laborious steps for separating water, and have discovered that these problems may be solved by using a novel compound, an ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid, as an intermediate in the production of xcfx89-hydroxyaliphatic acid, and have thereby completed the present invention.
It is an object of the present invention to provide methods, with high yield, improved selectively, and industrial advantages, for making 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide and its derivatives, such as an alkaline metal salt, using readily obtainable and inexpensive dicarboxylate ester.
The present inventors have also discovered a method for effectively separating the condensation products, alkaline metal of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide and its derivative from the unreacted ester by extraction using an inactive solvent with water or an aqueous alkaline solution or by solid-liquid separation using an inactive solvent in the separation of the reaction product and the unreacted dicarboxylate ester from the condensation solution which is prepared from xcex3-butyrolactone and an excess of dicarboxylate ester in the presence of a base, and have completed the present invention.
It is another object of the present invention to provide a novel compound, ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid, which is advantageously used as an intermediate in the industrial production of xcfx89-hydroxyaliphatic acid being an important intermediate for a large cyclic lactone-based perfume, and to provide a method for producing with high yield the ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid and derivatives thereof.
It is a further object of the present invention to provide a method for separating and recovering highly selectively xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid and salts thereof, dicarboxylic acid and salts thereof as byproducts, and xcex1,xcfx89-dihydroxy-xcex4,(xcfx89-3)-alkanedione, in the industrial production of xcfx89-hydroxyaliphatic acid, being an important intermediate for a large cyclic lactone-based perfume.
The present invention, for achieving the above-mentioned objects, provides a method for making 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (2) and an alkaline metal salt of the 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (3) comprising condensation reaction of xcex3-butyrolactone with a dicarboxylate ester represented by the general formula (1):
ROOC(CH2)nCOORxe2x80x83xe2x80x83(1)
wherein n is an integer of 7 to 13 and R is an alkyl group;
wherein n is an integer of 7 to 13 and R is an alkyl group;
wherein n is an integer of 7 to 13, R is an alkyl group, and M is an alkaline metal,
wherein the dicarboxylate ester represented by the general formula (1) is heated and stirred, and xcex3-butyrolactone and an alkaline metal alcoholate are added to perform the condensation reaction.
In preferred embodiments, R in the general formula (1) is an alkyl group having 1 to 6 carbon atoms, the condensation reaction is performed while removing alcohol by distillation under reduced pressure, and the condensation reaction is performed by varying the reduced pressure by two stages or more.
The alkaline metal salt of the 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide produced by the foregoing step and represented by the general formula (3) and the unreacted dicarboxylate ester are separated from each other and purified. A method in accordance with the present invention for separating and purifying an alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (3) and unreacted dicarboxylate ester from a condensation solution of xcex3-butyrolactone and the dicarboxylate ester represented by the general formula (1) comprises solid-liquid separation using a solvent unreactive to the alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide.
Another method in accordance with the present invention for separating and purifying an alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (3), a derivative thereof being an alkaline metal salt of xcfx89-hydroxy-(xcfx89-2)-carboxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (4), an alkaline metal salt of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5), an alkaline metal salt of xcfx89-hydroxy-(xcfx89-2)-carboxy-(xcfx89-3)-ketoaliphatic acid ester represented by the general formula (6), and an unreacted dicarboxylate ester from a condensation solution of xcex3-butyrolactone and a dicarboxylate ester represented by the above-mentioned general formula (1) comprises extraction using water or an aqueous alkaline solution:
wherein n is an integer of 7 to 13 and M is an alkaline metal;
wherein n is an integer of 7 to 13 and M is an alkaline metal; and
wherein n is an integer of 7 to 13, R is an alkyl group, and M is an alkaline metal. The compounds represented by the general formulae (3), (4), (5) and (6) may be extracted using an inactive solvent with water or an aqueous alkaline solution.
Also, in the present invention, an ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (7) is produced:
wherein n is an integer of 7 to 13 and R is an alkyl group.
A method in accordance with the present invention for producing an ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid comprises selective hydrolysis and decarboxylation of the xcex3-butyrolactone portion of an alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (3):
wherein n is an integer of 7 to 13, R is an alkyl group, and M is an alkaline metal. In the present invention, the ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid is obtainable by hydrolysis and decarboxylation of an alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (3) in the presence of a weak acid:
wherein n is an integer of 7 to 13, R is an alkyl group, and M is an alkaline metal.
The ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (7) obtained in the present invention is a novel compound:
wherein n is 10 or 11, and R is an alkyl group. R in the general formula (7) is preferably an alkyl group having 1 to 6 carbon atoms.
In the present invention, xcex1,xcfx89-dihydroxy-xcex4,(xcfx89-3)-alkanedione represented by the general formula (9) is recovered by adding a required amount of alkaline to a mixture containing the compounds represented by the general formulae (3), (4), (5) and (6) separated from the condensation solution for hydrolysis and decarboxylation, and then by extracting the xcex1,xcfx89-dihydroxy-xcex4,(xcfx89-3)-alkanedione represented by the general formula (9) with an organic solvent from a mixture containing three compounds, an alkaline metal salt of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5), an alkaline metal salt of a long-chain dicarboxylic acid represented by the general formula (8), and the xcex1,xcfx89-dihydroxy-xcex4,(xcfx89-3)-alkanedione represented by the general formula (9), or by selectively crystallizing the xcex1,xcfx89-dihydroxy-xcex4,(xcfx89-3)-alkanedione represented by the general formula (9) from the mixture:
wherein n is an integer of 7 to 13 and M is an alkaline metal;
wherein n is an integer of 7 to 13 and M is an alkaline metal;
wherein n is an integer of 7 to 13.
In the present invention, the alkaline metal salt of the xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5) is selectively crystallized from the mixture containing the alkaline metal salt of the xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5) and the alkaline metal salt of long-chain dicarboxylic acid represented by the general formula (8), and these are separated into a cake and a filtrate by solid-liquid separation to separate and recover the alkaline metal salt of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5) and the alkaline metal salt of long-chain dicarboxylic acid represented by the general formula (8):
wherein n is an integer of 7 to 13 and M is an alkaline metal;
wherein n is an integer of 7 to 13 and M is an alkaline metal.
Adjusting the pH value of the mixture containing the xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5) to 5 to 7 with a mineral acid permits separation and recovery of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (10) and the alkaline metal salt of long-chain dicarboxylic acid represented by the general formula (8):
wherein n is an integer up to 13.
In addition, adjusting the pH value of the filtrate containing the alkaline metal salt of long-chain dicarboxylic acid represented by the general formula (8) to 3 to 5 with a mineral acid permits separation and recovery of a long-chain dicarboxylic acid represented by the general formula (11):
wherein n is an integer up to 13.
The target of the present invention is also achieved by a combination of these methods.
In the present invention, xcex3-butyrolactone is first allowed to react by condensation with a dicarboxylate ester represented by the general formula (1) to form 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (2) or an alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (3):
ROOC(CH2)nCOORxe2x80x83xe2x80x83(1)
wherein n is an integer of 7 to 13 and R is an alkyl group;
wherein n is an integer of 7 to 13 and R is an alkyl group;
wherein n is an integer of 7 to 13, R is an alkyl group, and M is an alkaline metal.
The condensation reaction of dicarboxylate ester and xcex3-butyrolactone in the presence of a basic condensation agent is complicated; hence, it is presumed that the selectivity and yield greatly depend on the reaction process, such as the method for feeding raw materials and the method for removing methanol formed. As a result of intensive research by the present inventors on the point aimed at the reaction mechanism regarding the formation of alcohol, it was discovered that 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide and its alkaline metal salt are obtained with satisfactory selectivity and yield, as will be described below.
In the first stage, xcex3-butyrolactone and an alkaline metal alcoholate are added as droplets to a hot dicarboxylate ester while stirring under reduced pressure which is sufficient to evaporate a formed alcohol to allow the reaction to proceed while distilling the alcohol from the system. In the second stage, heating with stirring is continued under a further reduced pressure to allow the reaction to proceed while distilling the alcohol from the system. It was discovered that 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide and its alkaline metal salt are obtained with satisfactory selectivity and yield by such stages.
Accordingly, a characteristic feature of the present invention is addition of xcex3-butyrolactone and an alkaline metal alcoholate to a hot dicarboxylate ester while stirring to allow condensation reaction. In this case, the xcex3-butyrolactone and the alkaline metal alcoholate may be added as a mixture or independently.
It is preferable that the reaction be performed while distilling alcohol from the system. In addition, it is preferable in view of further satisfactory selectivity and yield that the reaction be continued while distilling the residual alcohol from the system under further reduced pressure.
R in the dicarboxylate ester represented by dicarboxylate ester represented by the general formula (1), ROOC(CH2)nCOOR wherein n is an integer of 7 to 13 and R is an alkyl group, is preferably an alkyl group having 1 to 6 carbon atoms, in view of convenience of use.
Examples of R include methyl, ethyl, propyl, butyl, isobutyl, pentyl, and hexyl groups. Among these, methyl is preferable.
Examples of preferable dicarboxylate esters represented by the general formula (1) include dimethyl 1,12-dodecanedicarboxylate and dimethyl 1,13-tridecanedicarboxylate (dimethyl brassylate).
In the present invention, the condensation reaction proceeds in the presence of an alkaline metal alcoholate. Preferable alkaline metal alcoholates are represented by the general formula Rxe2x80x2OM wherein Rxe2x80x2 is an alkyl group having 1 to 4 carbon atoms and M is an alkaline metal.
Examples of the alkaline metal alcoholates include sodium methylate, sodium ethylate, sodium propylate, sodium butylate, potassium methylate, potassium ethylate, potassium propylate, and potassium butylate.
Although the amount of the alkaline metal alcoholate used in the present invention is not limited, the amount is preferably 0.1 to 5 equivalents and more preferably 0.5 to 3 equivalents with respect to xcex3-butyrolactone. When the amount of alkaline metal alcoholate used is small, the yield will decrease. When the amount used is higher than the predetermined level, the selectivity may decrease.
It is preferable in the present invention that the dicarboxylate ester represented by the general formula (1) be used in an excess amount on a molar basis to xcex3-butyrolactone, and particularly 2 times or more by mole. The use of the dicarboxylate ester in an amount of 2 times or more by mole results in a particular improvement in selectivity.
If unreacted dicarboxylate ester is present when the present invention is executed, it is preferable in view of effective reaction that the unreacted dicarboxylate ester be recovered from the reaction mixture to recycle it to the condensation reaction. In the present invention, the unreacted dicarboxylate ester can be readily recovered from the reaction mixture by extraction with water or an aqueous alkaline solution or by solid-liquid separation; hence a combination of the excessive use and recycling use of the dicarboxylate ester permits more effective reaction.
The condensation reaction in the present invention is preferably performed under reduced pressure to effectively remove alcohol. A preferable reduced pressure is in a range of 50 to 760 mmHg, and more preferably 100 to 600 mmHg. The pressure may be diminished by two or more stages. For example, the pressure during the reaction is diminished to approximately 500 to 700 mmHg which is sufficient for distillation of alcohol in the first stage, and then further diminished to approximately 50 to 300 mmHg in the second stage.
Although the heating temperature in the condensation reaction is not limited, a preferable condition is set in relation to the reduced pressure. A preferable temperature lies in a range of 30 to 200xc2x0 C., and more preferably 50 to 150xc2x0 C.
Although no solvent is required in the present invention, a solvent used in general ester condensation may be used in this reaction as long as it does not decrease the activity of the alkaline metal alcoholate.
The reaction in accordance with the present invention may be performed by a batch system, a continuous system, or a multistage system.
The alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide obtained in the present invention can be readily converted with high yield into xcfx89-hydroxyaliphatic acid, which is an important intermediate for a large cyclic lactone-based perfume, as will be described later.
The product of the condensation reaction of the dicarboxylate ester represented by the general formula (1) with xcex3-butyrolactone is a xcex2-ketoester type compound which is generally present as an alkaline salt represented by the general formula (3) in the reaction solution:
wherein n is an integer of 7 to 13, R is an alkyl group, and M is an alkaline metal. It was discovered that the alkaline metal salt represented by the general formula (3) has significantly lower solubility in an organic solvent such as n-hexane. The salt is readily soluble in an aqueous alkaline solution. The xcex3-butyrolactone portion and the ester terminal are rapidly hydrolyzed to form an alkaline metal salt of dicarboxylic acid represented by the general formula (4), and the salt is partly decarboxylated to form an alkaline metal salt represented by the general formula (5) when a certain amount of alkaline metal hydroxide is added:
wherein n is an integer of 7 to 13 and M is an alkaline metal;
In contrast, the dicarboxylate ester represented by the general formula (1) used in excess in the condensation reaction of the present invention remains without reaction in the solution. The compound is significantly soluble in an organic solvent such as n-hexane.
Accordingly, the present inventors have intensively studied solubility of the alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide in organic solvents and water, have discovered a purification method for independently recovering the alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide with its derivative, and the unreacted dicarboxylate ester with ease and high yield, and have completed the present invention.
The method in the present invention separates the alkaline metal salt represented by the general formula (3) and the unreacted dicarboxylate ester represented by the general formula (1) by solid-liquid separation such as filtration (hereinafter referred to as a solid-liquid separation method).
An organic solvent, which can dissolve the unreacted dicarboxylate ester and is unreactive to the alkali and the alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide, is added to the condensation solution to sufficiently dissolve the unreacted dicarboxylate ester and to form a salt suspension. The suspension is separated into a liquid component and a solid component by any known method such as filtration or centrifugal separation. The solid component is thoroughly washed with the solvent to remove the unreacted dicarboxylate ester. The liquid component and the washings are concentrated together and recycled to the next condensation reaction.
On the other hand, the solid component can be used without further treatment or after converting it into 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide by acidification. It can also be used for hydrolysis and decarboxylation in an aqueous alkaline solution.
The present invention also relates to a method for extracting the salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide with water and the unreacted dicarboxylate ester with an organic solvent for separation thereof (hereinafter referred to as an alkaline extraction method).
Water or an aqueous alkaline solution is added to the condensation solution to dissolve the alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide, the unreacted dicarboxylate ester is recovered into an organic layer from the mixture by a separative operation, and then washed with water to recycle it for the next condensation reaction.
On the other hand, the aqueous layer contains the alkaline metal salt represented by the general formula (3), the compound represented by the general formula (6), the alkaline metal salt represented by the general formula (4) in the case of addition of a given amount of alkaline metal hydroxide, and the alkaline metal slat represented by the general formula (5) formed by partial decarboxylation in the case of addition of a given amount of alkaline metal hydroxide. This phenomenon was clarified by determining the composition of the crystal extract after acidification of the aqueous layer obtained by the above-mentioned operation.
It was found that the crystal extract primarily contains the compound represented by the general formula (2), long-chain dicarboxylic acid, 2-(xcfx89-carboxyundecanoyl)-4-butanolide represented by the general formula (12), and xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (10):
wherein n is an integer of 7 to 13;
wherein n is an integer of 7 to 13.
It is presumed in the present invention that the crystal extract contains the 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (2) and the 2-(xcfx89-carboxyundecanoyl)-4-butanolide represented by the general formula (12) for the following reason. When the alkaline metal salt represented by the general formula (3) is dissolved in an aqueous alkaline solution, the xcex3-butyrolactone portion is rapidly hydrolyzed to form the compound represented by the general formula (6).
Acidification of the extract forms a compound represented by the general formula (13):
wherein n is an integer of 7 to 13. The product is rapidly dehydrated to form a lactone ring and thus the compound represented by the general formula (2). When a given amount of alkaline is added, the terminal ester group in the general formula (6) is also presumably hydrolyzed to form the alkaline metal salt of dicarboxylic acid represented by the general formula (4).
Acidification of the compound represented by the general formula (4) forms a dicarboxylic acid represented by the general formula (14):
wherein n is an integer of 7 to 13. The product is rapidly dehydrated to form a lactone ring and thus 2-(xcfx89-carboxyundecanoyl)-4-butanolide represented by the general formula (12).
The formation of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid is caused by decarboxylation of the xcex2-ketoacid occurring when the amount of the alkaline metal salt is in excess with respect to hydrolysis.
The resulting aqueous layer can be used for the subsequent hydrolysis and decarboxylation.
Solvents used in the present invention are not limited as long as they are unreactive to the alkali and the salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide. Examples of such solvents include organic solvents, such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, diethylether, and isopropyl ether.
Although the alkaline extraction method can be achieved without using a solvent, the use of a solvent is preferable. The amount of the solvent is preferably 0 to 10 times by weight, and more preferably 0.5 to 5 times by weight with respect to the condensation solution. The temperature of dissolution into the solvent and the temperature of the alkaline extraction are not limited within a range not causing solidification of the organic solvent, and lie in a range of generally 0xc2x0 C. to 100xc2x0 C., and preferably 20xc2x0 C. to 50xc2x0 C.
The alkaline compounds used in the alkaline extraction in the present invention are not limited as long as they can extract 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide and its alkaline metal salt and derivative. Examples of usable alkaline compounds include alkaline metal hydroxide, such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline metal carbonates, such as sodium carbonate and potassium carbonate; and alkaline earth metal hydroxides, such as barium hydroxide.
The concentration of the aqueous alkaline solution is not limited, and lies in a range of preferably 0.5 to 50%, and more preferably 1 to 15%. In addition, the amount is not limited, and lies in a range of preferably 0.1 to 10 times by weight and more preferably 0.5 to 2 times by weight with respect to the condensation solution. The purification in accordance with the present invention can be performed by either a batch system or a continuous system.
Furthermore, the present inventors have discovered that heating of the alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide obtained in the above-described operation with a weak acid such as phosphoric acid forms the ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (7) with high yield:
wherein n is an integer of 7 to 13 and R is an alkyl group. The present inventors have also discovered that the compound represented by the general formula (7) is oil-soluble and thus can be readily separable from the reaction solution, and have completed the present invention. The ester of xcfx89-hydroxyketoaliphatic acid is useful as an intermediate in the production of xcfx89-hydroxyaliphatic acid which is an important intermediate for a macro cyclic lactone-based perfume in the perfume industry.
Among the esters of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (7), novel compounds are esters of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid wherein n is 10 or 11.
In the present invention, selective hydrolysis and decarboxylation of the xcex3-butyrolactone portion in the alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide obtained in the above-mentioned operation forms the ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (7):
wherein n is an integer of 7 to 13 and R is an alkyl group. In addition, in the present invention, hydrolysis and decarboxylation of the alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (3) by heating with a weak acid forms the ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (7).
Types of the weak acids used in hydrolysis and decarboxylation in the present invention are not limited. Examples of weak acids include phosphoric acid, pyrophosphoric acid, and carbonic acid. Sodium dihydrogen-phosphate and the like are also usable. The amount of the weak acid used is not limited, and lies in a range of 0.5 to 3 equivalents, and more preferably 0.5 to 1 equivalents with respect to 1 mole of alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide.
The amount of water used in the reaction in the present invention is not limited, and preferably lies in a range of 2 to 20 times with respect to the alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide.
A water-soluble organic solvent may or may not be used in the hydrolysis and decarboxylation in the present invention. Examples of the water-soluble organic solvents include methanol, ethanol, diethylene glycol, triethylene glycol, dioxane, tetrahydrofuran, and 1,2-dimethoxyethane. The water-soluble organic solvent is preferably used in an amount of 0.05 to 3 parts by weight to 1 parts by weight of water.
The reaction in accordance with the present invention requires heating. The heating is performed in the presence of a weak acid such as phosphoric acid in the present invention. The heating temperature preferably lies in a range of 80 to 110xc2x0 C. The reaction time is appropriately determined depending on the reaction temperature and fed raw materials, and generally lies in a range of 1 to 20 hours. The reaction can be performed by a batch system or a continuous system. Isolation and purification of the reaction products can be achieved by any conventional unit operations including liquid separation, extraction, washing and recrystallization.
The ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (7) obtained in the present invention can be easily converted into xcfx89-hydroxy-aliphatic acid as an important intermediate for a macro cyclic lactone-based perfume with high yield and industrial advantages.
The xe2x80x94COOR group of the ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid is hydrolyzed to form the alkaline metal salt of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5) by heating in an aqueous alkaline metal hydroxide solution or a mixed solvent of a water-soluble organic solvent and water. The xe2x80x94COxe2x80x94 group is reduced to xe2x80x94CH2xe2x80x94 group by the conventional Wolff-Kishner ketone reduction process, and thus yields xcfx89-hydroxyaliphatic acid. As described above, the ester of xcfx89-hydroxyaliphatic acid is useful as a raw synthetic material and as an intermediate, and particularly as an intermediate in the production of xcfx89-hydroxyaliphatic acid which is an important intermediate for large cyclic lactone-based perfumes, such as cyclopentadecanolide and cyclohexadecanolide, in the perfume industry.
The present invention relates to separation of the compound represented by the general formula (9) by extraction with an organic solvent or crystallization, in which the compound is formed by hydrolysis and decarboxylation of the byproduct in the condensation reaction which is present in the reaction mixture after extraction, hydrolysis, and decarboxylation under a basic condition of the condensation products of the above-mentioned dicarboxylate ester and xcex3-butyrolactone:
wherein n is an integer of 7 to 13. The residual aqueous solution is treated at a predetermined temperature to selectively crystallize the alkaline metal salt of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid, and then subjected to solid-liquid separation to separate the solution into the cake and the filtrate. The alkaline metal salt of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5) and the alkaline metal salt of dicarboxylic acid represented by the general formula (8) are thereby separately recovered. Alternatively, the resulting cake and filtrate are independently treated with a mineral acid to separately recover the xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (10) and the dicarboxylic acid represented by the general formula (11):
wherein n is an integer of 7 to 13;
wherein n is an integer of 7 to 13.
Alternatively, the pH of the mixture containing the alkaline metal salt of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5) and the alkaline metal salt of long-chain dicarboxylic acid represented by the general formula (8) is adjusted to 5 to 7 with a mineral acid to precipitate the compound represented by the general formula (10), and is then subjected to solid-liquid separation to separately recover the xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (10) and the alkaline metal salt of long-chain dicarboxylic acid represented by the general formula (8). The pH of the filtrate is adjusted to 3 to 5, if necessary, to recover the long-chain dicarboxylic acid represented by the general formula (11) by precipitation and then solid-liquid separation.
For example, the compound represented by the general formula (9) is removed by extraction from, or selectively crystallized by treatment at a predetermined temperature from, the mixture containing the alkaline metal salt of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5), the alkaline metal salt of long-chain dicarboxylic acid represented by the general formula (8), and the xcex1,xcfx89-dihydroxy-xcex4,(xcfx89-3)-alkanedione represented by the general formula (9). Next, the aqueous solution after removing the cake by solid-liquid separation is treated at a predetermined temperature to selectively crystallize the compound represented by the general formula (5) and then separated into a cake and a filtrate by solid-liquid separation. When the filtrate contains a small amount of compound represented by the general formula (5), the pH of the filtrate is adjusted to 5 to 7 to crystallize the compound represented by the general formula (10) and to separately recover the xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (10) and the alkaline metal salt of long-chain dicarboxylic acid represented by the general formula (8) after the subsequent solid-liquid separation. The pH of the resulting filtrate is adjusted to 3 to 5 to crystallize the compound represented by the general formula (11) and to separately recover the alkaline metal salt of long-chain dicarboxylic acid represented by the general formula (8) after the subsequent solid-liquid separation.
Any organic solvent which is unreactive in basic conditions and insoluble in water can be used without limitation to separate the xcex1,xcfx89-dihydroxy-xcex4,(xcfx89-3)-alkanedione represented by the general formula (9) from the reaction mixture. Examples of the organic solvents include benzene, toluene, xylene, tetralin, decalin, pentane, hexane, heptane, octane, cyclohexane, isopropyl ether, and dibutyl ether. Among them, toluene is preferably used.
The amount of the organic solvent used in the present invention is not limited, and lies in a range of preferably 0.5 to 20 parts by weight, and more preferably 1 to 10 parts by weight with respect to the reaction mixture in view of processing and material cost.
The extraction temperature of the compound represented by the general formula (9) is not limited in the present invention, and lies in a range of 50 to 110xc2x0 C., and preferably 60 to 90xc2x0 C. in view of the boiling points of the organic solvent and water used for the extraction; however, the higher the extraction temperature, the higher the extraction efficiency. Although the organic layer may contain the compound represented by the general formula (5), the compound can be substantially recovered by reverse extraction with hot water.
Although the crystallization temperature of the compound represented by the general formula (9) in the present invention significantly depends on the composition of the reaction mixture and particularly the water content, it is not limited as long as the compound represented by the general formula (9) is crystallized and the salts represented by the general formulae (5) and (8) are dissolved. The crystallization temperature is preferably in a range of xe2x88x9220 to 80xc2x0 C., and more preferably 0 to 40xc2x0 C., in view of processing.
In the crystallization of the compound represented by the general formula (9), although the water content in the reaction mixture is significantly affected by the composition and temperature of the reaction mixture, it is not limited as long as the water content permits crystallyzation of the compound represented by the general formula (9) and dissolution of the salts represented by the general formulae (5) and (8). The water content is preferably in a range of 50 to 99 percent by weight, and more preferably 70 to 90 percent by weight in view of processing.
Solid-liquid separation of the crystal represented by the general formula (9) in the present invention may be performed by any conventional method such as centrifugal sedimentation, centrifugal hydroextraction, or filtration. Although the resulting cake may contain the salts represented by the general formulae (5) and (8) in some cases, washing with water enables an increase in purity of the compound represented by the general formula (9) in the cake and recovery of the salts represented by the general formulae (5) and (8) as an aqueous solution.
The extraction step in the present invention may be of a batch type or a multi-vessel type, or a continuous type.
The crystallization conditions of the alkaline metal salt of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5) will now be described.
Although the crystallization temperature of the compound represented by the general formula (5) significantly depends on the composition and particularly on the water content of the reaction mixture, it is not limited as long as the crystals of the compound represented by the general formula (5) forms and the compound represented by the general formula (2) is dissolved. The crystallization temperature is in a range of preferably xe2x88x9220 to 80xc2x0 C., and more preferably 0 to 40xc2x0 C. in view of processing.
Although the water content in the present invention significantly depends on the composition and temperature of the reaction mixture, it is not limited as long as the crystals of the compound represented by the general formula (5) forms and the compound represented by the general formula (8) is dissolved. The water content is in a range of preferably 50 to 99 percent by weight, and more preferably 70 to 90 percent by weight in view of processing.
The solid-liquid separation of the crystal formed in the present invention can be performed by any conventional method, such as centrifugal sedimentation, centrifugal hydroextraction, or filtration. Although the resulting cake may contain the compound represented by the general formula (8) in some cases, washing with water enables an increase in purity of the compound represented by the general formula (5) in the cake and recovery of the compound represented by the general formula (8) as an aqueous solution.
The cake obtained in the production of the large cyclic lactone can be used in the next reductive reaction without further treatment or after acidification. The reductive reaction can be achieved by a conventional method, such as Wolff-Kishner reduction, or Clemmensen reduction.
The mineral acid used for acidifying the alkaline metal salts represented by the general formulae (5) and (8) is not limited, and sulfuric acid and hydrochloric acid are often used. The aliphatic acid after the acidification can be recovered by a solid-liquid separation method, such as centrifugal sedimentation, centrifugal hydroextraction, or filtration; or extraction with an organic solvent, such as benzene, toluene, xylene, pentane, hexane, heptane, octane, cyclohexane, diethyl ether, isopropyl ether, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, or dichloroethane, although the method depends on the shape of the aliphatic acid.
When the compound represented by the general formula (10) is obtained from the mixture of the compounds represented by the general formulae (5) and (8) with a mineral acid, the pH is preferably in a range of 5 to 7, and more preferably 5.5 to 6.5. When the compound represented by the general formula (11) is obtained after acidification of the compound represented by the general formula (8), the pH is preferably in a range of 3 to 4, and more preferably 3.5 to 4.5. A further reduction in the pH value is not preferable due to an increased amount of mineral acid used and increased material cost, although the recovery rate and purity of the compound represented by the general formula (11) are not affected.

Methods for making 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide, ester of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid, and derivatives thereof

Abstract: Condensation reaction of xcex3-butyrolactone with a dicarboxylate ester represented by the general formula (1) ROOC(CH2)nCOOR wherein n is an integer of 7 to 13 and R is an alkyl group forms a condensation solution containing an alkaline metal salt of 2-(xcfx89-alkoxycarbonylalkanoyl)-4-butanolide represented by the general formula (3):

Abstract: wherein n is an integer of 7 to 13, R is an alkyl group, and M is an alkaline metal; the solution is extracted with water or an aqueous alkaline solution and subjected to hydrolysis and decarboxylation to form an alkaline metal salt of xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (5):

Abstract: wherein n is an integer of 7 to 13 and M is an alkaline metal; and the compound is selectively and effectively separated and recovered and then acidified to form an xcfx89-hydroxy-(xcfx89-3)-ketoaliphatic acid represented by the general formula (10):

Abstract: wherein n is an integer of 7 to 13.


A system and method to rapidly perform emissions measurements of in-use vehicles being driven by the general public under normal driving use for determining whether the vehicles are performing in accordance to the regulatory standards by which they were certified. The system and method require no recruitment testing of in-use vehicles with potentially detectable connections, but instead incorporate a vehicle emissions remote sensing device that does not require mechanical or electrical connection to the vehicle, with the measured values being recorded and the vehicles identified, including based on, for example, make and model, engine size, engine combustion management technology and/or pollution control technology. The system and method additionally operates to perform data analysis on the collected data to identify abnormal emissions-related conditions of a particular make and model for the purpose of in-use surveillance, thus allowing actual emissions results to be detected, determined and compared for compliance with regulatory standards.

The present invention is directed to a system and method for determining without recruiting vehicles, or physically or electronically connecting to vehicle systems, whether the emission systems of in-use vehicles perform according to the regulatory standards by which they were initially certified, and in particular whether particular models of vehicles are performing to their regulatory standard.
In-use vehicle emissions testing typically involves recruiting such in-use vehicles from active service and testing them on driving simulators at set conditions, such as with respect to engine load and RPMs, and/or performed when vehicle exhaust systems or computers are connected with portable emissions measurement testing equipment while the vehicle is driven on the road. These testing techniques include connections to the vehicle that are potentially detectable by the vehicle. In certain instances, vehicle manufacturers have manipulated vehicle emissions control systems, such as software controls, to circumvent the emissions controls when the vehicle on board computer system detects the vehicle is in normal on-road use, as compared to performing a regulatory compliance test drive. For example, vehicle software has been improperly configured to deactivate particular emissions equipment or functions during regular driving conditions. Such circumventions, which are generally referred to as defeat devices, violate emissions regulations and are employed to improperly obtain performance gains.

System and method to detect vehicle emissions noncompliance


An apparatus to effect the reclaiming of waste water includes a storage tank in operative communication through filtration tanks, that in turn receives water from an enclosed preliminary filtration container. From the storage tank, a delivery pump provides for the coupling of water hoses to obtain water from the storage tank structure.

1. Field of the Invention
The field of invention relates to water reclaiming apparatus, and more particularly pertains to a new water reclaiming apparatus wherein the same is arranged to provide for plural stage filtration and subsequent storage of water.
2.Description of the Prior Art
Domestic waste water and its reclamation for potable drinking water has been directed in the prior art and exemplified by the U.S. Pat. No. 4,812,237, with further domestic waste water being utilized and indicated in U.S. Pat. Nos. 4,112,972; 5,059,330; and 5,004,536.
The instant invention attempts to overcome deficiencies of the prior art by providing for an economical and readily employed filtration facility permitting the reuse of domestic waste water after plural filtering stages, and this respect, the present invention substantially fulfills this need.


An acoustic nonlinearity parameter (xcex2) measurement method and system for Non-Destructive Evaluation (NDE) of materials and structural members novelly employs a loosely mounted dielectric electrostatic ultrasonic transducer (DEUT) to receive and convert ultrasonic energy into an electrical signal which can be analyzed to determine the xcex2 of the test material. The dielectric material is ferroelectric with a high dielectric constant ∈. A computer-controlled measurement system coupled to the DEUT contains an excitation signal generator section and a measurement and analysis section. As a result, the DEUT measures the absolute particle displacement amplitudes in test material, leading to derivation of the nonlinearity parameter (xcex2) without the costly, low field reliability methods of the prior art.

The invention described herein was made by employees of the U.S. Government and may be manufactured and used by or for the Government for governmental purposes without the payment of any royalties thereon or therefor.
1. Field of the Invention
The present invention generally relates to ultrasonic measurement techniques for non-destructive evaluation (NDE) of materials and structural members, including the determination of fatigue damage. More particularly, the present invention relates to improved ultrasonic-based approaches to determining the nonlinearity parameter (xcex2) for assessing the fatigue damage to structural members.
The fields of use include, inter alia, ultrasonic fatigue sensor technology, process monitor technology for optimum strength of materials, bond strength analysis technology, and other nonlinear acoustic data information technology.
2. Background
NDE of materials involves the inspection of materials without having to damage the materials or dismantle structures to which the materials are incorporated. Among the many important NDE operations are the inspection of aircraft, bridge, and building structural members to detect fatigue damage that could possibly lead to catastrophic failure, as well examining bonds (e.g., adhesive junctions) between members for indications of prospective failure.
Prior art methods of fatigue damage detection include bombarding material under test with acoustic finite amplitude waves in the ultrasonic range, and examining, via a transducer, the response waves (including the fundamental and harmonics) produced by the material to determine a nonlinearity parameter (xcex2) which may be correlated to material fatigue.
One prior art approach of note requires that a piezoelectric transducer be bonded directly to the material being tested. The test material is excited by introducing finite-amplitude ultrasonic waves perpendicular to the surface of the test material, whereupon the surface vibration energy is received by the transducer and analyzed to determine the nonlinearity parameter (xcex2). Among the drawbacks of this approach is the fact that the results must be corrected for the layer of bond material between the test material and the transducer, and it is assumed that the test,material and transducers are both flat and parallel. Further, the attenuation characteristics of the test material must also be known. This approach is therefore impractical at times, and can lead to over-correction (assuming that corrections can be practically made), and therefore inconsistent results.
Another approach of note uses an air-gap capacitive transducer. That is, the surface of the test material serves as part of an air-gap capacitive transducer, with the surface being xe2x80x9cfree.xe2x80x9d The direction of acoustic wave propagation is ideally perpendicular to the test material surface, although corrections can be made if the relative wave propagation angle is known. While this approach generally works well if the parameters are carefully controlled, as in a laboratory, it does not work reliably, for example, if the test material surface is not optically flat. Therefore, it is not a practical approach for most field testing of structures.
Yet another approach of note known as laser interferometry impinges laser light on the surface of a vibrating test material. The reflected light is analyzed, employing for example, Michelson or Fabry-Perot demodulation techniques, by complex and often expensive equipment. While a strong approach, it requires that the test material have good optical reflection characteristics, which is not the case for many in-field structures. Additionally, the equipment must be optically aligned (due to temperature and other environmental changes) often to produce reliable results. Those skilled in the art will also appreciate that the excitation waves must be aimed so that the reflection energy exits the surface vibrations precisely in the center of the sound field, which is extremely difficult to locate in practice.
What is therefore needed but sorely lacking in the prior art, is an ultrasonic transducer method of NDE that is reliable in the field, does not require a highly optically reflective test material surface, is cost-effective, and requires minimal preparation of the test equipment and test material in the field.
In view of the aforementioned problems and deficiencies of the prior art, the present invention provides a system for measuring acoustic nonlinearity (xcex2) in test materials. In at least one embodiment, the system can at least include an acoustic signal generator adapted to apply an acoustic signal to a test material, a dielectric electrostatic ultrasonic transducer (DEUT) comprising a plate member and a dielectric member coupled to the plate member, the dielectric member being a high dielectric constant insulator, and being adapted to convert received ultrasonic energy into an output electrical signal, and a measurement system coupled to the DEUT, the measurement system being adapted to calculate the nonlinearity xcex2 in response to the output signal from the DEUT. The DEUT is adapted to be loosely mounted to a surface of the test material, and the DEUT is adapted to receive acoustic energy from the surface of the test material.
The present invention also provides a method of measuring acoustic nonlinearity (xcex2) in test materials. The method can at least include the steps of generating and applying an acoustic signal to a test material, providing a DEUT comprising a plate member and a dielectric member coupled to the plate member, the dielectric member being a high dielectric constant insulator, and being adapted to convert received ultrasonic energy into an output electrical signal, and loosely mounting the DEUT to a surface of the test material. The method further can at least include the steps of via the DEUT, receiving acoustic energy from the surface of the test material, and via a measurement system coupled to the DEUT, calculating the nonlinearity xcex2 in response to the output signal from the DEUT.

Non-destructive evaluation method employing dielectric electrostatic ultrasonic transducers

The United States of America as represented by the Administrator of the National Aeronautics and Space Administration


Systems and processes that incorporate teachings of the subject disclosure may include, for example, receiving from a mobile device, by way of a cellular network, a request for delivery of high-bandwidth application service. A location of the mobile device can be obtained and used to determine availability of any nearby wireless packet-network services. If it is determined that a wireless packet-network service is available, a network connection between the mobile device and the wireless packet-network service can be established. The request for delivery of high-bandwidth services can then be forwarded to an application server that delivers the requested services by way of the wireless packet-network service. Other embodiments are disclosed.

Cellular radio communication services have evolved in a relatively brief period from early implementations offering voice only services, to voice with limited data services, such as short messaging service, to ever more robust data networks capable of delivering rich data services (e.g., 3G and long term evolution or LTE). Data services routinely expected by cellular subscribers may now include email, web browsing, and even streaming media services, such as streaming audio and streaming video. Unfortunately, demand for data rich applications seems to outpace technological advances.
At least one reason for such demand in a mobile cellular service is that subscribers have become accustomed to data rich services. Subscribers are familiar with Web browsing and their ever-expanding online experiences through their home and office networks. Home wireless networks and Wireless Fidelity (also known as Wi-Fi) hotspots provide subscribers with a sense that such data rich features are easily deliverable to any mobile device. Additionally, as mobile phones tend to become more like mobile computers, the line between phone and computer is blurred.
For the time being, mobile cellular radio networks have bandwidth constraints imposed by their very nature as radio networks. Namely, there are a limited number of frequencies available within a given geographic region to be shared by multiple cellular service providers and other wireless applications. Cellular services can be subject to more stringent regulatory constraints (e.g., wireless operational requirements imposed by the Federal Communications Commission (FCC)) than Wi-Fi services, which operate at much lower power levels. Accordingly, despite advances in processing power, storage capacity, and network availability, the constraints of limited over-the-air capacity of mobile cellular radio communications remain as a gating factor in delivery of rich data services.

Method and apparatus for delivery of application services


A portable back support device for providing vertebrae decompression support and therapeutic heating and/or cooling while preventing pressure against an incision or injured portion of the back. The support device can be made adjustable to fit different size persons.

1. Field of the Invention
The invention relates to a back support device which applies supportive pressure to desired areas of a person""s back in a manner which protects a prescribed area of the back from pressure due to contact with other objects.
More particularly, the invention relates to an adjustable back support device which is portable and can be used basically anywhere, in any setting as needed to provide support for a person""s back while avoiding the application of pressure or contact in a sensitive area such as where surgery has been performed. The device is useful for persons recovering from back surgery or those with a back injury.
2. Description of the Related Technology
U.S. Pat. No. 5,547,251 discloses a wheel chair having a sling construction back support and a cushioning arrangement for providing support to the side of the sling opposite the person""s back. The cushioning arrangement is configured to modify the support provided by the sling. The cushioning arrangement adjusts the distribution of support provided to the occupant by the upholstery of the backrest to contour the sitting profile of the wheelchair occupant. The cushioning arrangement does not contact the person""s back, but modifies the support provided by the sling.
U.S. Pat. No. 5,146,625 discloses a protective vest having cooling means comprising a plurality of elongated pockets on front and back panels, each of which has an opening to receive a cooling pack into the pocket. In one embodiment, each pocket has inner and outer walls with a structural layer and an insulation layer. The insulation layer of the inner wall inhibits too rapid cooling of the user""s torso which might otherwise occur during cooling by the gel packs. The vest is not designed to distribute pressure as described with respect to the present invention.
U.S. Pat. No. 5,062,414 discloses a back brace of elastic material which carries a gel pad and an air bladder with three individually inflatable chambers, including left, right, and overall areas, so that the user may adjust the pressure exerted on the pad and hence the support of the lower back. The gel pad may also contain an adjustable heating element to electrically heat the gel-like material. The back brace does not have a panel which applies pressure except in a prescribed area and which relieves spinal pressure.
The invention is directed to a portable back support device for applying back supportive pressure selectively such that a confined area is not subject to the supportive pressure of the other areas. The device also assists in reducing gravitational, or other, compression of the vertebrae in a person""s spine.

Back support device with surgical area protection