A timepiece with a dynamic, analogue display of the time. The timepiece has a first hand which rotates at a first speed and a second hand which rotates at a second speed, wherein the time is displayed with respect to a time unit when the two hands coincide in that the angular position of the coincidence indicates the current time of the time unit viewed on a dial.

This invention relates to a timepiece with a dynamic, analogue display of the time.
The analogue display of the time on a timepiece usually is effected by means of a two- or three-hand system, wherein one hand indicates the hour, one hand indicates the minute, and one possibly present third hand indicates the second. The fundamental principle of reading the time is the mental processing of the static, geometric image of the display, as it is indicated by the two or three hands of the display at a certain time.
Reading the time as the mental processing of a static, geometric image, however, contradicts the dynamic character of the time, which naturally does not stand still and is not static.

Timepiece with dynamic, analogue display of the time


A fixture having a plurality of upright panels joined together with connectors extending into grooves on adjacent ends of the panels. End caps have inwardly directed lips that extend into longitudinally aligned vertical grooves on the ends of the panels to hold the caps on the panels ends and form the end grooves. The connectors have downwardly directed legs located in the end grooves to join the adjacent panels together at either a 45 degree relationship or a 90 degree relationship or a 180 degree relationship relative to each other. The outer faces of the panels are interrupted with at least one horizontal groove for accommodating merchandise support hangers.

Several panel support structures and connectors have been used to assemble shelving, display stands, partitions, walls and the like. Examples of these support structures are disclosed by Radek in U.S. Pat. No. 3,101,817; and Berman et al in U.S. Pat. No. 3,174,592. Radek discloses a wall panel support structure comprising a generally upright framework having a plurality of transverse brackets. The brackets have upper and lower channels to accommodate the top and bottom edges of the panels. Berman et al discloses clips mounted on the ends of panels that engage a slotted vertical support standard to hold the panels in assembled relation.
Numerous joint structures and connectors have been used to join adjacent panels together. These structures include dowels, pins, clips, wood strips and metal extrusions. Examples of structural joints for panels are disclosed by Williamson in U.S. Pat. No. 1,888,523; Barker in U.S. Pat. No. 3,323,819; and Logan in U.S. Pat. No. 4,438,578. Williamson discloses a structural joint comprising a generally L-shaped locking strip having bent longitudinal ends. The locking strip fits into linear grooves of adjacent panels to hold adjacent mitered edges of the panels together. Barker discloses a joinder described as a symmetrical L-bar located between bent end flanges of normally disposed panels. A pair of cylindrical wedges cooperate with the joinder to hold the panels in assembled relation with each other. Logan disclose a right angle bracket adapted to fit into channels in adjacent beveled ends of a frame structure. The outer ends of the bracket have bent over portions that fit into cavities in the channels.


This invention relates generally to an electrical connector assembly for interconnecting printed circuit boards. More specifically, this invention relates to a high speed, high density electrical connector and connector assembly having wafers with an improved pin conductor. The connector contains a shield plate having at least one contact end that is bent in a direction perpendicular to the plane of the shield plate.

Electrical connectors are used in many electronic systems. It is generally easier and more cost effective to manufacture a system on several printed circuit boards ("PCBs") which are then connected to one another by electrical connectors. A traditional arrangement for connecting several PCBs is to have one PCB serve as a backplane. Other PCBs, which are called daughter boards or daughter cards, are then connected through the backplane by electrical connectors.
Electrical connectors can be designed for single-ended signals, as well as for differential signals. A single-ended signal is carried on a single signal conducting path, with the voltage relative to a common ground reference set of conductors being the signal. For this reason, single-ended signal paths are very sensitive to noise present on the common reference conductors. It has thus been recognized that this presents a significant limitation on single-ended signal use for systems with growing numbers of higher frequency signal paths.
Differential signals are signals represented by a pair of conducting paths, called a "differential pair." The voltage difference between the conductive paths represents the signal. In general, the two conducing paths of a differential pair are arranged to run near each other. If any other source of electrical noise is electromagnetically coupled to the differential pair, the effect on each conducting path of the pair should be similar. Because the signal on the differential pair is treated as the difference between the voltages on the two conducting paths, a common noise voltage that is coupled to both conducting paths in the differential pair does not affect the signal. This renders a differential pair less sensitive to cross-talk noise, as compared with a single-ended signal path. One example of a differential pair electrical connector is the GBX™ connector manufactured and sold by the assignee of the present application.
While presently available differential pair electrical connector designs provide generally satisfactory performance, the inventors of the present invention have noted that current high density connectors contain very small pins that are weak and sometime break when inserted into vias on the circuit board. This problem is especially apparent on the pins, particularly the press-fit tails, on the shield plate.
Therefore, there remains a need for a high speed, high density electrical connector and connector assembly design that provides stronger pins on the shield plate of the connector.

Electrical connector having a shield plate with contact ends with neck portions


In a method for manufacturing storage plates, plate frames (5) of storage batteries are material-coated by active material supply means which is provided with at least one rotating material application wheel. The wheel includes a dispensing element (14) with which the active material is dispensed to a conveyor belt or equivalent means which travels under the supply means (10) and conveys plate frames (5). The material application wheel/wheels (11,1a) of the supply means (10) is/are rotated at such a high speed that the material application wheel/wheels (11,1a) dispenses/dispense the active material (1) from the dispensing element (14) to the mobile conveyor belt (20) under the effect of centrifugal force. The invention also concerns a means for manufacturing storage batteries.

The present invention concerns a procedure for manufacturing storage batteries in which procedure a plate frame of storage battery plates is compound-applied with an active material applying apparatus. The apparatus includes at least one rotating compound application wheel provided with dispensing members for dispensing the active material on a conveyor belt of equivalent moving support. The belt travels under the application apparatus for conveying the active material to the plate frame.
The invention also concerns a device for manufacturing storage battery plates, the device comprising an active material application apparatus located above the conveyor belt, or equivalent moving support, for conveying the plate frames for storage battery plates. The material application apparatus includes at least one rotary compound applying wheel provided with dispensing members, the wheel being disposed when rotating to dispense the active material on the conveyor belt travelling thereunder.
The storage battery plates are in general manufactured in such manner that a plate blank, placed on a conveying base, e.g. on a belt, can receive active material which e.g. in a lead battery consists of lead oxide, water, sulphuric acid and requisite additives. For the lead battery, the plate frame has been formed of a lead wire reticle. The active material is compressed on the plate frame and is smoothed thereafter e.g. with the aid of rollers or equivalent. Thereafter, the storage battery plate is detached from the conveying base in an appropriate manner.
The active material is in nature claylike and sticky, which causes considerable problems in applying the compound on the plate frame. A means for applying the active compound is known in the art in which lead wire nets, that is, the plate frames, have been placed on a mobile conveyor belt which moves the plate frames past the active compound applying head. In the designs known in the art, a silo or equivalent has been disposed in the head applying the active compound. The head employs a rotary blade wheel, and an application roller thereunder applies the active compound on the plate frame passing under the silo.
However, the designs of the prior art have numerous drawbacks. A considerable drawback is that the dispensing with the blade wheel and with the application roller is inaccurate because the application roller does not permit dispensing an appropriate layer of the compound on a plate frame passing on the conveyor belt with sufficient accuracy. When passing under the silo, the plate frame has to "tear" the requisite layer of compound in place. This kind of design known in the prior art requires considerable and time-consuming subsequent cleaning of the storage battery plates as well as calibration of the completed storage battery plates to provide sufficiently homogenous plates. The mechanical strength of the plate frame is also required to be very high.

Procedure and means for manufacturing storage battery plates


Transmission properties of a telecommunications transmission line may be estimated with improved accuracy by numerical solution for Γ of Zin·jω^C=Γcoth(Γ). At least one curve is adapted to Γ solutions already obtained and a starting point for numerical solution is selected in dependence of the at least one curve and in dependence of an already obtained solution close in frequency. In a first frequency range, starting points for numerical solution may be calculated from a biquadratic equation. In a second frequency range, a line in the complex plane may be adapted to solutions already obtained and new starting points selected in dependence of the line and in dependence of the previous solution. In a third frequency range, two lines in the frequency plane may be adapted to solutions already obtained and new starting points selected in dependence of the lines.

In patent application WO2005SE01619 (publication number WO2007050001) a method is described wherein line constants of a telecommunications transmission line are estimated using estimates of the line input impedance Zin at a number of angular frequencies ω as input values. Values of Zin for at least two angular frequencies ω are required in order to estimate the line constants {circumflex over (R)} (line resistance), {circumflex over (L)} (line inductance) and Ĉ (line capacitance). (line conductance Ĝ neglected)
Zin is expressed as a polynomial in jω with the line constants as coefficients. This relationship is solved for the line constants by means of two systems of equations, where in each system there is one equation per spectral component of Zin, i.e. at least two equations per system.
Only spectral components of Zin for which the propagation constant of the line times the line length is less than π (|γd|<π or |Γ|<π) can be used.
The estimates so obtained suffer from some inaccuracy, in particular the inductance estimate has an accuracy of about 30%.
The disclosure suggests that better accuracy can be achieved by using more frequencies, i.e. measuring Zin at more frequencies and using these values as input.
In GB 2180073 A (corresponding to FR 2586818 A), a method for detecting wear in underwater cables is disclosed. The primary parameters of the cable are measured before deployment of the cable and, using the propagation constant (calculated from the measured primary parameters) as an intermediate value, an input impedance Za of the line in good condition is determined.
When the apparent impedance Za changes, a model is applied in which a position and impedance of a fault are varied until the Za calculated according to the model matches the measured Za, and hence the fault position and impedance used as input for the model correspond to the position and impedance of the actual fault or wear point.
U.S. Pat. No. 4,313,169 discloses a system for detecting the position of a fault in an electrical power line. Current and voltage measurements, along with the propagation constant and characteristic impedance of the line are used to estimate the location of a fault. The propagation constant and characteristic impedance are assumed to be known a priori. It is assumed that both the resistance and the conductance per unit length are negligible.

Method for estimating transmission properties of a telecommunications transmission line


A guide device for compressing a fibre web exiting from a transverse conveyor arrangement at the outlet of a card. The fibre web leaving the card outlet rolls is conveyed to one side of the card, where it is guided downward by the guide device. The rolls are disposed above the transverse conveyor and each has a step-like constriction at an end associated with the guide device and outwardly of a point at which the fibre web is deflected around a deflection roller of the transverse conveyor. The guide device is partially received in the constriction and a nip or a nip zone is formed between the guide device and the adjacent deflection roller of the transverse conveyor. The guide device is situated to the side of and at least mainly above the axis of rotation of the deflection roller.

In a known transverse conveyor arrangement, the guide device is a roller disposed next to the associated deflection roller, so that a perpendicular line connecting the axes of rotation of the roller and the deflection roller extends horizontally. The cylindrical surfaces of the rotatable rolls forming the nip also extend in the horizontal direction beyond the roller, up to a bottleneck constriction formed for drive purposes.
Although known transverse conveyor arrangements have given good results in practice, the desire for continually higher card outputs is leading towards higher take-off speeds of the card web. There are technological limits to this process, since the card web is a relatively weak structure and tends to overshoot and form loops near the transverse conveyor outlet.

Transverse conveyor arrangement at the outlet of a card


A semiconductor device having an improved protection scheme and a temperature compensated sustaining voltage is provided by integrating a plurality of temperature compensated voltage reference diodes between the drain and the gate of the semiconductor device. The diodes protect the device by clamping the device's sustaining voltage to the total avalanche voltage of the diode. The device will dissipate any excessive energy in the conduction mode rather than in the more stressful avalanche mode. In addition, the plurality of diodes will provide for a temperature compensated sustaining voltage of the semiconductor device. The plurality of diodes are formed back-to-back in polysilicon. The positive temperature coefficient of the avalanching junction of each diode pair is compensated for by the negative temperature coefficient of the forward biased junction.

This invention relates, in general, to semiconductor devices and, more particularly, to a monolithic temperature compensated voltage reference diode and method of integration into a semiconductor device to achieve a temperature compensated sustaining voltage and high energy sustaining capabilities.
In the past, several schemes have been used to protect semiconductor devices from potentially destructive voltages and currents. Such conditions are commonly encountered in the application of power semiconductor devices. For example, a power semiconductor device such as a power MOSFET, is frequently used to switch inductive loads. When the power MOSFET is switched off, the energy stored in the inductor will force the drain voltage of the power MOSFET to rise rapidly above the supply voltage. If no limiting means are employed, this rise will continue until the drain-source avalanche voltage of the power MOSFET is reached, whereupon the energy stored in the inductor will be dissipated in the power MOSFET during device avalanche. Such dissipation can cause avalanche stress-induced failure of the power MOSFET.
A more manageable form of stress commonly occurs in the operation of power semiconductor devices as the device switches current on and off within its normal mode of conduction. Such operation of a power MOSFET occurs when the current in the power MOSFET channel region is, and remains, under the control of the power MOSFET gate. In this state, the device conduction stress can be regulated by appropriately modulating the signal on the power MOSFET gate. It is understood in the art of power MOSFET design and processing that device avalanche stress is more potentially destructive than device conduction stress.
Various processing techniques are commonly employed to render the internal parasitic elements of a power MOSFET less susceptible to avalanche-stress induced failure. A problem with these techniques is that normal variations in the processing parameters of a power MOSFET may inhibit optimization or reduce the effectiveness of these techniques.
Other methods of protection involve the application of external devices to render the power MOSFET less susceptible to avalanche stress. One such method involves using a drain-source clamp diode: an external diode connected between the drain and source of the power MOSFET, whose avalanche voltage is less than that of the power MOSFET. When the rising drain-source voltage reaches the avalanche voltage of the drain-source clamp diode, the energy stored in the inductor is dissipated in the drain-source clamp diode rather than the power MOSFET. The amount of energy that can be safely dissipated in this fashion depends on the dissipation capability of the drain-source clamp diode--large amounts of energy require large clamp diodes. While the drain-source clamp diode is dissipating the inductive energy, the power MOSFET is idle.
A more advantageous method of protection involves diverting a small fraction of the inductive energy to the power MOSFET gate by means of a drain-gate clamp diode whose avalanche voltage is about two to three volts less than the avalanche voltage of the power MOSFET. A suitable gate-source termination resistor is also employed in this method. When the rising drain voltage reaches the avalanche voltage of the drain-gate clamp diode, the resulting avalanche current develops a voltage across the gate-source termination resistor which turns on the power MOSFET, effectively clamping its drain to the sum of the drain-gate diode avalanche voltage and the voltage across the gate-source termination resistor. In this method the power MOSFET acts as its own clamp, and dissipates the inductive energy in the less stressful conduction mode. It is customary to add a second blocking diode in back-to-back configuration with the drain-gate clamp diode to enable the gate-source voltage in normal operation to exceed the drain-source voltage.
An advantage of using a drain-gate clamp over using a drain-source clamp is that the drain-gate diode, blocking diode, and gate-source termination resistor handle only enough energy to charge the power MOSFET input capacitances and therefore may be small in size and cost.
A disadvantage of these external clamp methods is that additional parts are employed to protect the power MOSFET, thus increasing the cost of the total system. In addition, the physical layout of some applications may preclude placing the clamp circuitry in close proximity to the power MOSFET. The resulting parasitic inductances act as impedances that slow the response time of the clamp circuitry. Therefore the power MOSFET may have to endure some avalanche stress until the clamps become active. It would be advantageous to provide a means of protecting the power MOSFET that achieves intimate proximity to the power MOSFET and does not increase the number of additional system components.
An additional problem that is difficult to control is the change in drain-to-source avalanche voltage of a semiconductor device with device junction temperature. For example, the drain-to-source avalanche voltage temperature coefficient of a 100V power MOSFET is about 9mV per degree Celsius. Additionally, wafer fabrication variations may result in an avalanche voltage spread of several volts for different wafer fabrication lots. While such variations are not a problem in many applications, some applications can require a tighter avalanche voltage distribution with less variation over temperature.
If a drain-gate clamp diode is selected to be a temperature compensated zener diode, the sustaining voltage of the power MOSFET, being clamped to that of the drain-gate clamp diode, will, to a great extent, also be temperature compensated. In the industry, temperature compensated zener diodes can be formed by arranging two diodes in back-to-back configuration, one with a zener avalanche voltage of about 5.5 volts and the other forward biased when the first is reverse biased. The zener diode has a positive temperature coefficient (TC) and the forward biased diode has a negative temperature coefficient. To achieve a temperature compensated voltage reference for the back-to-back to configuration, the positive temperature coefficient of the zener diode must be approximately equal in magnitude to that of the negative temperature coefficient of the forward-biased junction. It is well known in the art that a zener diode of about 5.5 bolts has a positive temperature coefficient approximately equal in magnitude to that of the negative temperature coefficient of a forward-biased junction. The resulting avalanche voltage of the two diode back-to-back "zero TC" configuration is about 6.2 bolts.
Higher sustaining voltage power MOSFETs with temperature compensation could be achieved by connecting a plurality of external zero TC zener diodes in series for use as a drain-gate clamp diode. Such a scheme would provide protection of the power MOSFET from avalanche stress and would provide a temperature compensated sustaining voltage, however, to do so would be cost prohibitive because it would greatly increase the system component count. In addition, the number of zero TC diodes may be limited by the physical layout of the system.
By now, it should be appreciated that it would be advantageous to provide an improved method of protecting a semiconductor device from avalanche stress which also provides a temperature compensated sustaining voltage of the semiconductor device.
Accordingly, it is an object of the present invention to provide a high voltage monolithic temperature compensated voltage reference diode which can be used to protect a semiconductor device and provide a temperature compensated sustaining voltage of the semiconductor device.
Another object of the present invention is to provide an integrated semiconductor device having an improved protection scheme and temperature compensated sustaining voltage.
A further object of the present invention is to provide a self-protecting, integrated semiconductor device which also exhibits a temperature compensated sustaining voltage.
An additional object of the invention is to provide a semiconductor device with a defined temperature coefficient of sustaining voltage.

Semiconductor device having high energy sustaining capability and a temperature compensated sustaining voltage


An exemplary system includes a blockchain system that includes a blockchain, a smart contract template, and a smart contract generated based on the smart contract template, the smart contract executable to facilitate, by way of the blockchain, exchanges between parties to the smart contract. The system further includes an interface system communicatively coupled to the blockchain system and configured to perform a set of operations to provide an interface to the blockchain system, the set of operations including receiving a user input from an application executed on a user computing device, translating the user input to a call to the blockchain system, and issuing the call to the blockchain system. The blockchain system is configured to perform, based on the call and the smart contract, an action on the blockchain that represents an exchange between the parties to the smart contract.

Blockchain technology uses cryptographic principles to create a series of time-stamped and unchangeable data records, i.e., a chain of blocks of data that is commonly referred to as a blockchain. A blockchain is managed across multiple computers in a decentralized architecture, making the blockchain useful as a distributed data store, such as a digital ledger that is used to record transactions across many computers in a manner that prevents undetected retroactive modification of recorded transactions.
However, implementation and use of blockchain technology can be difficult and typically requires a blockchain developer to build a blockchain system that is customized to a specific use or application. The developer may also need to build one or more custom interfaces to the blockchain system (e.g., a custom off-chain interface and/or a custom user interface to the blockchain system). Such conventional requirements have slowed the implementation of blockchain technology.

Systems, methods, and interfaces for smart contract based exchanges via a blockchain


The invention relates to a wet chemical method for the surface modification of products made of low-energy synthetic fibers, to the products produced by the method and to the use of the products produced by the method. The material surface is permanently provided with functional groups by contact with an aqueous polyvinylalcohol solution containing silanol(ate) groups. Depending upon the design, the materials have a high water consumption or transmission capacity or exhibit a capillary activity. The range of uses for surface-modified materials is extended by the possibility of reacting the functional groups, inter alia, with biologically active components.

The invention relates to a method for the surface modification of products made of low-energy synthetic fibres, to the products produced by the method and to the use of the products produced by the method.
The term "synthetic fibres" as it is used here refers to linear, thread-like macromolecules which, for example, can belong to the material classes of aramids, polyesters, polyamides, polyacrylates, polyacrylonitriles, polyurethanes, (per)fluorinated polyolefins, such as polytetrafluoroethylene or polyvinylidene(di)fluoride, polysulfones, polyimides, polyolefins etc., as well as co- or terpolymers thereof.
In the following the term "products made of low-energy synthetic fibres" refers to molded articles in 1 and/or 2-dimensional form. Articles in 1-dimensional form include, for example, filaments, monofilaments, multifilaments, fibres, threads, yarns, strings, rovings etc. Their diameter can be in the lower μm range or in the lower mm range, for example at 6 μm on the one hand or 3.4 mm on the other hand. The length can be in the mm range (staple fibres) or in the km range (filaments). The cross section of the fibres can be round, elliptical, triangular, rectangular, polygonal, star-shaped, lobular, cylindrical etc. The unmodified fibre surface may be rough or smooth. In mainly 2-dimensional form these are textile materials which exist as filament composite material such as tissue, knitted fabrics, fleece, nets, braids etc. or as fibre composite material such as non-wovens, felts, wadding etc. or as combinations of filament and fibre composite materials such as textile multilayer composites.
The area density is limited only by the technical feasibility and can range, for example, from 6 g/m2 to 1,600 g/m2. In particular in connection with surface modification(s), the term "material" is also used in the following for the abovementioned products made of synthetic fibres.
The term "surface modification" used here means that the surfaces of non-surface-modified materials differ from surface-modified materials in at least one of the following features:                in the results of surface analysis using, for example, ESCA (Electron Spectroscopy for Chemical Analysis) or SIMS (Secondary Ion Mass Spectroscopy)        in the wettability with water        in the electrostatic properties        in the chemical reactivity, e.g. in the ability to be dyed with water-soluble dyes
The term "low-energy" as used here means that products made of low-energy synthetic fibres have at least one of the following properties:                the free surface energy is less than 40 mN/m        the contact angle of water is greater than 45°, i.e. the wettability is low or absent, the material is hydrophobic        they cannot be dyed from the aqueous phase        they can easily become electrostatically charged.
Products made of low-energy synthetic fibres, particularly those made of polyolefins, have several disadvantages:                the material surfaces are chemically inert; they have no functional groups or only functional groups that can be activated with (chemically) drastic means, so that, for example, dyeing directly from the aqueous phase is not possible.        the materials easily become electrostatically charged, which prevents any further technical use.        the materials are not wettable with water. They cannot be used as lining in garments for example, as the inability to absorb perspiration would leave the wearer sweating. They cannot be used for wound dressings/hygiene products as they cannot absorb or convey wound secretions/body fluid. They cannot be used as filter material for aqueous media as the water cannot penetrate the material.
Solutions proposed to overcome the abovementioned disadvantages involve either finishing the surface of low-energy materials with surface-active substances such as wetting agents or surfactants, or depositing hydrophilic polymers such as polyvinyl pyrrolidone or polyvinyl alcohol on the surface. The proposed solutions are not satisfactory as the finishing with surface-active substances is not permanent; they are washed off/out on contact with water. In order for hydrophilic polymers to be retained on the surface, they have to be linked with certain substances, some of which are toxic; this is complicated and costly.

Method for the surface modification of products made of low-energy synthetic fibers


Boron particles in bead-like form suitable for use in the preparation of doped, single crystal silicon can be prepared using a fluidized bed technique for chemical vapor deposition of a boron hydride, such as diborane or decaborane.

This invention relates to high purity boron pellets, useful as dopants in the manufacture of single crystal, low resistivity, silicon ingots. Such ingots are starting materials for preparation of semiconductor devices. This invention also relates to a process for producing high purity boron in free-flowing, bead-like form.
Current methods for preparing electronic grade crystalline boron for doping, comprise decomposing boron halides in Siemens-type reactors. Operating temperatures are customarily within the range of 1,000.degree. to 1,300.degree. C. Such processes are energy intensive and inefficient, and corrosive by-products are produced. The boron product is in rod-like form.
The boron rods are customarily purified by float-zoning, or a similar technique. Such purifications comprise another energy intensive, high temperature process. After purification, the material is crushed, separated into desired particle sizes, and blended to produce the desired product. Impurities may be introduced during the crushing, size separation, and blending operations. Moreover, these steps have fairly significant yield losses.
Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume IV, Page 65, says in part "Direct thermal decomposition of boron compounds to high purity boron is limited to halides and hydrides. Boron tribromide or triiodide, and boron hydrides (from diborane to decaborane) have been decomposed on a wide variety of substrates ranging from glass to tungsten at temperatures from 800.degree.-1500.degree. C."


A switching regulator having a power switch arranged in a main circuit of the primary side in series with a current-measuring resistor and having a delta voltage source in series with the current-measuring resistor. The delta voltage source can be realized in a simple manner in that the current-measuring resistor is arranged in the emitter circuit of an auxiliary transistor whose base is connected to a periodically chargeable and dischargeable capacitor. A regulation of at least one output voltage is preferably provided by underlying voltage regulation in combination with a current-dependent inductance. The switching regulator can be advantageously employed as a feeding apparatus in electrical communications transmission technology.

The present invention is directed to a switching regulator having at least one regulated output voltage.
A switching regulator is disclosed in U.S. Ser. No. 941,448 filed Oct. 26, 1992. In this switching regulator, a device for peak value current limitation is provided, whereby a comparator has one input connected to a reference voltage and the other input connected to a current-measuring resistor. A delta voltage source is arranged in series with the current-measuring resistor.
The delta voltage source supplies an external, synchronous delta signal that is superimposed on the current-meter voltage. Such a superimposition of an external, synchronous delta signal, (disclosed in German Published application 26 13 896) is advantageous in the evaluation of the current-meter voltage with the use of a comparator. On one hand, a defined switch criterion is acquired; on the other hand, the stability in the sub-harmonic range is enhanced.
In a version of the known converter, the multiplier resistor simultaneously serves as actual value generator of a current regulator having superimposed voltage regulation, whereby the actual value of the voltage is the rated value of the current regulation. In such a current mode regulation, a current signal, that serves as turn-off criterion for the pulse duty control, is necessary that is made available to the control circuit as voltage drop-off across a current-measuring resistor or as load voltage of a current transformer.
European reference EP 0 302 433 A1 discloses that forward converters or reverse converters should be provided with current-dependent magnet component parts, for example with what are referred to as non-linear inductors whose inductance decreases with decreasing DC load.
In the reverse converter, a storage transformer having a current-dependent ferrite core effects a noticeably extended current conduction time in the secondary circuit given a weak load. This improves to a considerable extent various properties of the converter, particularly the smallness of the superimposed alternating voltage and the radio interference suppression.
In the forward converter, use of current-independent storage inductors in the low-ass filter that forms the average value is expedient when, for example, a gap-free operation is to be avoided given a great load range and a plurality of output circuits. Such a current-dependent magnet component part also allows extremely low thresholds, so that the internal losses in the current supply device can be kept low.
When a converter is only slightly loaded at the output, then there is a comparatively small voltage drop across the current-measuring resistor. When the level of the current-meter voltage serving as a turn-off criterion is selected so high that an adequately exact turn-off is guaranteed given low-load operation, there is a correspondingly high dissipated power at the current-measuring resistor given maximum nominal load.
In order to utilize the advantages of a magnet component part having current-dependent inductance in combination with the advantageous voltage regulation with underlying current regulation (current mode regulation), then the problem arises that the current-meter voltage and the chronological rise of the current-meter voltage given low load is even lower than when a current-independent inductance is used.

Switching regulator having at least one regulated output voltage


An electronic cigarette case includes a box body, a box cover hinged to the box body and an opening and closing mechanism. The opening and closing mechanism includes a spring piece built in the box body and an arc-shaped bulge formed on the box cover. The arc-shaped bulge clamped between the spring piece and inner wall of the box body and slidingly contact with the spring piece. When the box cover rotates a first predetermined angle relative to the box body, the spring piece drives the bulge to slide relative to the spring piece until the box cover is fully open. When the box cover rotates a second predetermined angle relative to the box body, the spring piece drives the arc-shaped bulge to slide relative to the spring piece until the box cover is fully closed. Thus, it is convenient to open or close the electronic cigarette case which has a simplified structure.

Nowadays, two methods are adopted to open flip-open covers of existing electronic cigarette cases. One method is manually opening, that is, opening a flip-open cover by a hand without the use of any flick mechanism. The other method is using torsional spring mechanisms, that is, opening a flip-open cover by torque force generated by a torsional spring mounted on a rotation axle of the electronic cigarette case cover. In the two above-mentioned methods, a drawback of manually opening is embodied in failing to open and close a flip-open cover automatically using a flick mechanism, which may cause the opening operation to be inconvenient. Adopting the torsional spring mechanism can provide force for opening the flip-open cover, however, the torsional spring mechanism has complicated structure and irregular appearance. This method needs to add a press button or push button, and, the appearance of an electronic cigarette case using the torsional spring mechanism may be affected by the torsional spring exposed out of a surface of the case.


The invention relates to cyclin dependent kinase inhibitor compounds and methods of identifying and using them. The invention further relates to pharmaceutical compositions for treating cell proliferative disorders, especially cancer.

Cancer is a disease of uncontrolled cell division. Tumor cells achieve this state by overriding signals from growth inhibitory factors such as Transforming Growth Factor-β (TGFβ) [2-4] and acquiring constitutive activation of mitogenic signaling pathways such as the mammalian Target of Rapamycin (mTOR)/p70s6k pathway [5,6]. It has been demonstrated that activation of the TGFβ signaling pathway and simultaneous inactivation of mTOR signaling by the TOR inhibitor rapamycin synergize to inhibit the proliferation of human mammary carcinoma cells [7,8]. TGFβ+rapamycin-induced inhibition of cancer cell proliferation is caused by a dramatic increase in the association of the cyclin-dependent kinase inhibitor p27kip1 with the cyclin-dependent kinase Cdk2.
Despite the potent cytostatic action of TGFβ+rapamycin treatment on cancer cells in vitro, it is unlikely that this therapeutic strategy can be directly employed clinically. In addition to inhibiting cell proliferation, TGFβ also exhibits pro-tumorigenic [9-11] and pro-fibrotic [12] effects, and it would be difficult to deliver to cancers. Rapamycin derivatives RAD001 and CCI-779 are currently in clinical trials against several types of human tumors, and based on current data, have the potential to prove useful as cancer therapeutics. A drawback of using rapamycin as a cancer therapeutic is that it acts as an immunosuppressant by inhibiting the proliferation of B-cells and T-cells in addition to inhibiting cancer cell division.

University of Florida Research Foundation, Inc.


The invention relates to machines and methods for separative machining of plate-shaped workpieces by a processing beam. The machines include a first movement unit configured to move the workpiece in a first direction and a second movement unit including a machining head configured to emit the processing beam. The second movement unit is configured to move the machining head in a second direction perpendicular to the first direction to direct the processing beam onto the workpiece. The machines include a first workpiece support unit including a first workpiece-bearing face and a second workpiece support unit including a second workpiece-bearing face spaced apart by a gap from the first workpiece support unit and the first workpiece-bearing face. The gap extends along the second direction. The machines include at least one support slide arranged to move in the second direction within the gap and including a support slide bearing face.

Japanese patent publication JP 5050346A discloses a machine for the separative machining of plate-shaped workpieces by means of a laser beam, in the form of a combined laser and punch machine. The machine disclosed by JP 5050346A implements hybrid motion control in which the workpiece is moved in a first direction (direction X), and the machining head is moved in a second direction (direction Y). The workpiece bearing is discontinuous in the displacement range of the machining head to prevent the workpiece bearing from being in a line of sight of the processing beam to avoid damaging the workpiece bearing by the processing beam. In particular, the workpiece bearing may be split and/or include a gap that extends in the Y direction between two workpiece-bearing faces or workpiece bearings. The processing beam that has passed through the workpiece and any slag and cutting waste that may arise are expelled therethrough. The processing beam may be a laser beam, but the use of a water jet or of another type of high power beam, for example in the form of a plasma arc, is also possible.
Particularly in the case of such a laser processing machine having an additional axis for moving the machining head in the direction X, it is advantageous for the gap in the workpiece bearing to have a minimum width that corresponds to at least the displacement range of the machining head in the direction X. The additional axis permits the machining head to be displaced with a high level of dynamics within the gap. On the other hand, a wide gap allows small to medium-size cutting waste, residual mesh parts, or comparatively small workpiece parts, which may be separated from one another and from the slag for example with the aid of parts chutes, to fall freely. Small parts may be removed from the cutting region in a significantly more rapid manner than by way of the pivoting movement of a discharge flap provided for this purpose.
However, a large gap width may also have a negative effect when performing the separating cuts of comparatively small workpiece parts, since small workpiece parts are not adequately supported in the gap region and by virtue of the high gas pressure of the cutting gas or water, respectively, that exits from the processing nozzle on the machining head and impacts the cut off workpiece parts, the small workpiece parts can potentially tilt in the gap and in some instances potentially catch on the residual workpiece.
Japanese patent publication JP2000246564 A2 discloses a laser and punch machine in which the workpiece is moved in the direction X and a punching die and blanking die are conjointly moved in the direction Y. For this purpose, the punching die and the blanking die by way of lever arms and universal joints are intercoupled and coupled to a common drive.
Japanese patent publication JP2030332 A1 describes a machine for thermal cutting and punching of workpieces, wherein a laser cutting-head is displaced in direction X and direction Y by means of two driven slides. The machine has a workpiece receptacle that is displaceable in direction Y synchronously to the laser cutting-head.
German publication DE 39 17 253 C2, discloses a device for cutting layered strip material that has a frame and a retaining belt that is moveable to and fro in the longitudinal direction of the frame. In certain examples, the device has a cutting head that in a running component, which is moveable to and fro in the longitudinal direction of the frame, is retained such that said cutting head is moveable to and fro in the transverse direction. The device has a lower receptacle component that is fastened to the running component and has a groove-shaped cross section. A plurality of interconnected locking plates that in the transverse direction are moveable to and fro so as to be synchronous with the cutting head are received in the receptacle component. A cutting-receptacle sleeve that supports a tip of the cutting unit may be fitted between the locking plates. Instead of the cutting head, a nozzle head for ejecting an ultra-high pressure liquid may be provided on the running component. In this case, a liquid receptacle sleeve is fitted between the locking plates.

Machines for the separative machining of plate-shaped workpieces


In accordance with embodiments of the present disclosure, a method may include receiving a digital input signal at a first integrated circuit from a second integrated circuit, receiving a supply voltage at the first integrated circuit from the second integrated circuit, generating an analog output signal from the digital input signal, predicting a distortion of the analog output signal based on the digital input signal and the supply voltage, and controlling a gain applied to at least one of the digital input signal and the analog output signal based on the predicting.

Personal audio devices, including wireless telephones, such as mobile/cellular telephones, cordless telephones, mp3 players, and other consumer audio devices, are in widespread use. Such personal audio devices may include circuitry for driving a pair of headphones or one or more speakers. Such circuitry often includes a power amplifier for driving an audio output signal to headphones or speakers.
In some personal audio devices, changes in a modulation index of a signal processing circuit may lead to signal distortion, such as a signal being clipped by a supply voltage providing power to the signal processing circuit.

Systems and methods for preventing distortion due to supply-based modulation index changes in an audio playback system


A device for simultaneously edge sealing and gas filling an insulated glass unit, the insulated glass unit including a supporting structure that supports the insulated glass unit in a working position and a gas filling module including a gas fill injection structure and a displaced air extraction structure and a gas metering unit. The device also includes an edge sealing module having a sealant metering device, an edge sealing dispensing head, and an edge sealing dispensing nozzle. The device also includes a control device programmed with an algorithm to initiate gas filling substantially simultaneously with initiating edge sealing of the insulated glass unit and to complete the gas filling of the insulated glass unit prior to completion of the edge sealing.

Insulated glass is heavily utilized in modern residential and commercial construction. In many areas of the country it is required by building code as an energy conservation measure. A single pane of glass alone has very little insulating value. Multi-pane insulated glass windows have much greater insulating value. Insulated glass units (IGUs) generally include two panes of glass separated by a space. Sealants and adhesives are used to bond the glass panes to a perimeter spacer which separates the two panes of glass. The entire perimeter including the two panes of glass and the spacer are sealed to one another to eliminate movement of ambient air into the space between the two panes of glass. The space is filled with dehydrated air or more commonly another gas such as argon, xenon or krypton. Sulfur hexafluoride is also used for gas filling. The filling of insulated glass units with argon or another gas that is not air has been found to increase the energy efficiency of the insulated glass units markedly. Some insulated glass units includes three panes of glass with two intervening spaces which are similarly filled with argon or another gas other than air and then edge sealed.
Current technology includes a number of techniques for filling insulated glass units with gases other than air. According to some techniques, the insulated glass unit is assembled in a chamber filled with the argon or other gas, trapping the argon between the two panes and within the spacer. In other techniques, the insulated glass unit is preassembled, the argon or other gas is injected while air is removed and then the insulated gas unit is edge sealed.
In any case, the construction of insulated glass units generally involves the use of two separate manufacturing stations, two separate processes and two separate operators to gas fill and edge seal insulated glass units plus time utilized to do the separate operations.

Apparatus for edge sealing and simultaneous gas filling of insulated glass units


A ceiling type air conditioner including an indoor unit having a built-in heat exchanger and a built-in blower, and having a plurality of blowing passages for discharging, to the outside, air having passed through the heat exchanger; a discharge panel having a plurality of inlets into which air discharged through the plurality of blowing passages is delivered, an inner space at least partially communicating with the partiality of inlets, and a ring-or arc-shaped opening for discharging, into a room, air flowing into the inner space; and an air guide module mounted to the discharge panel, and moved upward and downward or rotated so as to vary airflow discharged through the opening.

An air conditioner is a device that creates a more comfortable indoor environment for a user.
An air conditioner may cool or heat a room by using a refrigerating cycle apparatus including a compressor, a condenser, an expansion mechanism, and an evaporator through which a refrigerant is circulated.
The air conditioner may be classified into a stand type air conditioner, a wall-mounted air conditioner, and a ceiling type air conditioner according to installation positions.
The ceiling type air conditioner is installed on the ceiling to discharge cold or warm air into the room.
Recently, ceiling type air conditioners having a circular shape have been manufactured.
For example, referring to Korean Patent Publication No. 10-0897425, an air conditioner including a front panel having an open portion formed with an intake port through which external air is introduced and a discharge port through which the introduced internal air is discharged and a separating guide provided in the open portion of the front panel and having a ring shape so that the intake port is located on an inner side and the discharge port is located at an outer circumference is disclosed.
According to the air conditioner of the related art as described above, heat-exchanged air may be evenly discharged in all directions (360°) in the room through the ring-shaped integrated discharge port.
However, the circular air conditioner as described above has a problem in that a vane for controlling an air flow angle is omitted due to a structural defect that a gap is formed at a central portion, and thus, air flow control is not smoothly performed.
In addition, it is necessary to induce a horizontal air flow to provide indirect air to the user in the case of cooling and it is necessary to induce a vertical air flow to prevent air returning (short-circuit) in the case of heating, but the circular air conditioner of the related art is difficult to induce both horizontal and vertical air flows.
In addition, during the heating operation, a weakly spreading flow is re-absorbed at a corner of the discharge port, thereby degrading performance of the air conditioner.


A method is provided for controlling the quality of a fiberglass mat. The method includes the steps of dyeing a test specimen of the fiberglass mat, scanning the test specimen with an optical detector to collect color data and comparing the color data to a predetermined standard to determine if the fiberglass mat is within the desired product specification.

Fiberglass mats are made from fiberglass and a polymer binder which is applied to hold the mat together. The fiberglass may take the form of a continuous strand or staple fibers that are cut and chopped to a desired length. Typically the fiberglass is deposited onto a moving belt where a binder is applied. The materials are then cured in an oven at a predetermined curing temperature for a predetermined curing time in order to bind the glass fibers together and provide the mat with consistent shape.
In order to be useful for its intended purpose, the fiberglass mat must be characterized by specified properties. The level of cure provided in the fiberglass mat determines a great many of these properties. As a consequence, good quality control requires the manufacturer to monitor and maintain a proper level of cure in a fiberglass mat product. Toward this end, a number of methods have been utilized to allow the manufacturer to monitor and determine the level of cure in a fiberglass mat product.
U.S. Pat. No. 7,063,983 to Chen discloses a method for determining cure in a polycarboxylic acid bindered material that uses a solution which indicates the degree of cure based on the color the solution turns after being sprayed upon the article.
U.S. Pat. No. 4,609,628 to Ashtenbeck discloses a method for determining binder content and degree of cure in a fibrous mat utilizing electromagnetic radiation.
U.S. Pat. No. 4,582,520 to Sterm and U.S. Pat. No. 5,457,319 to Moe et al disclose processes for measuring a degree of cure through the use of infrared radiation.
It is also known to utilize what is referred to in the art as the "red dye test" in order to determine the level of cure in a fiberglass mat. In accordance with the state of the art red dye test, a test sample is cut from a finished roll of fiberglass mat. The sample is then submerged into a red dye bath to ensure that it is completely saturated with the dye. The sample is then rinsed with fresh water. Excess water is then removed from the sample. The sample is then visually compared to a predetermined standard to determine if the finished mat is within specification.
The present invention relates to a new and improved method for controlling quality of a fiberglass mat that is more accurate and efficient than the state of the art red dye test.

Method for controlling quality of a fiberglass mat


A frequency detector for use with a PLL utilizes a counter and a preset value to produce frequency information related to a VCO signal. The frequency information is used to control the frequency of the VCO signal and to determine whether the VCO signal should be controlled by the frequency detector or a phase detector. Using the counter and preset value involves establishing a preset value that is used to obtain the desired frequency information. The preset value is set such that the counter is at one-half full-scale at the end of a known time period when the VCO signal is oscillating at a target frequency. When the preset value is set to such a value, the most significant bit of the counter after the known time period indicates whether the frequency of the VCO signal is above or below the target frequency.

Phase-locked loops (PLLs) are used in data communications and telecommunications applications to lock onto the frequency of a signal. In particular, PLLs are often used in serializer/deserializer (SerDes) applications. A typical PLL includes a phase detector, a loop filter, and a voltage controlled oscillator (VCO) that produces a VCO signal. The phase detector compares an input signal with a portion of the VCO signal and produces an output that indicates the relative phase of the two signals. The output is provided to the loop filter and in response, the loop filter produces a voltage that causes the phase of the VCO signal to move closer to the input signal. A portion of the VCO signal is then looped back to the phase detector in a continuous process. When the loop is locked, the frequency and phase of the VCO signal track the frequency and phase of the input signal.
An important characteristic of a PLL is its ability to lock the VCO signal to the input signal even when the initial frequency of the VCO signal is far away from the frequency of the input signal. For example, the frequency of the input and VCO signals may be far apart when a PLL is first powered up, when there is a change to the applied input signal frequency, or when the input signal is reapplied to the PLL after a long absence.
A central component in ensuring signal lock is the phase detector. There are generally two classes of phase detectors, analog and digital. With a digital phase detector, if the frequency difference between the input and VCO signals is too large (typically greater than 1%), it is difficult for the PLL to achieve lock. Separate frequency detectors have been added to PLLs with digital phase detectors to ensure that the PLLs are able to achieve lock when the frequencies of the input and VCO signals are far apart (i.e., outside the capture range of the digital phase detector). A frequency detector typically uses an external reference clock to measure the frequency of the VCO signal. The measured frequency of the VCO signal is used to determine. whether or not the frequency detector should assert control over the VCO signal. If the frequency detector is to assert control over the VCO signal, then the frequency detector is used to pull the frequency of the VCO signal close to a pre-established target frequency. Once the frequency of the VCO signal is within the capture range of the phase detector, control of the VCO is switched over to the phase detector.
Many different techniques for frequency detection in PLLs have been developed. Although these techniques work well, there is still a need for a flexible frequency detection technique that supports a wide range of target and reference clock frequencies and that asserts control over the VCO signal at the proper time.

Programmable frequency detector for use with a phase-locked loop


A system and method for efficiently scheduling memory access requests from a display controller pipeline. The display controller monitors the amount of data in the line buffers in the internal pixel-processing pipelines. The display controller waits until the amount of data in a given line buffer has fallen below an amount equal to the pixel width of the region being rendered by the internal pixel-processing pipeline before issuing memory requests to the memory controller. When the memory controller is not processing received memory requests, the memory controller transitions to a low-power state.

1. Field of the Invention
This invention is related to the field of digital systems and, more particularly, to low power mechanisms for managing displays in digital systems.
2. Description of the Relevant Art
As the power and complexity of computer systems increase, graphics operations are increasingly being performed using dedicated graphics rendering hardware. Accordingly, a graphics processing unit (GPU) may include various built-in and configurable structures within a display pipe for rendering images of pixel data to be presented via a display. These structures may implement various pipeline stages corresponding to, for example, rasterisation, overlaying, blending, clipping, dithering, color space conversion, frame rotation, frame buffering, etc.
In one embodiment, a video subsystem in a computing system may include multiple sources for video data. The design of a smartphone or computer tablet may include user interface layers, cameras, and video sources such as media players. Each of these sources may utilize video data stored in memory. A corresponding display controller may include multiple internal pixel-processing pipelines for these sources. Each memory request sent from the video subsystem includes both overhead processing and information retrieval processing. A large number of requests may create a bottleneck in the memory subsystem, and the repeated overhead processing may reduce the subsystem performance.
In order to minimize power consumption of the overall system, the system should attempt to enter a low-power mode whenever traffic is not being sent over the communication fabric to the memory controller. However, the memory subsystem may be unable to enter a low-power mode as one or more display pipelines continuously access the memory. The memory may be off-die synchronous dynamic random access memory (SDRAM) used to store frame data in frame buffers. The accesses of the SDRAM consume an appreciable amount of power in addition to preventing the memory subsystem from entering a low-power mode.
In view of the above, methods and mechanisms for minimizing the power consumption of a display pipeline are desired.


A video content matching system includes a computing platform having a hardware processor and a memory storing a software code. When executed, the software code obtains a reference digital profile of a reference video segment, obtains a target digital profile of target video content, and compares the reference and target digital profiles to detect a candidate video segment of the target video content for matching to the reference video segment. The software code also frame aligns reference video frames of the reference video segment with corresponding candidate video frames of the candidate video segment to provide frame aligned video frame pairs, pixel aligns the frame aligned video frame pairs to produce frame and pixel aligned video frame pairs, and identifies, using the frame and pixel aligned video frame pairs, the candidate video segment as a matching video segment or a non-matching video segment for the reference video segment.

Due to the popularity of video as an entertainment medium, video distribution via television (TV) broadcasts and Internet video streams are also very effective channels for the distribution of advertising (ads). Some of those ads may be relatively insensitive to the passage of time due to their being directed to goods that are consistently available. For example, ads directed to clothing or over-the-counter medications may change seasonally but not daily or weekly, while ads directed to automobiles or cosmetics may remain substantially unchanged for many months. Other types of ads may be highly time sensitive, however, and may lose their value, or even become liabilities if their presentation to consumers is mistimed. Examples of such time sensitive ads are ads for upcoming events, such as a sporting events or movie releases, or for video content scheduled to air at a future date or at a later time.
Time sensitive ads for an upcoming event may be produced in multiple versions, and the order and timing with which those versions of the same core ad are presented to consumers may be very important. Mistakes with respect to that order or timing may undermine the success of an advertising campaign, and may even affect the reputation of the ad sponsor. For instance, an ad promoting an "upcoming event" that airs after the event may damage the credibility of the ad sponsor with consumers. Nevertheless, the policing of ad placement can be a time consuming and expensive process when performed manually, by a human editor. Even conventional automated techniques for searching video are typically too inefficient to provide an effective solution. Consequently, there is a need in the art for a fast video content matching solution enabling the identification of ads or other short video segments included in a longer video broadcast or stream.


Disclosed are a signal distortion component adjusting apparatus and method capable of adjusting error vector magnitude of subcarriers of a predetermined position by adjusting a signal distortion component occurring while decreasing a peak to average power ratio (PAPR) in a communication system of an orthogonal frequency division multiplexing (OFDM) technology or an orthogonal frequency division multiple access (OFDMA) scheme, and a system using the same. The present invention includes a signal distortion component adjusting unit to add an additional signal distortion component Pe((n+N/2) % N) to a signal distortion component e(n) that is obtained by subtracting a threshold Th value, set to decrease peak power, from an absolute value of a time domain signal x(n) of an input signal, and to thereby adjust the signal distortion component. The present invention may transmit a highly reliable signal by adjusting error vector magnitude of subcarrier of a frequency domain.

As a demand for a large data service such as various multimedia Internet services is increasing in wireless communication, an orthogonal frequency division multiplexing (OFDM) technology and an orthogonal frequency division multiple access (OFDMA) scheme are in the spotlight as a wireless transmission technology capable of satisfying the demand.
The OFDM technology is a multiplexing technology in an aspect of simultaneously transmitting data using multiple channels and is also a kind of modulation technology in an aspect of dividing data and thereby transmitting the data using multiple subcarriers.
The OFDMA scheme is a scheme in which a plurality of users is differently allocated with a set of valid subcarriers and thereby uses the allocated subcarriers instead of a scheme in which a single user exclusively uses all the valid subcarriers.
The OFDM technology or the OFDMA scheme is applied to standards such as an Institute of Electrical and Electronics Engineers (IEEE) 802.16e wireless broadband (WiBro) standard, a mobile worldwide interoperability for microwave access (WiMAX) standard, a wireless local area network (WLAN) standard, a 3rd generation partnership project-long term evolution (3GPP-LTE) standard, and the like.
In the OFDM technology or the OFDMA scheme, a transmitted signal becomes a time domain signal that is inverse fast Fourier transformed (IFFT) based on a symbol unit. The IFFT signal has a characteristic in which magnitude of a signal is not consistently maintained. Due to the above characteristic, a peak to average power ratio (PAPR) is very great in the OFDM technology or the OFDMA scheme compared to other modulation schemes.
Since a PAPR is great in the OFDM technology or the OFDMA scheme, the OFDM technology or the OFDMA scheme may not efficiently use a power amplifier. Accordingly, the OFDM technology or the OFDMA scheme requires a technology to efficiently decrease the PAPR.
A variety of methods, for example, a peak cancellation crest factor reduction (PC-CFR) using a cancellation pulse generator (CPG), filtering, and the like may be employed as a method to decrease a PAPR. However, such method to decrease a PAPR may generate a signal distortion in all the frequency domains using a scheme of removing a predetermined portion of a peak value and the like.

Apparatus and method for controlling distortion signal and system by using the same

Electronics and Telecommunications Research Institute


Alpha-olefins are manufactured in high yield and with very high selectivity by contacting ethylene with an iron complex of a selected 2,6-pyridinedicarboxaldehyde bisimine or a selected 2,6-diacylpyridine bisimine, and in some cases a selected activator compound such as an alkyl aluminum compound. Novel bisimines and their iron complexes are also disclosed. The xcex1-olefins are useful as monomers and chemical intermediates.

Alpha-olefins may be manufactured in high yield and with very high selectivity by contacting ethylene with an iron complex of a selected 2,6-pyridinedicarboxaldehyde bisimine or a selected 2,6-diacylpyridine bisimine, and usually a selected activator compound.
Alpha-olefins, especially those containing about 6 to about 20 carbon atoms, are important items of commerce, with about 1.5 million tons reportedly being produced in 1992. The xcex1-olefins are used as intermediates in the manufacture of detergents, as monomers (especially in linear low density polyethylene), and as intermediates for many other types of products. As a consequence, improved methods of making these compounds are of interest.
Most commercially produced xcex1-olefins are made by the oligomerization of ethylene, catalyzed by various types of compounds, see for instance B. Elvers, et al., Ed. Ullmann""s Encyclopedia of Industrial Chemistry, Vol. A13, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p. 243-247 and 275-276, and B. Cornils, et al., Ed., Applied Homogeneous Catalysis with Organometallic Compounds, A Comprehensive Handbook, Vol. 1, VCH Verlagsgesellschaft mbH, Weinheim, 1996, p. 245-258. The major types of commercially used catalysts are alkylaluminum compounds, certain nickel-phosphine complexes, and a titanium halide with a Lewis acid such as AlCl3. In all of these processes significant amounts of branched and/or internal olefins and/or diolefins, are produced. Since in most instances these are undesired, and often difficult to separate from the desired linear xcex1-olefins, minimization of these byproducts is sought.
This invention concerns a first process for the production of xcex1-olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +300xc2x0 C., a compound of the formula
with ethylene and:
(a) a first compound W, which is a neutral Lewis acid capable of abstracting Xxe2x88x92 an alkyl group or a hydride group from Fe to form WXxe2x88x92, (WR20)xe2x88x92 or WHxe2x88x92 and which is also capable of transferring an alkyl group or a hydride to Fe, provided that WXxe2x88x92 is a weakly coordinating anion; or
(b) a combination of second compound which is capable of transferring an alkyl or hydride group to Fe and a third compound which is a neutral Lewis acid which is capable of abstracting Xxe2x88x92, a hydride or an alkyl group from Fe to form a weakly coordinating anion;
wherein:
each X is an anion;
n is 1, 2 or 3 so that the total number of negative charges on said anion or anions is equal to the oxidation state of an Fe atom present in (I);
R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R8 is a primary carbon group, a secondary carbon group or a tertiary carbon group; and
R20 is alkyl;
and provided that:
when R8 is a primary carbon group none, one or two of R12, R13 and R17 are primary carbon groups, and the remainder of R12, R13 and R17 are hydrogen;
when R8 is a secondary carbon group, none or one of R12, R13 and R17 is a primary carbon group or a secondary carbon group and the remainder of R12, R13, and R17 are hydrogen;
when R8 is a tertiary carbon group all of R12, R13 and R14 are hydrogen; and
any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 vicinal to one another, taken together may form a ring.
Also disclosed herein is a compound of the formula
wherein:
each X is an anion;
n is 1, 2 or 3 so that the total number of negative charges on said anion or anions is equal to the oxidation sate of a Fe atom present in (I);
R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and
R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R8 is a primary carbon group, a secondary carbon group or a tertiary carbon group;
and provided that:
when R8 is a primary carbon group none, one or two of R12, R13 and R17 are primary carbon groups, and the remainder of R12, R13 and R17 are hydrogen;
when R8 is a secondary carbon group, none or one of R12, R13 and R17 is a primary carbon group or a secondary carbon group and the remainder of R12, R13, and R17 are hydrogen; and
when R8 is a tertiary carbon group all of R12, R13 and R14 are hydrogen; any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 vicinal to one another, taken together may form a ring.
This invention includes a compound of the formula
wherein:
R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and
R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R8 is a primary carbon group, a secondary carbon group or a tertiary carbon group;
and provided that:
when R8 is a primary carbon group none, one or two of R12, R13 and R17 are primary carbon groups, and the remainder of R12, R13 and R17 are hydrogen;
when R8 is a secondary carbon group, none or one of R12, R13 and R17 is a primary carbon group or a secondary carbon group and the remainder of R12, R13, and R17 are hydrogen;
when R8 is a tertiary carbon group all of R12, R13 and R14 are hydrogen; and
any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 vicinal to one another, taken together may form a ring.
This invention also concerns a second process for the production of xcex1-olefins, comprising contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +300xc2x0 C., a Fe[II] or Fe[III] complex of a tridentate ligand of the formula
with ethylene, wherein:
R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R8 is a primary carbon group, a secondary carbon group or a tertiary carbon group;
and provided that:
when R8 is a primary carbon group none, one or two of R12, R13 and R17 are primary carbon groups, and the remainder of R12, R13 and R17 are hydrogen;
when R8 is a secondary carbon group, none or one of R12, R13 and R17 is a primary carbon group or a secondary carbon group and the remainder of R12, R13, and R17 are hydrogen;
when R8 is a tertiary carbon group all of R12, R13 and R14 are hydrogen;
any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 vicinal to one another, taken together may form a ring;
an Fe[II] or Fe[III] atom also has bonded to it an empty coordination site or a ligand that may be displaced by said ethylene, and a ligand that may add to said ethylene.
This invention also includes a compound of the formula
wherein:
R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl,
R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R8 is a primary carbon group, a secondary carbon group or a tertiary carbon group;
T1 is hydride or alkyl or any other anionic ligand into which ethylene can insert;
Y is a vacant coordination site, or neutral ligand capable of being displaced by ethylene;
Q is a relatively non-coordinating anion; and
P is a divalent (poly)ethylene group of the formula xe2x80x94(CH2CH2)xxe2x80x94 wherein x is an integer of 1 or more;
and provided that:
when R8 is a primary carbon group none, one or two of R12, R13 and R17 are primary carbon groups, and the remainder of R12, R13 and R17 are hydrogen;
when R8 is a secondary carbon group, none or one of R12, R13 and R17 is a primary carbon group or a secondary carbon group and the remainder of R12, R13, and R17 are hydrogen;
when R8 is a tertiary carbon group all of R12, R13 and R14 are hydrogen; and
any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 vicinal to one another, taken together may form a ring.
This invention also concerns a third process for the production of xcex1-olefins, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +300xc2x0 C., ethylene and a compound of the formula
wherein:
R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl,
R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R8 is a primary carbon group, a secondary carbon group or a tertiary carbon group;
T1 is hydride or alkyl or any other anionic ligand into which ethylene can insert;
Y is a vacant coordination site, or a neutral ligand capable of being displaced by ethylene;
Q is a relatively non-coordinating anion; and
P is a divalent (poly)ethylene group of the formula xe2x80x94(CH2CH2)xxe2x80x94 wherein x is an integer of 1 or more;
and provided that:
when R8 is a primary carbon group none, one or two of R12, R13 and R17 are primary carbon groups, and the remainder of R12 R13 and R17 are hydrogen;
when R8 is a secondary carbon group, none or one of R12, R13 and R17 is a primary carbon group or a secondary carbon group and the remainder of R12, R13, and R17 are hydrogen;
when R8 is a tertiary carbon group all of R12, R13 and R14 are hydrogen; and
any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 vicinal to one another, taken together may form a ring.
Herein, certain terms are used. Some of them are:
A xe2x80x9chydrocarbyl groupxe2x80x9d is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
By xe2x80x9csubstituted hydrocarbylxe2x80x9d herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of xe2x80x9csubstitutedxe2x80x9d are heteroaromatic rings.
By xe2x80x9c(inert) functional groupxe2x80x9d herein is meant a group other than hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions to which the compound containing the group is subjected. The functional groups also do not substantially interfere with any process described herein that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo), ether such as xe2x80x94OR18 wherein R18 is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be near an iron atom, such as R4, R5, R8, R12 R13, and R17 the functional group should not coordinate to the iron atom more strongly than the groups in compounds containing R4, R5, R8, R12, R13 and R17 which are shown as coordinating to the iron atom, that is they should not displace the desired coordinating group.
By an xe2x80x9calkyl aluminum compoundxe2x80x9d is meant a compound in which at least one alkyl group is bound to an aluminum atom. Other groups such as alkoxide, oxygen, and halogen may also be bound to aluminum atoms in the compound. See below for preferred alkylaluminum compounds.
By xe2x80x9cneutral Lewis basexe2x80x9d is meant a compound, which is not an ion, which can act as a Lewis base. Examples of such compounds include ethers, amines, sulfides, and organic nitriles.
By xe2x80x9ccationic Lewis acidxe2x80x9d is meant a cation which can act as a Lewis acid. Examples of such cations are sodium and silver cations.
By relatively noncoordinating (or weakly coordinating) anions are meant those anions as are generally referred to in the art in this manner, and the coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al., Chem. Rev., vol. 88 p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942 (1993), both of which are hereby included by reference. Among such anions are those formed from alkylaluminum compounds, defined above, and Xxe2x88x92, including R93AlXxe2x88x92, R92AlClXxe2x88x92, R9AlCl2Xxe2x88x92, and xe2x80x9cR9AlOXxe2x88x92xe2x80x9d. Other useful noncoordinating anions include BAFxe2x88x92 {BAF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate}, SbF6xe2x88x92, PF6xe2x88x92, and BF4xe2x88x92, trifluoromethanesulfonate, p-toluenesulfonate, (RfSO2)2Nxe2x88x92 (wherein Rf is perfluoroalkyl), and (C6F5)4Bxe2x88x92.
By formation of an xcex1-olefin is meant formation of a compound (or mixture of compounds) of the formula H(CH2CH2)qCHxe2x95x90CH2 wherein q is an integer of 1 to about 18. In most such reactions, a mixture of compounds will result which have differing values of q, and in most reactions to form the xcex1-olefins some of the xcex1-olefins formed will have q values of more than 18. Preferably less than 50 weight percent, more preferably less than 20 weight percent of the product mixture will have q values over 18. The product mixture may contain small amounts (preferably less than 30 weight percent, more preferably less than 10 weight percent, and especially preferably less than 2 weight percent) of other types of compounds such as alkanes, branched alkenes, dienes, and/or internal olefins.
By an empty coordination site is meant a potential coordination site that does not have a ligand bound to it. Thus if an ethylene molecule is in the proximity of the empty coordination site, the ethylene molecule may coordinate to the metal atom.
By a xe2x80x9cprimary carbon groupxe2x80x9d herein is meant a group of the formula xe2x80x94CH2 xe2x80x94xe2x80x94xe2x80x94, wherein the free valence xe2x80x94xe2x80x94xe2x80x94 is to any other atom (the bond represented by the hyphen is to the benzene ring to which the primary carbon group is attached). Thus the free valence xe2x80x94xe2x80x94xe2x80x94 may be bonded to a hydrogen atom, halogen atom, a carbon atom, an oxygen atom, a sulfur atom, etc. In other words, the free valence xe2x80x94xe2x80x94xe2x80x94 may be to hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group. Examples of primary carbon groups include xe2x80x94CH3, xe2x80x94CH2CH(CH3)2, xe2x80x94CH2Cl, xe2x80x94CH2C6H5, xe2x80x94OCH3 and xe2x80x94CH2OCH3.
By a secondary carbon group is meant the group
wherein both free bonds represented by the dashed lines are to an atom or atoms other than hydrogen. These atoms or groups may be the same or different. In other words the free valences represented by the dashed lines may be hydrocarbyl, substituted hydrocarbyl or functional groups. Examples of secondary carbon groups include xe2x80x94CH(CH3)2, xe2x80x94CHCl2, xe2x80x94CH(C6H5)2, cyclohexyl, xe2x80x94CH(CH3)OCH3, and xe2x80x94CHxe2x95x90CCH3.
By a xe2x80x9ctertiary carbon groupxe2x80x9d is meant a group of the formula
wherein the solid line is the bond to the benzene ring and the three free bonds represented by the dashed lines are to an atom or atoms other than hydrogen. In other words, the bonds represented by the dashed lines are to hydrocarbyl, substituted hydrocarbyl or inert functional groups. Examples of tetiary carbon groups include xe2x80x94C(CH3)3, xe2x80x94C(C6H5)3, xe2x80x94CCl3, xe2x80x94C(CH3)2OCH3, xe2x80x94Cxe2x89xa1CH, xe2x80x94C(CH3)CHxe2x95x90CH2, and 1-adamantyl.
By a ligand that may add to ethylene is meant a ligand coordinated to a metal atom into which an ethylene molecule (or a coordinated ethylene molecule) may insert to start or continue an oligomerization. For instance, this may take the form of the reaction (wherein L is a ligand):
Note the similarity of the structure on the left-hand side of this equation to compounds (V) and (VI) (see below).
Compounds useful as ligands are diimines of 2,6-pyridinedicarboxaldehyde or 2,6-diacylpyridines of the general formula
wherein all of the xe2x80x9cRxe2x80x9d groups are as defined above. In preferred compounds (I) and (II), and all other preferred compounds in which the following xe2x80x9cRxe2x80x9d groups appear:
R4 and R5 are methyl or hydrogen; and/or
R1, R2, and R3 are all hydrogen; and/or
R9, R10, R11, R14, R15 and R16 are all hydrogen; and/or
R12 and R17 are each independently methyl, ethyl, propyl or isopropyl, more preferably both are methyl or ethyl; and/or
each X is a monovalent anion, more preferably selected from the group consisting of halide and nitrile.
It is also preferred that in all compounds in which they appear:
if R8 is a primary carbon group, R13 is a primary carbon group and R12 and R17 are hydrogen;
if R8 is a secondary carbon group, R13 is a primary or secondary carbon group, more preferably a secondary carbon group, and R12 and R17 are hydrogen.
In all specific preferred compounds in which they appear it is preferred that:
R4 and R5 are methyl, R9, R10, R11, R14, R15 and R16 are all hydrogen, and R12 and R17 are both methyl;
R4 and R5 are methyl, R9, R10, R11, R14 R15 and R16 are all hydrogen, and R12 and R17 are both ethyl;
R4 and R5 are methyl, R9, R10, R11, R14, R15 and R16 are all hydrogen, and R12 and R17 are both isopropyl;
R4 and R5 are methyl, R9, R10, R11, R14, R15 and R16 are all hydrogen, and R12 and R17 are both n-propyl;
R4 and R5 are methyl, R9 R10, R11, R14, R15 and R16 are all hydrogen, and R12 and R17 are both chloro; and
R4 and R5 are methyl, R9, R10, R11, R14, R15 and R16 are all hydrogen, and R12 and R17 are both trifluoromethyl.
In all of the above specific compounds it is preferred that X is selected from the group consisting of chloride, bromide and nitrate, and more preferably that it is chloride.
Compounds such as (II) and may be made by the reaction of a compound of the formula
with a compound of the formula H2NR6 or H2NR7, wherein R6 and R7 are as described above. These reactions are often catalyzed by carboxylic acids, such as formic acid. Reactions such as these are described in Examples 1-3.
The iron complexes may be formed by reacting the appropriate tridentate ligand with an iron salt such as an iron halide or a compound such as iron [III] nitrate. See Examples 4-6 for preparation of iron complexes.
In the first oligomerization process (to produce xcex1-olefins) described herein an iron complex (I) is contacted with ethylene and a neutral Lewis acid W capable of abstracting Xxe2x88x92, hydride or alkyl (R20) from (I) to form a weakly coordinating anion, and must alkylate or be capable of adding a hydride ion to the iron atom, or an additional alkylating agent or an agent capable of adding a hydride anion to the iron atom must be present. The neutral Lewis acid is originally uncharged (i.e., not ionic). Suitable neutral Lewis acids include SbF5, Ar3B (wherein Ar is aryl), and BF3. Suitable cationic Lewis acids or Bronsted acids include NaBAF, silver trifluoromethanesulfonate, HBF4, or [C6H5NH(CH3)2]+ [B(C6F5)4]xe2x88x92. In those instances in which (I) (and similar catalysts which require the presence of a neutral Lewis acid or a cationic Lewis or Bronsted acid), does not contain an alkyl or hydride group already bonded to the iron atom, the neutral Lewis acid or a cationic Lewis or Bronsted acid also alkylates or adds a hydride to the iron or a separate alkylating or hydriding agent is present, i.e., causes an alkyl group (R20) or hydride to become bonded to the iron atom.
It is preferred that R20 contains 1 to 4 carbon atoms, and more preferred that R20 is methyl or ethyl.
For instance, alkyl aluminum compounds (see next paragraph) may alkylate (I). However, not all alkylaluminum compounds may be strong enough Lewis acids to abstract Xxe2x88x92 or an alkyl group from the iron atom. In that case a separate Lewis acid strong enough to do the abstraction must be present. For instance, (C6F5)3B or (C6H5)3B are useful Lewis acids, and could be used in combination with, for example, an alkylaluminum compound such as triethylaluminum.
A preferred neutral Lewis acid, which can alkylate the iron, is a selected alkyl aluminum compound, such as R193Al, R19AlCl2, R192AlCl, and xe2x80x9cR19AlOxe2x80x9d (alkylaluminoxanes), wherein R19 is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminum compounds include methylaluminoxanes (which are oligomers with the general formula [MeAlO]n), (C2H5)2AlCl, C2H5AlCl2, and [(CH3)2CHCH2]3Al.
Metal hydrides such as NaBH4 may be used to bond hydride groups to the Fe.
In the second oligomerization process described herein an iron complex of (II) is either added to the oligomerization process or formed in situ in the process. In fact, more than one such complex may be formed during the course of the process, for instance formation of an initial complex and then reaction of that complex to form an active ended oligomer containing such a complex.
Examples of such complexes which may be formed initially in situ include
wherein the xe2x80x9cRxe2x80x9d substituents are as defined above, T1 is hydride or alkyl or any other anionic ligand into which ethylene can insert, Y is a vacant coordination site, or a neutral ligand capable of being displaced by ethylene, and Q is a relatively non-coordinating anion. Complexes may be added directly to the process or formed in situ. For instance, (TV) may be formed by the reaction of (I) with a neutral Lewis acid such as an alkyl aluminum compound. Another method of forming such a complex in situ is combining a suitable iron compound such iron chloride, (II) and an alkyl aluminum compound. Other iron salts in which anions similar to chloride are present, and which may be removed by reaction with the Lewis or Bronsted acid. For instance iron halides, nitrates and carboxylates (such as acetates) may be used, particularly if they are slightly soluble in the process medium. It is preferred that these precursor iron salts be at least somewhat soluble in the process medium.
After the ethylene oligomerization has started, the complex may be in a form such as
wherein, as before, the xe2x80x9cRxe2x80x9d substituents and Q are as defined above, and P is a divalent (oligo)ethylene group of the formula xe2x80x94(CH2CH2)xxe2x80x94 wherein x is an integer of 1 or more. The xe2x80x9cend groupxe2x80x9d on P in this instance is written as H, since as the oligomerization proceeds to form
xcex1-olefins, the end group must of necessity be H. It could at some time, especially at the beginning of the oligomerization, be T1. It is preferred that Fe be in +2 oxidation state in (I), (IV), (V) and (VI).
Compounds such as (IV), (V) and (VI) may or may not be stable away from an environment similar to that of the oligomerization process.
(IV), (V) and (VI) may also be used, in the absence of any xe2x80x9cco-catalystsxe2x80x9d or xe2x80x9cactivatorsxe2x80x9d to oligomerize ethylene in a third oligomerization process. Except for the ingredients in the process, the process conditions for the third process, such as temperature, pressure, oligomerization medium, etc., may be the same as for the first and second oligomerization processes, and preferred conditions for those processes are also preferred for the third oligomerization process.
In all the oligomerization processes herein, the temperature at which it is carried out is about xe2x88x92100xc2x0 C. to about +300xc2x0 C., preferably about 0xc2x0 C. to about 200xc2x0 C., more preferably about 50xc2x0 C. to about 150xc2x0 C. It is preferred to carry out the oligomerization under ethylene (gauge) pressures from about 0 kPa to about 35 MPa, more preferably about 500 kPa to about 15 MPa. It is preferred that the oligomerization be carried under conditions at which the reaction is not significantly diffusion limited.
The oligomerization processes herein may be run in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, ethylene, and xcex1-olefin product may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the oligomerization from occurring. Suitable liquids include alkanes, alkenes cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Specific useful solvents include hexane, toluene, the xcex1-olefins themselves, and benzene.
The formation of the xcex1-olefins as described herein is relatively rapid in many instances, and significant yields can be obtained in less than an hour. Under the correct conditions very high selectivity for an xcex1-olefin is shown, see for instance Examples 8-17.
Also under the correct conditions mixtures of xcex1-olefins containing desirable numbers of carbon atoms are obtained. A measure of the molecular weights of the olefins obtained is factor K from the Schulz-Flory theory (see for instance B. Elvers, et al., Ed. Ullmann""s Encyclopedia of Industrial Chemistry, Vol. A13, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p. 243-247 and 275-276. This is defined as:
K=n(Cn+2 olefin)/n(Cn olefin)
wherein n(Cn olefin) is the number of moles of olefin containing n carbon atoms, and n(Cn+2 olefin) is the number of moles of olefin containing n+2 carbon atoms, or in other words the next higher oligomer of Cn olefin. From this can be determined the weight (mass) fractions of the various olefins in the resulting oligomeric reaction product mixture. The K factor is preferred to be in the range of about 0.7 to about 0.8 to make the xcex1-olefins of the most commercial interest. It is also important to be able to vary this factor, so as to produce those olefins which are in demand at the moment. Examples 8 to 17 show that this can be done in the present oligomerization processes.
The xcex1-olefins made herein may be further polymerized with other olefins to form polyolefins, especially linear low density polyethylenes, which are copolymers containing ethylene. They may also be homopolymerized. These polymers may be made by a number of known methods, such as Ziegler-Natta-type polymerization, metallocene catalyzed polymerization, and other methods, see for instance World Patent Application 96/23010, see for instance Angew. Chem., Int. Ed. Engl., vol. 34, p. 1143-1170 (1995), European Patent Application 416,815 and U.S. Pat. No. 5,198,401 for information about metallocene-type catalysts, and J. Boor Jr., Ziegler-Natta Catalysts and Polymerizations, Academic Press, New York, 1979 and G. Allen, et al., Ed., Comprehensive Polymer Science, Vol. 4, Pergamon Press, Oxford, 1989, p. 1-108, 409-412 and 533-584, for information about Ziegler-Natta-type catalysts, and H. Mark, et al., Ed., Encyclopedia of Polymer Science and Engineering, Vol. 6, John Wiley and Sons, New York, 1992, p. 383-522, for information about polyethylenes, and all of these are hereby included by reference.
The xcex1-olefins made herein may be converted to alcohols by known processes, these alcohols being useful for a variety of applications such as intermediates for detergents or plasticizers. The xcex1-olefins may be converted to alcohols by a variety of processes, such as the oxo process followed by hydrogenation, or by a modified single step oxo process (the xe2x80x98modified Shell processxe2x80x99), see for instance B. Elvers, et al., Ed., Ullmann""s Encyclopedia of Chemical Technology, 5th Ed., Vol. A18, VCH Verlagsgesellschaft mbH, Weinheim, 1991, p. 321-327, which is hereby included by reference.
The ethylene oligomerizations herein may also initially be carried out in the solid state by, for instance, supporting and active catalyst or catalyst precursor on a substrate such as silica or alumina. If a catalyst precursor, such as an iron halide or nitrate, it may be activated with a Lewis (such as W, for instance an alkylaluminum compound) and exposing it to ethylene. Alternatively a solution of the catalyst precursor may be exposed to a support having an alkylaluminum compound on its surface. The support may also be able to take the place of the Lewis or Bronsted acid, for instance an acidic clay such as montmorillonite. Another method of making a supported catalyst is to start a polymerization or at least make an iron complex of another olefin or oligomer of an olefin such as cyclopentene on a support such as silica or alumina. All of these xe2x80x9cheterogeneousxe2x80x9d catalysts may be used to catalyze oligomerization in the gas phase or the liquid phase. By gas phase is meant that the ethylene is transported to contact with the catalyst particle while the ethylene is in the gas phase.
Some of the compounds made or used in the Examples are shown below: