A receiver for receiving a broadcast channel comprising a spectrum analyzer physically integrated into the receiver and operative to receive an intermediate frequency signal and process the spectral contents of the receive signal.

The frequency band that the broadcasters use for electronic news gathering (ENG) is transitioning from 17 MHz bandwidth channels to 12 MHz bandwidth channels. To maintain a substantially consistent level of quality, the current analog FM modulation scheme will be changed to a digital modulation scheme. The current workflow for establishing and maintaining a link between antennas typically requires aligning a simplex link using verbal feedback from the receive site back to the transmitter site. The feedback is usually provided by having an operator at a transmit site make a voice connection using 2-way radio or cell phone. The operator then performs initial antenna alignment in the analog FM domain using feedback from another operator at a receive antenna. Once antenna alignment is confirmed in the analog domain, a switch is then made to digital modulation. This process works adequately in a static environment. Once in the digital mode it is typically impossible to detect the presence of an adjacent channel transmitter that may cause interference until the picture starts to breakup or the BER deteriorates. By then, however, it is usually too late. When this occurs the user must switch back to analog mode to diagnose the problem.
In general, there are no tools currently available to adequately assist the operator in diagnosing link reliability issues in the digital mode. A solution that has been proposed and implemented is to add a spectrum analyzer to the 70 MHz intermediate frequency (IF) output of the receiver. This has proven to be a viable solution for isolating or identifying only a few problems related to on channel or co-channel interference. Such problems are incorrect modulation type of the transmitter or co-channel interference.
FIG. 1 is a diagram that illustrates a standard system configuration 100. As shown, a radio frequency (RF) signal 110 is received and amplified with an amplifier (LNA) 116. This signal is then down converted from the received RF frequency to a first IF frequency typically using a mixer 118 and synthesizer 122. The signal is then filtered with a wide band pass filter 126. The frequency of this first conversion is generally in the 800 MHz range. The specific frequency may vary based on the manufacturer's architecture. The signal is then further amplified at amplifier 130 and further down converted to a second IF frequency using mixer 134 and synthesizer 138. This is typically 140 or 70 MHz but not limited to these frequencies. The signal, now at a lower frequency, can be further filtered via filter 142 to remove adjacent channel signals located above and below the desired channel. After the filter 142, which is typically a narrow band-pass filter, the signal is usually further amplified using amplifier 146, i.e., automatic gain control (AGC), and applied to a demodulator 150 to recreate the original signal transmitted. Manufacturers of receivers will often provide an auxiliary IF output 156 for monitoring purposes. In this system architecture, a spectrum analyzer 160 can be connected external to the IF monitor point 156.
The system of FIG. 1 has generally been deployed and used to conduct link reliability analysis. The architecture of FIG. 1 has not, however, proven to be optimal for diagnosing the majority of link conditions that lead to link failure or reduce link reliability. A reason the aforementioned architecture is flawed is that many problems cannot be detected after filtering and after AGC amplification. Specifically, most interfering signals cannot be detected unless the transmitter is placed into standby mode, which results in the inability to see some types of adjacent or co-channel interference. Furthermore, when the transmitter is placed in standby mode, it is also very difficult to diagnose link problems because the AGC circuit in the receiver brings the noise floor or interference up to a level similar to the desired signal thereby disguising the real problem. This can cause operators or maintenance personnel to become confused and further complicate their job.
One place to monitor the link spectrum would be at the RF input. In this way, the full spectrum can be viewed relative the power levels of the channels of interest. But this architecture is relatively expensive as it duplicates the LNA and synthesizer circuitry. This method may also reduce the receiver's sensitivity because power intended for the receiver will be diverted to the spectrum analyzer.

Broadcast receiver having integrated spectrum analysis


A processor (100, 500) that executes applications (99) which require access to time slots of a time-division multiplexed (TDM) communications medium (110) uses spare processing capacity and/or spare hardware of the processor to interface to the TDM medium and to implement a time-slot interchange (TSI) function in a simple and low-cost manner. The processor has a control store (104, 300, 504, 604) that stores a bit map of the time slots of the TDM medium. The bit map is either examined by the processor during each time slot (FIG. 2) to determine, or is used by external circuitry (301, 302) or spare internal circuitry (511) of the processor to generate interrupts (406) or DMA requests that indicate to the processor or to a host interface (510) of the processor, which time slots to access. The processor has a read buffer (105, 505) and a write buffer (106, 506) for effecting data transfers between the TDM medium and the applications. The applications have random access to the buffers, thereby effecting a time-slot-interchange function.

Various modern-day telecommunications switching systems use a time-division multiplexed (TDM) communications medium as their switching fabric. An illustrative example of such systems is the Lucent Technologies Inc. Definity.RTM. private branch exchange (PBX). Port circuits that interface communications links and devices (applications) to the TDM medium normally provide access to only a relatively small number of the medium's time slots. For example, the port circuit packs of the Definity PBX provide access to any 32 time slots of the PBX's 256 time-slot TDM bus. Applications that need access to more than 32 time slots either use multiple port circuit packs or custom (and generally complex and expensive) time-slot interchange (TSI) circuits.
Applications that require access to more time slots than conventional port circuits provide, are becoming ever-more common. If such applications use multiple port circuit packs, they consume multiple circuit-pack slots on the TDM medium and thereby reduce the number of applications that the switching system can serve. If such applications use custom complex and expensive TDM interface circuits, they significantly increase the system's cost.
An ideal TDM interface would provide each application served by a port circuit pack access to all of the TDM medium's time slots that the application requires, in a simple, low-cost, manner.

Simplified interface to a time-division multiplexed communications medium


An interior structure of a water control valve for faucets includes a control valve body, a control valve stem, and a valve plug wherein the control valve body has an upper coupling end with a valve stem hole defined therein disposed at the upper step thereof, a pair of symmetrical positioning slide blocks with an inner valve chamber disposed at the lower step thereof, and a pair of symmetrical water outlet ports with retaining grooves defined thereon in communication with the valve chamber thereof. The control valve stem has an upper engaging end, an abutting block properly disposed thereon, and a linkage rib extending at the bottom side thereof. A stop disc is provided with a central elongate inserting slot and a pair of abutting flanges symmetrically extending at the outer edge thereon. An upper switch valve with plane edges symmetrically cut at both sides thereof has a central elongate inserting recess, and water inlet chambers properly defined therein. A lower switch valve has a pair of protrusive locating blocks symmetrically disposed at the outer periphery thereof, water inlet ports disposed at the top surface thereon, and a connecting cavity disposed at the inner bottom end therein. The valve plug has a stepwise central water inlet hole to form a support face therein, an upper connecting end with a retaining space defining the outer periphery thereon and an upper water sealing ring protruding at the upper edge thereon, and a plurality of lower water sealing rings mounted at the lower end thereof so that the valve plug can be accurately engaged with the lower switch valve to achieve the best leakage-proof effect in water supply thereby.

The present invention is related to an interior structure of a water control valve for faucets, including a control valve body, a control valve stem, and a valve plug wherein the valve plug, integrally made of rubber, is equipped with a connecting end protruding at the upper side thereof to be mutually engaged with a connecting cavity of a lower switch valve thereby, and a plurality of upper and lower water sealing rings mounted at predetermined positions thereon; therefore, in the status of water supply, the upper/lower water sealing rings of the valve plug will be expanded outwards by water flow to respectively abut tight and close against the inner wall of the connecting cavity of the lower switch valve and that of a valve chamber of the control valve body for more accurate and secure mutual engagement therewith so as to achieve the best leakage-proof effect thereby.
Please refer to FIG. 1. A conventional water control valve for faucets includes a control valve body 10, a control valve stem 20, and a valve plug 30. The control valve body 10, made in a two-stepwise cylindrical shape, is equipped with a coupling end 11 disposed at the upper step thereof to be mutually engaged with a seat cover B of a faucet handle A thereby, a valve stem hole 12 properly defining the interior of the upper step thereof, a pair of positioning slide blocks 13 symmetrically extending at the upper section of the lower step thereof, and two sealing O-rings 14 mounted at the middle section of the lower step thereof. Inside the lower step of the control valve body 10 thereof is disposed a three-staged valve chamber 15 that, having a lower opening to be communicated with the valve stem hole 12 thereof, is made up of a smaller-diameter upper stage, a medium-diameter middle stage with a pair of limiting blocks 151 symmetrically protruding at the bottom edge thereon, and a larger-diameter lower stage with a pair of water outlet ports 16 symmetrically cut at proper positions thereon to be mutually connected with the valve chamber 15 thereof and with a pair of retaining grooves 161 symmetrically preset at the water outlet ports 16 thereof. The control valve stem 20 is equipped with an upper engaging end 201 to be mutually registered with the faucet handle A thereby, a plurality of water sealing rings 202 mounted at preset positions thereon, an abutting block 203 with a retaining ring 204 having a pair of symmetrical stop protrusions 2041 properly disposed thereof, and a linkage rib 205 extending at the bottom side thereon. A stop disc 21 is equipped with an elongated inserting slot 211 disposed at the center thereof and a pair of abutting flanges 212 symmetrically extending downwards at the bottom outer edge thereon. An upper switch valve 22 and a lower switch valve 23 are integrally made of ceramic material wherein the upper switch valve 22, made in an annular disc with plane edges symmetrically cut at both sides thereof, is provided with an elongated inserting recess 221 indented at the center of the top side thereon, and triangular water inlet chambers 222 each defined by an arched side tilting downwards from both cut edges to the central point thereof. The lower switch valve 23, made in a disk shape, has a pair of protrusive locating blocks 231 symmetrically disposed at both sides of the outer periphery thereof, and a plurality of quarter-shaped water inlet ports 232 distributed at the top surface thereon. The valve plug 30 is made in an annular shape, having a water inlet hole 31 disposed at the center thereof, a coupling end 62 extending at the upper side thereof, a positioning flange 33 extending at the lower side, and an upper packing ring 321 and a lower packing ring 322 mounted at the upper and bottom sides thereof respectively.
Please refer to FIG. 2. In assembly, the control valve stem 20 is joined to the valve chamber 15 of the control valve body 10 thereof, permitting the upper engaging end 201 thereof to extend outside the valve stem hole 12 of the control valve body 10 and the abutting block 203 to locate precisely between the limiting blocks 151 thereof for movement limited within 90 degrees therein. Then, the stop disc 21 is placed into the valve 15 of the control valve body 10 with the inserting slot 211 mutually engaged with the linkage rib 205 of the control valve stem 20, and the upper switch valve 22 in turn is located into the valve chamber 15 thereof with the inserting groove 221 thereof precisely mated with the linkage rib 205 of the control valve stem 20 thereof and the plane edges cut at both sides thereof closely joined to the abutting flanges 212 of the stop disc 21 respectively. The lower switch valve 23 is then guided to the valve chamber 15 till the protrusive locating blocks 231 thereof precisely inserted to the retaining grooves 161 of the control valve body 10 thereof, permitting the upper switch valve 22 to abut closely on top of the lower switch valve 23 thereof. Finally, the coupling end 32 of the valve plug 30 is joined to the valve chamber 15 thereof, permitting the upper packing ring 321 mounted at the coupling end 32 thereof to abut closely against the bottom surface of the lower switch valve 23 and the positioning flange 20 precisely abut against the bottom outer edge of the control valve stem 20 to complete the assembly thereof.
In practical use, the water inlet chambers 222 of the upper switch valve 22 are wide open for the discharge of water. Water coming out from a water inlet pipe C will go through the water inlet hole 31 of the valve plug 30 and flush upwards at the underside of the lower switch valve 23 to flow out through the water inlet pores 232 of the lower switch valve 23 and come into the water inlet chambers 222 of the upper switch valve 22 thereof. Finally, the water flowing out from the water inlet chambers 222 will go through the water outlet holes 16 of the control valve body 10 to be discharged there-from via water outlet pipes to complete the water supply thereof. When the water inlet chambers 222 of the upper switch valve 22 are in a closed-off status, the water inside the water inlet chambers 222 is cut off from the water outlet holes 16 of the control valve body 10 without any water flowing out from the water outlet pipes to shut off the water supply thereof.
However, there are some drawbacks to such conventional water control valve structure for faucets. First, the upper packing ring 321 of the valve plug 30 is simply contacted and abutted against the bottom surface of the lower switch valve 23, which, poor in the mutual engagement thereof, is prone to produce gaps and result in the problem of water leakage. Thus, the conventional water control valve structure is featured by a bad leakage-proof effect. Second, when the control valve body 10 is mounted to the seat cover B of the faucet handle A, the downwards pressure will force the lower packing ring 322 thereof to abut tight against the inner bottom edge of the water inlet pipe C and the upper packing ring 321 to press closer at the bottom surface of the lower switch valve 23 thereof. Under the impact of high water pressure on and off in a long time, the upper and lower switch valves 22, 23 tend to get squeezed and crushed up into pieces.

Interior structure of water control valve for faucets


A pesticidal composition comprises a synergistically effective amount of an acetyl CoA carboxylase inhibitor compound and a pesticide selected from N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide (I), N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide (II), or any agriculturally acceptable salt thereof. A method of controlling pests comprises applying the pesticidal composition near a population of pests. A method of protecting a plant from infestation and attack by insects comprises contacting the plant with the synergistic pesticidal composition.

Controlling pest populations is essential to human health, modern agriculture, food storage, and hygiene. There are more than ten thousand species of pests that cause losses in agriculture and the worldwide agricultural losses amount to billions of U.S. dollars each year. Accordingly, there exists a continuous need for new pesticides and for methods of producing and using such pesticides.
The Insecticide Resistance Action Committee (IRAC) has classified insecticides into categories based on the best available evidence of the mode of action of such insecticides. Insecticides in the IRAC Mode of Action Group 23 are inhibitors of acetyl CoA carboxylase. The insecticides in this class are believed to inhibit acetyl coenzyme A carboxylase, part of the first step in lipid synthesis, resulting death of the affected insects. Examples of insecticides in this class are tetronic acid derivatives (i.e., 4-hydroxy-[5H]furan-2-one derivatives) such as spirodiclofen and spiromesifen, and tetramic acid derivatives (i.e., pyrrolidine-2,4-dione derivatives) such as spirotetramat.
Spirotetramat (cis-3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-azaspiro[4.5]dec-3-en-4-yl ethylcarbonate) is a tetramic acid derivative. Spirodiclofen (3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl 2,2-dimethylbutanoate) and spiromesifen (2-oxo-3-(2,4,6-trimethylphenyl)-1-oxaspiro[4,4]non-3-en-4-yl 3,3-dimethylbutanoate) are tetronic acid derivatives.
Although the rotational application of pesticides having different modes of action may be adopted for good pest management practice, this approach does not necessarily give satisfactory pest control. Furthermore, even though combinations of pesticides have been studied, a high synergistic action has not always been found.

Synergistic pesticidal compositions and related methods


Benzoic acid compounds of the formula ##STR1## wherein each symbol is as defined in the specification, optical isomers thereof and pharmaceutically acceptable salts thereof; pharmaceutical composition comprising this compound and pharmaceutically acceptable additive; and serotonin 4 receptor agonists, gastrointestinal prokinetic agents and therapeutic agents for various gastrointestinal diseases, which comprise this compound as active ingredient. The compounds of the present invention have high and selective affinity for serotonin 4 receptor, and show agonistic effects thereon. Accordingly, they are useful medications for the prophylaxis and treatment of various gastrointestinal diseases, central nervous disorders, cardiac function disorders, urinary diseases, and the like, as well as useful anti-nociceptors for analgesic use which increase threshold of pain.

When control mechanism of gastrointestinal motility fails and prokinetic function is declined, atonic constipation and digestive symptoms such as abdominal distention, anorexia and heartburn emerge. Declined gastrointestinal motility is found with aging, stress or diseases such as chronic gastritis, non-ulcer dyspepsia, reflux esophagitis, peptic ulcer, diabetes and the like, and gastrointestinal prokinetic agents have been used for treatment.
Ever since metoclopramide (The Merck Index, vol. 11, 6063) was developed as a gastrointestinal prokinetic agent, various substituted benzamide derivatives have been synthesized. At present, cisapride (The Merck Index, vol. 11, 2318) and others have been clinically used as gastrointestinal prokinetic agents besides metoclopramide. While benzamide derivatives such as metoclopramide and cisapride have been speculated to show effects via certain receptors in the digestive organs, the actual function of the receptors involved in the promotion of gastrointestinal motility has long been unclarified. Recently, however, 5-HT.sub.4 receptor has been identified to be a new serotonin receptor subtype which stimulates adenylate cyclase activity, and benzamide derivatives have been found to promote gastrointestinal motility by activating 5-HT.sub.4 receptor in the digestive organs The Journal of Pharmacology and Experimental Therapeutics, vol. 252, pp. 1378-1386 (1990), European Journal of Pharmacology, vol. 196, pp. 149-155 (1991)!. Having found the action of metoclopramide and cisapride as 5-HT.sub.4 receptor agonists, many attempts have been made to use 5-HT.sub.4 receptor agonists as gastrointestinal prokinetic agents. The Journal of Pharmacology and Experimental Therapeutics, vol. 264, pp. 240-248 (1993) reports that substituted benzamide (SC53116) which is a 5-HT.sub.4 receptor agonist stimulated gastrointestinal motility. As 5-HT.sub.4 receptor agonists, Japanese Patent Unexamined Publication No. 157518/1994 discloses oxadiazole derivatives; Japanese Patent Unexamined Publication No. 10881/1995 discloses oxazabicyclo derivatives; and WO 94/12497 discloses endo-N-(8-methyl-8-azabicyclo3.2.1!oct-3-yl)-1-isopropyl-2(1 H)-quinolone-3-carboxamide and acid addition salts thereof.
The 5-HT.sub.4 receptor has been found to be also present in brain (e.g., prefrontal area, nigra, hippocampus and amygdaloid complex), heart, endocrine system and urinary system British Journal of Pharmacology, vol. 109, pp. 618-624 and Naunyn-Schmiedeberg's Archives of Pharmacology, vol. 344, pp. 150-159, Trends in Pharmacological sciences, vol. 13, pp. 141-145 (1992), Pharmacological Reviews, vol. 46, pp. 182-185 (1994)!.
In addition, since activation of 5-HT.sub.4 receptor in the central nervous system promotes release of acetylcholine in prefrontal area, 5-HT.sub.4 receptor is responsible for memory and learning mechanism through release of acetylcholine. Therefore, a 5-HT.sub.4 agonist has a potential for a drug for the prophylaxis and treatment of disturbance of memory, dementia and the like. In view of a report documenting that 5-HT.sub.4 receptor on GABA neuron is involved in anxiety, it also has a potential for a drug for the prophylaxis and treatment of anxiety. Furthermore, the action of 5-HT.sub.4 receptor on heart and urinary system has been reported Trends in Pharmacological Sciences, vol. 16, pp. 391-398 (1995)!.
In view of such disclosures, a compound having affinity for 5-HT.sub.4 receptor is considered to be clinically applicable to digestive organs, brain, heart and urinary system. In other words, a 5-HT.sub.4 receptor agonist should be useful as a medication for the prophylaxis and treatment of various gastrointestinal diseases (e.g., reflux esophagitis; gastroesophageal reflux such as that accompanying cystic fibrosis; Barrett syndrome; intestinal pseudoileus; acute or chronic gastritis; gastric or duodenal ulcer; Crohn's disease; non-ulcer dyspepsia; ulcerative colitis; postgastrectomy syndrome; postoperative digestive function failure; delayed gastric emptying caused by gastric neurosis, gastroptosis, diabetes, and the like; gastrointestinal disorders such as indigestion, meteorism, abdominal indefinite complaint, and the like; constipation such as atonic constipation, chronic constipation, and that caused by spinal cord injury, pelvic diaphragm failure and the like; and irritable bowel syndrome), central nervous disorders (e.g., schizophrenia, depression, anxiety, disturbance of memory and dementia), cardiac function disorders (e.g., cardiac failure and myocardial ischemia), urinary diseases (e.g., dysuria caused by urinary obstruction, ureterolith, prostatomegaly, spinal cord injury, pelvic diaphragm failure, etc.) and the like.
In addition, a report has documented that 5-HT.sub.4 receptor antagonist shows an antagonistic action on analgesic action of cisapride and metoclopramide Arzneimittel Forschung,-vol. 43, pp. 913-918 (1993)!. Thus, a 5-HT.sub.4 receptor agonist is expected to be useful as an anti-nociceptor for analgesic use which increases threshold of pain.
While there have been documented some compounds which selectively activate 5-HT.sub.4 receptors Journal of Medicinal Chemistry, vol. 35, pp. 1486-1489 (1992)!, a compound has not been known at all, which has, at an alkyl moiety bound to nitrogen atom of cyclic amine, amide, urea, amino, (thio)ether, (thio)carbonyl, sulfinyl, sulfonyl or a heterocycle having amide or urea bonding in the ring.
The above-mentioned substituted benzamide derivatives, such as metoclopramide, have, besides 5-HT.sub.4 receptor agonistic effect, dopamine 2 (hereinafter referred to as D.sub.2) receptor antagonism or serotonin 3 (hereinafter referred to as 5-HT.sub.3) receptor antagonism, and are not entirely satisfactory in terms of efficacy and safety, since they cause side effects such as extrapyramidal disorders due to D.sub.2 receptor antagonism, and side effects such as constipation due to 5-HT.sub.3 receptor antagonism Drugs, vol. 41, pp. 574-595 (1991)!, and are associated with such problems to be solved.
As gastrointestinal prokinetic agents, Japanese Patent Unexamined Publication Nos. 262724/1993, 50883/1989 and 211685/1992 disclose compounds having 5-HT.sub.3 receptor antagonism. These compounds again cause side effects such as constipation, as mentioned above, and are not satisfactory. Since 5-HT.sub.4 receptors are reportedly distributed widely in the entirety of digestive organs, a 5-HT.sub.4 receptor agonist which shows low affinity for D.sub.2 receptor and 5-HT.sub.3 receptor, but shows high and selective affinity for 5-HT.sub.4 receptors and activate same is expected to make a superior gastrointestinal prokinetic agent.
Accordingly, the present invention aims at providing a compound having high and selective affinity for 5-HT.sub.4 receptors and capable of activating same in various tissues, which is useful as a medication for the prophylaxis and treatment of various gastrointestinal diseases (e.g., reflux esophagitis; gastroesophageal reflux such as that accompanying cystic fibrosis; Barrett syndrome; intestinal pseudoileus; acute or chronic gastritis; gastric or duodenal ulcer; Crohn's disease; non-ulcer dyspepsia; ulcerative colitis; postgastrectomy syndrome; postoperative digestive function failure; delayed gastric emptying caused by gastric neurosis, gastroptosis, diabetes, and the like; gastrointestinal disorders such as indigestion, meteorism, abdominal indefinite complaint, and the like; constipation such as atonic constipation, chronic constipation, and that caused by spinal cord injury, pelvic diaphragm failure and the like; and irritable bowel syndrome), central nervous disorders (e.g., schizophrenia, depression, anxiety, disturbance of memory and dementia), cardiac function disorders (e.g., cardiac failure and myocardial ischemia), urinary diseases (e.g., dysuria caused by urinary obstruction, ureterolith, prostatomegaly, spinal cord injury, pelvic diaphragm failure, etc.), and the like, and also useful as an anti-nociceptor for analgesic use which increases threshold of pain.
According to the present invention, there has now been found a new benzoic acid compound, namely, a benzoic acid compound having, at an alkyl moiety bound to nitrogen atom of cyclic amine of the following formulas (II-a)-(II-f) and (III), amide, urea, amino, (thio)ether, (thio)carbonyl, sulfinyl, sulfonyl or a heterocycle having amide or urea bonding in the ring, which shows superior selective activation of 5-HT.sub.4 receptors.

Benzoic acid compounds and use thereof as medicaments

Yoshitomi Pharmaceutical Industries, Ltd.


A system and method for stabilizing a mating is provided. One embodiment comprises an apparatus for stabilizing a mating between signal connectors. The apparatus comprises a body operable to be coupled to a unit comprising a first signal connector, said body forming an aperture operable to receive at least a portion of a surface to which a second signal connector is coupled, wherein said apparatus restrains movement of the at least a portion of the surface received by the aperture when the first signal connector and the second signal connector are mated.

Objects operable to receive signals from and/or transfer signals to other objects often include a signal connector. Non-limiting examples of such objects include electrical device components, such as disk drives, power supplies, etc. A signal connector is operable to be mated with a matching connector of another object whereby the two objects become communicatively coupled (and in most instances, physically coupled as well). The signals that may be exchanged between two objects by way of such connectors may comprise numerous energy forms, non-limiting examples of which include power signals, electrical signals, optical signals, radio-frequency (RF) signals, etc.
Typically, at least one of the two objects at least communicatively coupled by way of such signal connectors is exposed to shock and/or vibration. Such vibration may potentially have an adverse effect on the mating. For example, such vibration may lead to rotation and/or translation of the mated connectors. The connectors, particularly if they are physically coupled together, may be worn down as a result.
As a non-limiting example of the above phenomena, disk drives typically include a signal connector whereby the disk drive may exchange data with other objects, as well as receive power signals from other objects. Moreover, disk drives are typically incorporated into disk drive units. Such disk drive units are normally adapted for disposition within a housing cabinet (e.g., a chassis). As part of such disposition, a disk drive unit may be integrally associated with the housing cabinet or may be removable therefrom. On average, as part of being disposed within a housing cabinet, a disk drive unit is communicatively coupled to one or more of the other contents of the cabinet. Often, such communicative coupling involves mating a signal connector of the disk drive unit with a compatible signal connector of another component within the cabinet. For example, in one instance, the disk drive unit connector is mated with a signal connector coupled to a circuit board disposed within the housing cabinet.
Quite often, a housing cabinet of the type described above is exposed to shock and/or vibration (e.g., during assembly, packaging, shipping or other types of handling). Such vibration may potentially have an adverse affect on any matings within the cabinet. For example, in some instances, in response to such shock and vibration, a large mass (e.g., a grouping of substantial surface circuit components on the circuit board) situated at a location on a circuit board proximate to a signal connector that is mated with a signal connector of a disk drive unit, influences the circuit board to vibrate. This vibration is often in a direction normal to a longitudinal surface of the circuit board. Similar to the above, such vibration may lead to rotation and/or translation of the mated connectors. The connectors may be worn down as a result.

System and method for stabilizing a mating

Hewlett-Packard Development Company, L.P.


A modified modulation transfer function of a device is determined. The modified modulation transfer function includes intentional deviations from a nominal modulation transfer function of the device. A digital content object is modified based on the modified modulated transfer function to optimize playback of the digital content object on the device, and the modified digital content object is distributed to the device.

Digital Rights Management (DRM) is a great concern for digital content owners, such as owners of songs, movies, electronic books, documents and other types of digital media. Content owners try to sell and/or distribute their content in such a way to prevent the illegal copying of their content. For example, content, such as movies are widely sold and distributed on digital video discs (DVDs). To prevent illegal copying, DVDs typically include copy protection mechanisms that prevent users from making copies.
It has currently become very convenient and popular to purchase and download digital content, such as purchasing and downloading songs or other types of digital content via the Internet. In practice, most online content delivery stores also use some form of DRM technology to protect against unauthorized copying.
Typically, the DRM protection downloaded content or content distributed via DVD or CD includes controlling the copying of the bits contained in the digital content. For example, hardware or software in devices operable to play the digital content, such as portable media players, DVD players, compact disc (CD) players, personal computers (PCs), etc., may include built-in protections that do not allow the device to play the digital content or copy the digital content unless playing or copying is authorized, for example, by purchasing the content. However, because of these protections, the device may prevent playing or copying of some content that would not be a violation of an owner's rights, such as playing or copying home-made movies or other home-made content. Furthermore, even though the distributed content includes copy protection mechanisms, just as many mechanisms exist that can make unauthorized copies of the copy-protected content.

Using a modulation transfer function of a device to create digital content for the device


Methods of regulating gene expression in subjects using tetracycline-responsive fusion proteins are disclosed. In one embodiment, the method involves introducing into a cell the subject a nucleic acid molecule encoding a fusion protein which activates transcription, the fusion protein comprising a first polypeptide which binds to a tet operator sequence in the presence of tetracycline or a tetracycline analogue operatively linked to a second polypeptide which activates transcription in eukaryotic cells; and modulating the concentration of a tetracycline, or analogue thereof, in the subject. In another embodiment, the cell further comprises a fusion protein which inhibits transcription, the fusion protein comprising a first polypeptide which binds to a tet operator sequence, operatively linked to a second polypeptide which inhibits transcription in eukaryotic cells. In yet another embodiment, the method involves obtaining a cell from a subject, introducing into the cell a first nucleic acid molecule which operatively links a gene to at least one tet operator sequence, introducing into the cell a second nucleic acid molecule encoding a fusion protein of the invention to form a modified cell, administering the modified cell to the subject and modulating the concentration of a tetracycline, or analogue thereof, in the subject. The first and second nucleic acid molecules can be linked or can be separate molecules.

Functional analysis of cellular proteins is greatly facilitated through changes in the expression level of the corresponding gene for subsequent analysis of the accompanying phenotype. For this approach, an inducible expression system controlled by an external stimulus is desirable. Ideally such a system would not only mediate an "on/off" status for gene expression but would also permit limited expression of a gene at a defined level.
Attempts to control gene activity have been made using various inducible eukaryotic promoters, such as those, responsive to heavy metal ions (Mayo et al. (1982) Cell 29:99-108; Brinster et al. (1982) Nature 2:39-42; Searle et al. (1985) Mol. Cell. Biol. 5:1480-1489), heat shock (Nouer et al. (1991) in Heat Shock Response, e.d. Nouer, L. , CRC, Boca Raton, Fla., pp167-220) or hormones (Lee et al. (1981) Nature 294:228-232; Hynes et al. (1981) Proc. Natl. Acad. Sci. USA 78:2038-2042; Klock et al. (1987) Nature 32:734-736; Israel & Kaufman (1989) Nucl. Acids Res. 17:2589-2604). However, these systems have generally suffered from one or both of the following problems: (1) the inducer (e,g, heavy metal ions, heat shock or steroid hormones) evokes pleiotropic effects, which can complicate analyses, and (2) many promoter systems exhibit high levels of basal activity in the non-induced state, which prevents shut-off the regulated gene and results in modest induction factors.
An approach to circumventing these limitations is to introduce regulatory elements from evolutionarily distant species such as E. coli into higher eukaryotic cells with the anticipation that effectors which modulate such regulatory circuits will be inert to eukaryotic cellular physiology and, consequently, will not elicit pleiotropic effects in eukaryotic cells. For example, the Lac repressor (lacR)/operator/inducer system of E. coli functions in eukaryotic cells and has been used to regulate gene expression by three different approaches: (1) prevention of transcription initiation by properly placed lac operators at promoter sites (Hu & Davidson (1987) Cell 48:555-566; Brown et al. (1987) Cell 49:603-612; Figge et al. (1988) Cell 52:713-722; Fuerst et al. (1989) Proc. Natl. Acad. Sci. USA 86:2549-2553: Deuschle et al. (1989) Proc. Natl. Acad. Sci. USA 86:5400-5405); (2) blockage of transcribing RNA polymerase II during elongation by a LacR/operator complex (Deuschle et al. (1990) Science 248:480-483); and (3) activation of a promoter responsive to a fusion between LacR and the activation domain of herpes simples virus (HSV) virion protein 16 (VP16) (Labow et al. (1990) Mol. Cell. Biol. 10:3343-3356; Baim et al. (1991) Proc. Natl. Acad. Sci USA 88:5072-5076).
In one version of the Lac system, expression of lac operator-linked sequences is constitutively activated by a LacR-VP16 fusion protein and is turned off in the presence of isopropyl-.beta.-D-thiogalactopyranoside (IPTG) (Labow et al. (1990), cited supra). In another version of the system, a lacR-VP16 variant is used which binds to lac operators in the presence of IPTG, which can be enhanced by increasing the temperature of the cells (Baim et al.(1991), cited supra). The utility of these lac systems in eukaryotic cells is limited, in part, because IPTG acts slowly and inefficiently in eukaryotic cells and must be used at concentrations which approach cytotoxic levels. Alternatively, use of a temperature shift to induce gene expression is likely to elicit pleiotropic effects in the cells. Thus, there is a need for a more efficient inducible regulatory system which exhibits rapid and high level induction of gene expression and in which the inducer is tolerated by eukaryotic cells without cytotoxicity or pleiotropic effects.
Components of the tetracycline (Tc) resistance system of E. coli have also been found to function in eukaryotic cells and have been used to regulate gene expression. For example, the Tet repressor (TetR), which binds to tet operator sequences in the absence of tetracycline and represses gene transcription, has been expressed in plant cells at sufficiently high concentrations to repress transcription from a promoter containing tet operator sequences (Gatz, C. et al. (1992) Plant J. 2:397-404). However, very high intracellular concentrations of TetR are necessary to keep gene expression down-regulated in cells, which may not be achievable in many situations, thus leading to "leakiness" in the system.
In other studies, TetR has been fused to the activation domain of VP 16 to create a tetracycline-controlled transcriptional activator (tTA) (Gossen, M. and Bujard, H. (1992) Proc. Natl. Acad. Sci. USA 89:5547-5551). The tTA fusion protein is regulated by tetracycline in the same manner as TetR, i.e., tTA binds to tet operator sequences in the absence of tetracycline but not in the presence of tetracycline. Thus, in this system, in the continuous presence of Tc, gene expression is kept off, and to induce transcription, Tc is removed.


A power storage device using an organic solvent as a nonaqueous solvent for a nonaqueous electrolyte, in which a CV charging period in CCCV charging can be prevented from being extended and which has high performance, can be provided. The power storage device includes a positive electrode, a negative electrode, and a nonaqueous electrolyte. The nonaqueous electrolyte includes an ionic liquid including an alicyclic quaternary ammonium cation having one or more substituents and a counter anion to the alicyclic quaternary ammonium cation, a cyclic ester, and an alkali metal salt. In particular, in the power storage device, the ionic liquid content is greater than or equal to 70 wt % and less than 100 wt % per unit weight of the ionic liquid and the cyclic ester in the nonaqueous electrolyte, or greater than or equal to 50 wt % and less than 80 wt % per unit weight of the nonaqueous electrolyte.

1. Field of the Invention
The present invention relates to a power storage device including an ionic liquid (also referred to as "room temperature molten salt").
Note that the power storage device refers to all elements and devices which have a function of storing power.
2. Description of the Related Art
A lithium secondary battery which is one of the power storage devices is used in a variety of applications including mobile phones and electric vehicles (EV). Characteristics such as high energy density, excellent cycle characteristics and safety under a variety of operating environments are necessary for the lithium secondary battery.
Many of the widely used lithium secondary batteries include a nonaqueous electrolyte (also referred to as "nonaqueous electrolyte solution") including a nonaqueous solvent and a lithium salt containing lithium ions. An organic solvent which is often used for the nonaqueous electrolyte is an organic solvent which is liquid at ordinary temperatures and pressures, such as ethylene carbonate which has high dielectric constant and excellent ion conductivity.
However, the organic solvent has volatility and a low flash point. For this reason, in the case where a nonaqueous solvent including the organic solvent is used for an electrolyte solution of a lithium secondary battery, the internal temperature of the lithium secondary battery might rise because of an internal short circuit, overcharge, or the like, and the lithium secondary battery might explode or ignite.
In view of the above, the use of an ionic liquid which has non-flammability and non-volatility as a solvent for a nonaqueous electrolyte of a lithium secondary battery has been proposed (see Parent Document 1).

This patent is subject to a terminal disclaimer.

Nonaqueous solvent, nonaqueous electrolyte, and power storage device

SEMICONDUCTOR ENERGY LABORATORY CO., LTD.


A distributed LiDAR comprises: an optical transceiver assembly, multiple distributed scanning units, and a distributed optical fiber connector assembly. The optical transceiver assembly includes: a light source emitting detection light, and a light receiving unit used for receiving a detection echo. The multiple distributed scanning units are distributed on the carrier of the distributed LiDAR. The distributed optical fiber connector assembly is in coupled connection with the optical transceiver assembly and the multiple distributed scanning units. The detection light emitted by the light source in the optical transceiver assembly is synchronously transmitted by the distributed optical fiber connector assembly to the multiple distributed scanning units. The multiple distributed scanning units emit the detection light to a detected area with a scanning device, and receive a reflected echo from the detected area. The reflected echo is transmitted to the optical transceiver assembly by the distributed optical fiber connector assembly.

Barrier detection in autonomous vehicles driving on the road constitutes an important part in the research area of environmental perception technology. In the application of barrier detection, sensors commonly used are LiDAR, camera, millimeter wave radar, ultrasonic sensor and so on. LiDARs measure a distance by measuring a time difference between emitted light and reflected light from the surface of an object. At present, the multi-channel LiDAR available on the market performs scanning of multiple channels by distributing multiple laser emitters in the vertical direction and by the rotation of the electric motor, for example, the 64-channel LiDAR produced by Velodyne. However, a great number of channels in a LiDAR leads to the increased costs, and its application is accordingly limited. In LiDARs, the highest costs lie in the transmitter and the receiver. In order to reduce the costs, LiDARs with a lower number of channels may usually be used for coupling, which is equivalent to a multi-channel LiDAR in terms of effect; meanwhile, the resolution is improved at the time of reducing the costs of the LiDARs. This has become a current focus of research.
At present, one of the common technical solutions is to couple multiple LiDARs. For example, four 16-channel LiDARs are coupled, and upon reasonable design and layout, a control unit is used to control the four LiDARs to meet the purpose of the free combination of mixed solid-state LiDARs point cloud density changes, by the joint calibration of the LiDARs and synchronous data processing, thereby.


The present invention relates to 5-Aryltetrazole Compounds, compositions comprising an effective amount of a a 5-Aryltetrazole Compound, and methods for treating an inflammation disease, a reperfusion disease, or hyperuricemia in an animal in need thereof comprising administering to the animal an effective amount of a 5-Aryltetrazole compound.

The level of xanthine oxidase ("XO") in an animal increases markedly (>400-fold in bronchoalveolar fluid in pneumonitis) during inflammation, ischemia-reperfusion injury, and atherosclerosis. Particularly, due to the spillover of tissue XO into the circulation, plasma levels of XO may be detected in an animal experiencing adult respiratory distress syndrome, ischemia-reperfusion injury, arthritis, sepsis, hemorrhagic shock, and other inflammatory conditions. Inflammation-induced histamine release by mast cells and basophils also enhances the activity of XO.
Superoxide radical (O2−) can be generated by xanthine oxidase and NADPH oxidase from the partial reduction of molecular oxygen. Neutrophils and macrophages are known to produce O2− and hydrogen peroxide (H2O2), which normally are involved in the killing of ingested or invading microbes (T. Oda et al., Science, 244:974–976). Under physiologic conditions XO is ubiquitously present in the form of a xanthine dehydrogenase (XDH). XDH is a molybdenum iron-sulfur flavin dehydrogenase that uses NAD+ as an electron acceptor to oxidize purines, pyrimidines, pteridins, and other heterocyclic nitrogen-containing compounds. In mammals, XDH is converted from the NAD-dependent dehydrogenase form to the oxygen-dependent oxidase form, either by reversible sulfhydryl oxidation or irreversible proteolytic modification (S. Tan et al., Free Radic. Biol. Med. 15:407–414). Xanthine oxidase then no longer uses NAD+ as an electron acceptor, but transfers electrons onto oxygen, generating O2−, H2O2, and hydroxyl radical (OH) as purines are degraded to uric acid (J. M. McCord et al., New Engl. J. Med. 312:159–163; R. Miesel et al., Inflammation, 18:597–612). Inflammatory activation converts XDH to XO, mainly by oxidizing structurally important thiolates. Inflammation also markedly up-regulates the conversion of xanthine dehydrogenase (T. D. Engerson et al., J. Clin. Invest. 79:1564–1570).
Inhibition of XO activity blocks the formation of O2− and prevents loss of purine nucleotides, and is therefore salutary in a variety of shock and ischemia reperfusion disorders. Pharmacologic inhibition of XO can also be beneficial by blocking the pro-inflammatory effect of O2− on gene expression (M. D. Schwartz et al., Am. J. Respir. Cell. Mol. Biol., 12:434–440). O2− has been implicated in the nuclear translocation of NF-kappa B and the expression of NF-icB-dependent genes. In mice subjected to hemorrhagic shock, depletion of XO by a tungsten-enriched diet decreased mononuclear mRNA levels of IL-113 and TNF-a. Similar results were obtained after pharmacologic inhibition of XO by in vivo administration of allopurinol. A vicious cycle can be created by oxidant stress, in which O2− induction of pro-inflammatory cytokines results in greater XDH to XO conversion, and thus more O2− production. This suggests that XO inhibitors can exert important anti-inflammatory actions by interrupting this process at multiple points, in particular, by blocking pro-inflammatory gene expression.
Pharmacologic inhibition of XO can also be beneficial in hemorrhagic shock by preserving the intracellular nucleotide pool. Under conditions of energetic failure, induced by hypoxia or by oxidant-induced poly(ADP-ribose) synthetase activation, high energy phosphate nucleotides are sequentially degraded to inosine monophosphate, xanthine, and hypoxanthine. In the presence of XO and molecular oxygen, xanthine and hypoxanthine degrade to uric acid, thereby depleting the purine pool. The loss of available purines with which to form ATP accelerates the loss of intracellular energetics and contributes to cell necrosis and organ failure. XO inhibitors block this terminal degradative pathway and permit the cell to recover and reestablish adequate stores of high energy phosphate nucleotides. In a canine model of severe hemorrhagic shock, pre-treatment with allopurinol resulted in a 6-fold increase in survival (J. W. Crowell et al., Am. J. Phys. 216:744–748). When the administration of allopurinol was delayed until after shock had been produced, allopurinol exerted no benefit. Infusion of the purine base hypoxanthine after the onset of shock similarly provided no benefit. When allopurinol and hypoxanthine were co-infused, however, there was a dramatic increase in survival (no survival in control group at 16 hours post-shock vs. a 40% survival in the treated group at 48 hours). Similar results were obtained in a canine model of hemorrhagic shock in which allopurinol significantly improved survival, whereas a cocktail of free-radical scavengers (superoxide dismutase, catalase, dimethylsulfoxide, and alpha tocopherol) had no effect (D. Mannion, et al., Circ. Shock, 42:39–43). Thus, XO blockade appears to be beneficial by three independent mechanisms: blockade of O2− formation; inhibition of O2− mediated pro-inflammatory gene expression; and preservation of the nucleotide pool available for ATP formation.
Accordingly, there is a clear need for compounds that inhibit the levels of xanthine oxidase in an animal and, accordingly, that are useful for treating or preventing an inflammation disease, a reperfusion disease, or hyperuricemia.
Citation of any reference in Section 2 of this application is not an admission that the reference is prior art to the application.

5-Aryltetrazole compounds and uses thereof


A method and apparatus for 2× oversampling of data having jitter. In some embodiments, the invention is a clock and data recovery device including an alternating edge sampling binary phase detector, and which is configured to stabilize loop characteristics in various jitter environments and can be implemented with small hardware overhead. A transceiver that embodies the invention can be implemented as a CMOS integrated circuit using a 0.18 μm CMOS process, with the transceiver chip being capable of recovering data having a data rate of up to 11.5 Gbps from a signal received over a serial link, while consuming no more than 540 mW from 1.8V supply, and with a bit error rate of less than 10−12.

The term "receiver" is used herein in a broad sense to denote any device capable of receiving and decoding data that has been transmitted over a serial link or other link (and optionally also performing additional functions, which can include decrypting the received data and other operations related to decoding, reception, or decryption of the received data). For example, the term receiver can denote a transceiver that performs the functions of a transmitter as well as the functions of a receiver.
The term "CDR" is used herein to denote a clock and data recovery device. Typically, a receiver includes a CDR. Throughout the disclosure, CDRs are described as devices that receive "data" and generate at least one sequence of samples of the data. It should be understood that the "data" can be a signal indicative of a clock, or a signal indicative of an arbitrary sequence of binary bits of data. Some CDRs include circuitry for recovering both a clock and data from one or more received signals. A "CDR," as the term is used herein (including in the claims) need not include circuitry for recovering both a clock and data from one or more received signals.
The expression "phase detector" is used herein to denote a circuit that determines the phase error (φΔ) present between a sampling clock and data (being sampled by the clock). A phase detector ("PD") is thus useful with a data sampling circuit including a feedback loop for controlling the phase of a sampling clock.
It should be understood that when phase error (φΔ), between a sampling clock and a data signal being sampled using the clock, is expressed herein in degrees, the quantity "360 degrees" corresponds to one bit time of the data signal (with "bit time" being synonymous with "bit period" and denoting the inverse of the bit rate) and typically does not correspond to one period of the sampling clock. Typically, a sampling clock employed in accordance with the invention (e.g., data sampling clock "dCLK" or edge sampling clock "xCLK" discussed below) has frequency equal to f/N, where "f" is the bit rate of the data signal being sampled and N is an integer greater than one (for example, N=4 or N is another small integer). It should also be understood that when a clock is referred to herein as being "X" degrees out of phase with respect to another clock having the same frequency (e.g., when a raw edge sampling clock is said to be 180 degrees out of phase with a raw data sampling clock), the quantity "360 degrees" corresponds to one bit time of a data signal being sampled using the clocks, and typically does not correspond to one period of either one of the clocks. For example, in the below-described preferred implementation of the FIG. 3(a) system, raw data sampling clock "idCLK[0]" and raw edge sampling clock "ixCLK[0]" are referred to as being 180 degrees out of phase with respect to each other because clock "ixCLK[0]" lags clock "idCLK[0]" by one half of a bit time, and "ixCLK[0]" and raw edge sampling clock "idCLK[1]" are 180 degrees out of phase with respect to each other because clock "idCLK[1]" lags clock "ixCLK[0]" by one half of a bit time.
The expression "binary phase detector" is used herein to denote a circuit that determines whether the phase error (φΔ) present between a sampling clock and data (being sampled by the clock) is positive or negative, without determining the magnitude of the phase error.
A binary phase detector (binary PD) based on a 2× oversampling technique has been widely used in transceivers (for receiving data transmitted over high speed serial links) due to its simple structure. A transceiver including such a PD is described in the paper by A. Fiedler, et al., entitled "A 1.0625 Gbps Transceiver with 2×-Oversampling and Transmit Signal Pre-Emphasis," ISSCC Digest of Technical Papers, pp. 238-239, February 1997. However, the loop characteristics of a CDR using such a binary PD are dependent on the jitter amplitude of the input data stream and the CDR might not be robust over a wide range of jitter amplitude. An example of this uncertainty is illustrated in FIG. 1(a), which includes data eye diagrams, 2× based sampling clocks, edge distribution diagrams, and Ia−φΔ curves for large and small amounts of jitter (where Iavg denotes average pumping current), assuming that some phase error (φΔ) is present between the sampling clocks and data. Typically, a CDR including a binary PD asserts a positive charge pump current (IP) to cause advancement of the sampling clock phase when the sampling clock lags the data, and a negative charge pump current (−IP) to cause retardation of the sampling clock phase when the sampling clock leads the data. Ideally (i.e., in the absence of jitter), the average pumping current (Iavg) is equal to the charge pump current (IP) when the sampling clock lags the data and the average pumping current (Iavg) is equal to the negative charge pump current (−IP) when the sampling clock leads the data. However, in a real world application in which there is high frequency jitter, the absolute value of the average pumping current (Iavg) is less than the absolute value of the charge pump current (when the sampling clock leads or lags the data) since the binary PD makes an up/down decision (a decision as to whether to increase or decrease the sampling clock phase) per each data transition and Iavg is proportional to an average difference of the up/down decisions (represented by the shaded area in FIG. 1(a)). Therefore, for the same charge pump current, larger jitter reduces the absolute magnitude of the average pumping current and reduces the gain KPD (the slope of the Iavg versusφΔ curve). So, the gain KPD and the absolute magnitude of Iavg are inversely proportional to the amount of jitter, as indicated by the bottom graph in FIG. 1(a).
It should be understood that the expression "average" pumping current (Iavg) herein denotes an average of instantaneous values of the charge pump current over a time interval in which averaged phase error (averaged φΔ) is positive or negative; not a time interval over which averaged phase error (averaged φΔ) is zero. An average of instantaneous values of charge pump current, over a time interval in which averaged phase error (averaged φΔ) is zero, would be zero (or nearly zero) and would typically be neither proportional nor inversely proportional to the amount of jitter.
The unstable gain (KPD) due to jitter variation, of a conventional CDR that includes a binary PD based on a 2× oversampling technique as described with reference to FIG. 1(a), results in unreliable CDR loop characteristics.
Conventional CDRs that include 2× oversampling PDs do not support any method to measure jitter. Estimation of jitter can be accomplished in accordance with the invention using a modified version of the "dead zone" PD described in Y. Moon, et al., "A 0.6-2.5 Gbaud CMOS Tracked 3× Oversampling Transceiver with Dead Zone Phase Detection for Robust Clock/Data Recovery," ISSCC Digest of Technical Papers, pp. 212-213, February 2001, and in S. Lee, et al., "A 5 Gb/s 0.25 μm CMOS Jitter-Tolerant Variable-Interval Oversampling Clock/Data Recovery Circuit," ISSCC Digest of Technical Papers, pp. 256-257, February 2002. Because the dead zone PD described in the cited papers by Moon, et al. and Lee, et al. is based on 3× oversampling, a CDR including the dead zone PD must employ 3× oversampling and thus requires more hardware to implement and consumes more power than does a CDR that employs 2× oversampling. The noted problems of the prior art can be overcome in accordance with the invention by using a CDR that employs 2× oversampling, has reliable CDR loop characteristics, and includes an embodiment of the inventive alternating edge sampling phase detector ("AES PD") which establishes a dead zone.

Data sampling method and apparatus with alternating edge sampling phase detection for loop characteristic stabilization


A heat exchanger, especially a heat exchanger for use in a motor vehicle as an engine cooling or cabin heating radiator, comprises a bundle of parallel tubes, a header plate formed with holes, each of which receives the respective ends of a plurality of adjacent tubes forming part of a common group of tubes in the bundle, and a compressible sealing gasket interposed between the edge of the hole and the ends of the tubes in the group. At least one of the tube ends in a group of tubes received in any one hole in the header plate has a different geometry from the end of the other tube or tubes in the same group.

Such heat exchangers, as is well known, are used especially in motor vehicles having internal combustion engines, so as to constitute either an engine cooling radiator or a cabin heating radiator. In either of these two applications, an engine coolant fluid, which is usually water with the addition of a suitable antifreeze preparation, flows through the tubes in the bundle, while a stream of air flows over the tubes in the bundle. In this familiar type of heat exchanger, it is usual to provide the same number of holes in the header plate as there are tubes in the bundle, so that each tube end is received individually in a respective hole in the header plate, to which it is sealingly secured.
In French patent application No. 91 03411 in the name of the present Applicant, a heat exchanger is proposed which is of the type comprising a bundle of parallel tubes and a header plate having holes, each of which receives the respective ends of a plurality of adjacent tubes which are part of a common group of tubes. A compressible sealing gasket is generally interposed between the edge of the hole and the tube ends in that group. Due to the fact that the respective ends of the tubes in a group are received in a single hole in the header plate, instead of each one being received individually in a separate hole of the plate, the pitch of the tubes is able to be reduced to a minimum value. In this way the thermal performance of the heat exchanger can be optimised while the dimensions of the header plate are minimised.
However, in the heat exchanger of the type just mentioned, the tubes of any one of the said groups are part of different rows of tubes in the bundle. In addition, this heat exchanger is most particularly suitable where there are two rows of tubes in the bundle, that is to say the latter is a twin-row bundle.

Heat exchanger with a bundle of parallel tubes, in particular for a motor vehicle


A method of watermarking a video signal includes encoding the video signal using at least one encoding parameter that is time-varied according to a watermarking pattern. The parameter affects information lost while encoding the signal. The parameter may be a quantization factor corresponding to a particular coefficient of an encoding transform. The parameter may be an element of a quantization matrix corresponding to a particular coefficient in a block DCT transform. The method may be implemented in devices with limited processing resources by means of a software update. The method enables the devices to imprint an encoded signal with a robust watermark, which may survive subsequent decompression and recompression. Alternatively, a video signal may be watermarked by modifying a magnitude of a non-dc spatial frequency component in a manner which varies with time according to a watermarking pattern. Corresponding watermark detection methods and watermarking devices also are disclosed.

Watermarking of video signals (that is, the embedding of some identifiable code, pattern or feature within the video signal) is known, and can be used to identify the source of a video signal or the signal's processing history, for example. It is also known to watermark a video signal as part of an encoding process, that is, to embed a watermark in the encoded signal, whether or not the source signal was already watermarked. Watermarking can also be regarded as imprinting a signal with an identifiable watermarking pattern. Throughout the remainder of this specification the term watermarking pattern will be used to encompass any such identifiable pattern, code or feature suitable for watermarking purposes.
Forensic tracking watermarks can form the basis for highly flexible and transparent copyright protection systems. For example, according to the watermark embedded in a signal, certain actions with that signal may be permitted (such as the recording of a watermarked movie on the storage device of a personal video recorder (PVR) or export of the movie to a user's portable player), whilst others denied (such as subsequent distribution of a received movie over a peer-to-peer network).
In general, video watermarking can be performed on baseband (uncompressed) or compressed video streams. Although the operations involved in baseband watermarking are generally simpler, the high data rates mean that the process either requires dedicated hardware or fast general-purpose processors. In contrast, the data rates for compressed domain watermarking are lower, but the complexity of parsing the bit-stream results in dedicated hardware or fast processors again being required. Thus, in either case, dedicated hardware or significant processor resources have in the past been necessary for video watermarking. Such dedicated hardware and/or the requisite processor resources have previously not been incorporated in consumer devices such as digital video recorders (DVRs), which are also known as personal video recorders (PVRs). These are devices that can record video without videotape to a digital storage device (typically a hard-drive-based storage medium), and include set-top boxes and software for personal computers. In other words, they permit capture and playback of video signals. Typically, current DVRs comprise limited processing resources and a dedicated encoder (such as a single encoder chip). Clearly, it would be problematic, if not impossible, to upgrade existing DVRs to increase their processing capabilities and to include additional hardware to enable them to watermark video signals.
A problem with certain known watermarking techniques is that it is possible to remove the watermark, for example by decompressing a watermarked encoded signal, and then re-compressing.


A discharging power supply including a direct current power supply unit, a control unit for controlling an output of the direct current power supply unit, and a vibrating current generation unit having a capacitance connected in parallel with a pair of outputs from the direct current power supply unit and an inductance connected to at least one of the pair of outputs, wherein the control unit controls the direct current power supply unit so that current outputted from the direct current power supply unit does not exceed a limit current value in at least a portion of a range of voltage that can be outputted from the direct current power supply unit. Thus, regardless of whether the discharge power is set to be high or low, discharge current exceeding the limit characteristic line can be prevented from flowing.

In various plasma application equipment, glow discharge application equipment and the like, occurrence of arc discharge during discharging often causes problems in the operation of the equipment. For this reason, a discharging power supply is often required that can definitely and quickly break arc discharge. In the following, as a specific example, a sputtering apparatus for use in forming thin film will be described.
FIG. 11 is a schematic diagram showing the structure of a relevant part of a DC sputtering apparatus. This sputtering apparatus comprises a vacuum chamber 101 and a sputtering DC power supply 110. The anode of the power supply 110 is connected via a connecting cable 120A to the chamber 101, and placed at ground potential. On the other hand, the cathode of the power supply 110 is connected via a connecting cable 120B to a sputtering target 104 provided inside the chamber 101. A substrate 100 on which thin film is to be deposited is placed inside the chamber 101.
In forming film, first, the inside of the chamber 101 is evacuated by a vacuum evacuation pump 106, and discharge gas such as argon (Ar) is introduced from a gas supply source 107 to maintain the inside of the chamber at a predetermined discharge pressure. Next, the power supply 110 applies an electric field between the target 104 and the chamber 101 to generate glow discharge 108. Then positive ions in plasma generated in the discharge space impinge on the surface of the target 104 to sputter atoms of the target 104. Such a sputter phenomenon can be used to form thin film made of the material of the target 104 on the substrate 100.
Such a sputtering apparatus is widely used in the process of forming thin film for various products including semiconductor devices, CDs (Compact Discs), DVDs (Digital Versatile Discs), and liquid crystal display devices.
However, arc discharge 150 may occur during such a sputter operation. Such arc discharge 150 occurs more often in the vicinity of the target 104. When such arc discharge 150 occurs, a large current locally flows, which damages the target 104 or the substrate 100.
For example, when arc discharge 150 occurs on the side of the target 104, a large current concentrates on a small region of the target 104, which causes a large amount of deposition material to emit instantaneously from the region. This phenomenon is referred to as "splash", which splashes particles of deposition material on the surface of the substrate 100, thus causing damage.
It is therefore required to provide arc suppressing means in the power supply 110 in order to prevent damage due to such arc discharge.
Methods of suppressing arc discharge in DC sputtering may include the following:
(1) Arc discharge is suppressed by periodically turning off the power supply output to provide a resting period.
(2) Arc discharge is quenched by inverting the current using the switching action of arc discharge and the oscillation of LC provided in the output circuit of the power supply.
(3) Arc discharge is detected, and the arc current is turned off by a switch element. In this case, the switch element may be inserted in series or parallel with the load to turn off the arc current.
(4) Arc discharge is detected, and then it is quenched by activating a switch element to apply reverse voltage.
(5) Arc discharge is suppressed by periodically activating a switch element to apply reverse voltage.
Among them, the inventors disclosed the methods that use a switch element in Japanese Patent Nos. 2835322 and 2835323.
On the other hand, the above method (1) has a problem of decreasing throughput because sputtering is interrupted.
In contrast, the above method (2) has the potential to simplify the apparatus configuration in that arc discharge can be suppressed without using switch elements and the like. More specifically, if an LC resonant circuit is provided at the output end of the DC power supply, and when arc discharge occurs, its switching action can be used to generate vibrating current. When this vibrating current has crossed 0 A (zero ampere) to change its polarity, the current can be turned off by the rectifying action of arc discharge (current does not flow under the reverse voltage because thermoelectrons are emitted only from the hot spot), thereby quenching arc.
However, after independent investigation, the inventors have found that such a discharging power supply having arc quenching mechanism with vibrating current has room for improvement with respect to its operation.
More specifically, the operation control for such a DC power supply using an LC resonant circuit may be performed so that a constant power control operation, a rated current limit operation, and a rated voltage limit operation are combined to prefer one of the signals that minimizes the output.
In other words, in such operation control, for a low sputter voltage, the flowing current is controlled to have the smaller of a value corresponding to the constant power control operation and a value limited by the rated current limit operation.
In contrast, in order to quench arc in the vibration mechanism, the amplitude of vibrating current that is generated at the transition from sputter voltage to arc voltage and that depends on LC circuit constants must exceed the sputter current to generate current vibration that crosses 0 A.
Two methods for generating such a large current vibration can be mentioned.
The first of the methods is to use LC constants for which a large current amplitude can be obtained corresponding to the rated current limit operation even for a low sputter voltage (e.g., 200 V).
The second is to set LC constants so that current amplitude corresponding to the rated current limit can be obtained at a lower value in the range of normal sputter voltage (e.g., 400 V), and below this sputter voltage, to variably control the power rating so that the upper limit of current is decreased corresponding to the voltage.
However, when the first method is used, an excessively large current vibration occurs during operation at normal sputter voltage (e.g., 600 V). As a result, large stress may be imposed on electric parts used in the power supply and/or noise may occur.
For this reason, the LC constants must be determined to correspond to a lower sputter voltage, and thus the second method described above must be used. For example, the discharge voltage may significantly decrease immediately after the target 104 is attached or after the chamber 101 is opened to the atmosphere because the surface of the target 104 is covered with oxides and the like. For this reason, the sputter power must be set to be sufficiently low. Thus, sputtering is performed initially in a sufficiently low power setting, which is referred to as "target cleaning mode". Then, as oxides are removed from the surface of the target 104 and the discharge voltage increases, the power setting is raised to transfer to normal sputter voltage.
However, this method has a problem that it involves cumbersome operations because the power setting is adjusted according to the sputter voltage.
The invention has been made on the basis of recognition of these problems. An object of the invention is to provide a discharging power supply and sputtering power supply being capable of quickly and definitely quenching arc discharge, having simple structure and being easy to operate, and a sputtering apparatus using the same.

Discharging power source, sputtering power source, and sputtering device


This invention relates to a two component catalyst system for the polymerization of metathesis polymerizable cycloolefins, comprising (a) a tungsten compound of the formula WOX.sub.4-x (OAr).sub.x where X is chlorine, bromine or fluorine, Ar is a hindered phenyl ring having 1-5 specified substituents and x = 1, 2 or 3; and (b) an activator compound.. Among the preferred molecules or groups that are substituted on the phenyl ring of the tungsten compound are phenyl, chlorine, bromine, methoxy and isopropyl groups. Ar can also represent a multi-substituted phenyl group such as 2,4-dichloro-6-methylphenyl.

Preparation of thermoset cycloolefin polymers via metathesis catalysts is a relatively recent development in the polymer art. Klosiewicz, in U.S. Pat. Nos. 4,400,340 and 4,520,181, teaches preparation of such polymers from dicyclopentadiene and other similar cycloolefins via a two stream reaction injection molding technique wherein a first stream, including the catalyst, and a second stream, including a catalyst activator, are combined in a mix head and immediately injected into a mold where, within a matter of seconds, polymerization and molding to a permanently fixed shape take place simultaneously.
In the typical system, according to Klosiewicz, the catalyst component is a tungsten or molybdenum halide and the activator is an alkyl aluminum compound. Most strained ring non conjugated polycyclic cycloolefins are metathesis polymerizable. These include, for example, dicyclopentadiene, higher order cyclopentadiene oligomers, norbornene, norbornadiene, 4-alkylidene norbornenes, dimethanooctahydronaphthalene, dimethanohexahydronaphthalene and substituted derivatives of these compounds, such as 5 vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methyl 2-norbornene, 5-phenyl-2-norbornene, ethylidenetetracyclododecane, methyltetracyclododecane, 5,6-dimethyl-2-norbornene, 5-ethyl 2-norbornene, 5-butyl-2-5-hexyl-2-norbornene, 5-octylnorbornene, 5-dodecyl-2-norbornene, tetracyclododecane, hexacycloheptadecene, methyltetracyclododecene and ethylidenetetracyclododecene. The preferred cycloolefin monomer is dicyclopentadiene or a mixture of dicyclopentadiene with other strained ring hydrocarbons in ratios of 1 to 99 mole % of either monomer, preferably about 75 to 99 mole % dicyclopentadiene.
The metathesis catalyst system is comprised of two parts, i.e., a catalyst component and an activator. The preferred catalyst component as taught by Klosiewicz has been a tungsten halide, and preferably a mixture or complex of tungsten hexachloride (WCl.sub.6) and tungsten oxytetrachloride (WOCl.sub.4).
The tungsten or molybdenum compound of Klosiewicz is not normally soluble in the cycloolefin, but can be solubilized by complexing it with a phenolic compound.
In U.S. Pat. No. 4,981,931, by Bell, was disclosed tungsten catalyst compositions for metathesis polymerization comprising ##STR1## where X is Cl or Br, n is 2 or 3, R.sup.1 is a H, a Cl, an alkyl group having 1-10 carbons, an alkoxy group having 1 to 8 carbons, or a phenyl group, R.sup.2 is H or an alkyl group having 1 to 9 carbon atoms and R.sup.3 is a H or an alkyl group having 1 to 10 carbon atoms for use with a trialkyltin hydride or a triphenyltin hydride activator. A process to employ such tin activator compounds in a system in which gelation and polymerization were delayed for at least a time sufficient to charge the reaction mixture to a mold. Both the catalyst and activator compounds had improved stability, with resistance to oxygen and moisture. The catalyst compounds were easy to isolate, instead of being mixtures as are those found in the prior art. Although certain advantages were found, these compounds when used to polymerize strained ring cycloolefins produced polymers with a higher than desired residual monomer level.
It is therefore an object of this invention to provide a catalyst composition that polymerizes strained ring polycyclic cycloolefins that have very low levels of residual monomer.
There is also a need for polymers of the type described by Klosiewicz to have higher levels of heat resistance, while maintaining other properties, such as impact and tensile strengths at levels similar to those found in prior art strained ring cycloolefin polymers. Previously, improved heat resistance was obtained through use of comonomers with the dicyclopentadiene (DCPD) monomer. The improved heat resistance was previously obtained at the cost of decreased impact resistance. Therefore it is a further object of this invention to provide catalyst compositions that polymerize strained ring polycyclic cycloolefins producing polymers with a higher level of heat resistance than prior art polymers while maintaining their impact strength.
Another object of this invention is to find catalysts that are more efficient in polymerizing dicyclopentadiene.
This invention is a process for preparing a polymer which comprises contacting a strained ring polycyclic polyolefin with a substantially pure tungsten complex, having the formula WOX.sub.4-x (OAr).sub.x wherein X represents a halogen selected from the group consisting of bromine, chlorine and fluorine; OAr represents a mono, di-, tri , tetra- or penta substituted phenoxy group and where x is 1, 2 or 3. In the preferred embodiments of this invention, X is chlorine. These catalysts are efficient and promote catalysis of dicyclopentadiene at catalyst concentration levels of 1 part catalyst to 4000 parts monomer or less.
Various activator compounds may be employed as are known in the art to act together with the tungsten catalyst complexes described above to cause the polymerization of strained ring polycyclic cycloolefins. Among the activator compounds that can be employed in the practice of this invention are trialkyltin hydrides, triaryltin hydrides, alkylaluminum compounds, alkylalkoxyaluminum halides, diethylaluminum chloride, diethylzinc, dibutylzinc, and triethylsilane. Mixtures of two or more activator compounds may produce more desirable polymerization conditions and more desirable polymer properties than a single activator compound in certain situations.
Of the trialkyltin hydrides, suitable for use in the process of the invention, tri-n-butyltin hydride is preferred. Among the triaryltin hydrides is triphenyltin hydride.
As stated already hereinbefore the DCPD monomer used herein was of highly pure grade, containing less than 2% impurities. The DCPD used in the following examples was about 98-99% pure monomer. Other monomers or comonomers employed in the practice of this invention should also be of about this degree of purity. However, it is also contemplated that the polymerization feed compositions of this invention can polymerize less pure grades of dicyclopentadiene when the appropriate tungsten catalyst compound, activator compound and other components are employed.
When the two parts of the catalyst system, the tungsten catalyst and the tin activator, are combined, the resulting cycloolefin (for example, DCPD) to catalyst compound ratio will be from about 500:1 to about 15,000:1 on a molar basis, preferably 2000:1 and the molar ratio of the tungsten complex versus the tin activator compound will be from about 1:2 to 1:6.
Generally the polymerization takes place in bulk, but the catalyst components may be dissolved in a small amount of solvent, such as toluene. It is preferred, however, to use DCPD as a solvent. When the liquid tri-n-butyltin hydride activator compound is used, no solvent is necessary for its addition and triphenyltin hydride is readily soluble in DCPD.
A preferred method in the practice of this invention for the polymerization of DCPD is to contact a tungsten compound catalyst containing component stream with a tin compound activator containing component stream wherein at least one of the streams contains the DCPD. For example, it is possible to dissolve the tungsten catalyst in DCPD and either to dissolve the activator in DCPD or in another solvent or to use the activator without any solvent. Usually both the tungsten catalyst and the tin activator are first dissolved in separate streams of DCPD prior to the mixture of said streams.
After the streams have contacted with each other the resulting mixture may be injected or poured into a mold, where the polymerization takes place. The polymerization is exothermic, but heating the mold from about 50 to 100.degree. C. is preferred.
The WOX.sub.4-x (OAr).sub.x complexes do not require any added solvent in order that they may become soluble in DCPD solution. In general, the solutions are quite stable in DCPD. The solutions can be used immediately, or within 48 hours, in the polymerization of DCPD with a suitable activator. When the tungsten complexes are stored in dicyclopentadiene/2-methoxy ethyl ether (diglyme) solution (storage up to four weeks at 40.degree. C.) the viscosity of the component remained constant. No difference in reactivity has been observed for solutions with added diglyme compared with those which possess no such additive. The stability of the solutions can also be improved to eight weeks, and beyond, by addition of an antioxidant, such as 2,6-di-tert-butyl-4-methylphenol. Monitoring of the tungsten phenoxide species in solution by electrochemical measurements, e.g., cyclic voltammetry, demonstrated that the integrity of the tungsten component is maintained during storage.
During the polymerization of DCPD various additives can be included in the reaction mixture to modify the properties of the polymer product of the invention. Possible additives include fillers, pigments, antioxidants, light stabilizers, plasticizers and polymeric modifiers.
The invention further relates to a two component catalyst system in which the first component is a tungsten compound of the formula WOX.sub.4-x (OAr).sub.x, wherein x is 1, 2 or 3; X is F, Cl or Br and wherein Ar represents a phenyl ring substituted with one or more of the following substituents: hydrogen (H), bromo (Br), chloro (Cl), fluoro (F), iodo (I), nitro (NO.sub.2), cyano (CN), aldehyde (CHO), carboxy (COOH), hydroxymethyl (CH.sub.2 OH), alkoxy (OR), alkylthio (SR), arylthio (SAr), acyl (COR), aroyl (COAr), acyloxy (OCOR), alkoxycarbonyl (COOR), cycloalkanes (cyclo R), dialkylamino (NR.sub.2), diarylamino (NAr.sub.2), alkylsulfonyl (SO,R), arylsulfonyl (SO.sub.2 Ar), alkylsulfonate (SO.sub.2 OR), arylsulfonate (SO.sub.2 OAr), aryl (Ar), aralkyl (CH.sub.2 Ar), aryloxy (OAr), aIkyI groups containing 1-20 carbon atoms, fluoroalkyl groups containing 1 to 10 carbon atoms and allyl (--CH.sub.2 --CH.dbd.CH.sub.2). Among the most preferred molecules or groups that are substituted on the phenyl ring include methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, octyl, nonyl, phenyl, bromo, chloro, fluoro, ethoxy (OEt), methoxy (OMe), cyclopropane (cyclo-C.sub.3 H.sub.5), trifluoromethyl, methylsulfonyl (SO.sub.2 Me), and benzyl (CH.sub.2 C.sub.6 H.sub.5). The substituents need not be identical on a particular phenyl ring. For example, a trisubstituted phenyl group such as 2,4-dichloro-6-methyl phenyl. A generalized formula to take the case of the mixed substituents into consideration is, e.g., WOCl.sub.p (OAr).sub.q (OAr).sub.r where p + q + r = 4. Mono, di, tetra, and penta substituted phenols, as well as the aforementioned tri substituted phenols, can also be employed in making the tungsten compounds employed in this invention. The desired tungsten compounds are prepared by reacting the appropriate phenol with WOCl.sub.4 in solution. The molar ratio of phenol to WOCl.sub.4 is about equal to x in the generalized formula WOCl.sub.4-x (OAr).sub.x. The invention is also contemplated to include the use of mixtures of two or more different tungsten compounds. The phenyl ring, symbolized by Ar in the above general formula, may have R substituted at the 1, 2, 3, 4 or 5 positions. In the monosubstituted phenyl ring, R may be at the 2, 3 or 4 positions. In the disubstituted phenyl ring the substituents R.sub.1 and R may be at the 2,6; 2,5; 2,4; 2,3; 3,4; or 3,5 positions. R and R.sub.1 may be the same or different groups. In the trisubstituted phenyl ring substituents R, R.sub.1 and R.sub.2 may be at the 2,3,4; 2,3,5; 2,3,6; 2,4,5; 2,4,6 or the 3,4,5 positions, where R, R.sub.1 and R.sub.2 may be the same or different. The tetra substituted structures for the phenyl ring have substituents at the 2,3,4,6; 2,3,5,6 or the 2,3,4,5 positions, where R, R.sub.1, R.sub.2, and R.sub.3 may be the same or different. An example of such would be made from 2,3,5,6 tetrachlorophenol. The penta substituted ring has substituents at the 2,3,4,5 and 6 positions, where each substituent may be the same or different. An example of the penta substituted structure would be made from C.sub.6 F.sub.5 OH.
The second component of the catalyst system is an activator compound that in combination with the tungsten compound is capable of yielding a catalyst able to polymerize DCPD in bulk. Such activators or co catalysts include, for example organoaluminum compounds such as trialklyaluminum, dialkylaluminum halides, alkylaluminum dihalides, dialkyl(alkoxy)aluminum, alkyl(alkoxy)aluminum halide; dialkylzincs, alkylzinc halides, diarylzinc, arylzinc halides, alkylsilanes (RSiH.sub.3, R.sub.2 SiH.sub.2 and R.sub.3 SiH, where R is an alkyl group), tetraalkyltins, trialkyltin hydrides, dialkyltin dihydrides, triaryltin hydrides and the corresponding alkyl and aryl lead hydrides. Specific examples of activators include ethylaluminum dichloride, diethylaluminum chloride, triethylaluminum, diethylzinc, dibutylzinc, ethyl n propoxyaluminum chloride, diphenylzinc, tributyltin hydride, trioctyltin hydride, diphenyltin dihydride, and triphenyltin hydride. Preferred activators include triphenyltin hydride and trialkyltin hydrides, such as a tributyltin hydride.
In order to maintain the stability of tungsten compounds of the present invention with the 98-99% dicyclopentadiene without premature gelation, it is usually necessary to add a stabilizer compound to the solution containing the tungsten compound, and a rate moderator to the solution containing the tin activator compound. It is preferred to store the tungsten compounds in solution in dicyclopentadiene. When the stabilizer compound is omitted, a slow polymerization of the monomer proceeds in the storage container. Stabilizer compounds include diethyl ether (OEt.sub.2); ethylene glycal dimethyl ether (monoglyme), Z-Methoxyethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), benzonitrile, acetonitrile, tetrahydrofuran, phenols with one aromatic ring {such as 2,6-di-t-butyl-4-methylphenol (BHT) or 2,6-di-tert-butyl-4-sec-butylphenol, e.g., Isonox 132}, bisphenols with two aromatic rings {such as 4,4'-methylenebis(2,6-dimethylphenol) sold under the tradename Lowinox 44M26 by Lowi Chemical Company of Akron, Ohio; 4,4'-methylenebis(2,6-di-tert-butylphenol sold under the tradename Lowinox 002; 2,2'-methylenebis(4-ethyl-6-butylphenol) sold under the tradename Cyanox 425; 2,2'-ethylenebis(4,6-di-tert-butylphenol sold under the tradename Vanox 1290; 2,2'-methylenebis-(4-ethyl-6-(1-methylcyclohexyl)phenol sold under the tradename Permanax WSP; 4,4'-butylidenebis(6-tert-butyl-3-methylphenol) sold under the tradename Lowinox 44B25; 4,4'-thiobis(6-tert butyl-3-methylphenol sold under the tradename Lowinox 44S36; 1,1'-thiobis-(2-naphthol) sold under the tradename SAO 30; 2,2'-thiobis(4-methyl-6-tert-butylphenol) sold under the tradename SAO-6; 2,2'-isobutylidene-bis(4,6-dimethylphenol sold under the tradename Lowinox 22IB46; or 2,2'-methylenebis(4-methyl-6-cyclohexyl)phenol) sold under the tradename Vulkanox ZKF} or polyphenols with more than two aromatic rings {such as 1,3,5-trimethyl-2,4-6-tris(3,5-di-t-butyl-4-hydroxybenzene)benzene sold under the tradename Ethyl Antioxidant 330; sterically hindered polynuclear phenols sold under the tradename Lowinox 22CP46 and Lowinox CPL by Lowi Chemical Company or the butylated reaction product of p-cresol and dicylopentadiene such as Wingstay L powder sold by the Goodyear Tire and Rubber Company of Akron, Ohio} may also be used. In addition, mixtures of the above stabilizer compounds such as a mixture of diglyme and one or more phenols or other Lewis bases can be employed in the practice of this invention.
The rate moderator compound prevents the polymerization process from being too rapid, provides for adequate mixing of the catalyst components, and allows the mold to be completely filled. The rate moderator compounds include various nitrogen or phosphorus compounds used for this purpose as described in U.S. Pat. Nos. 4,727,125; 4,883,849; and 4,933,402. These rate moderators are generally selected from the group consisting of phosphines, phosphites, phosphinites, phosphonites, pyridines, and pyrazines. Preferred rate moderators include pyridine (py); pyrazine (pyz); 2,6-dimethylpyrazine (Me.sub.2 pyz); tributylphosphine (Bu.sub.3 P); triethylphosphine (PEt.sub.3); tricyclohexylphosphine (PCy.sub.3); triphenylphosphine (PPh.sub.3); methyldiphenylphosphine (PMePh.sub.2); dimethylphenylphosphine (PMe.sub.2 Ph); triethylphosphite (P(Oet).sub.3); tributylphosphite (P(OBu).sub.3); triisopropylphosphite (P(O-i-Pr).sub.3); ethyldiphenylphosphonite (P(OEt)Ph.sub.2 ; triphenylphosphite (P(OPh).sub.3); triisopropylphosphine (P-i-Pr.sub.3); trimethylphosphite (P(OMe).sub.3); tri-tert butylphosphine (P tert-Bu.sub.3); diethylphenylphosphonite (P(OEt).sub.2 Ph); and tribenzylphosphine (P(CH.sub.2 Ph).sub.3). The more preferred rate moderators are phosphines and phosphites, e.g., tributylphosphine (Bu.sub.3 P) and tributylphosphite ((BuO).sub.3 P). The stabilizer and rate moderator compounds are not necessary when lower purity dicyclopentadiene is employed, unless prolonged storage times are desired. Also, the stabilizer is not necessary when prolonged storage of the catalyst in the monomer is not desired.
In some embodiments of this invention, a preformed elastomer which is soluble in the reactant streams is added to the metathesis catalyst system in order to increase the impact strength of the polymer. The elastomer is dissolved in either or both of the reactant streams in an amount from about 3 to about weight percent range, based on the weight of monomer. Illustrative elastomers include natural rubber, butyl rubber, polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene copolymer, styrene butadiene-styrene triblock rubber, random styrene butadiene rubber, styrene-isoprene-styrene triblock rubber, ethylene-propylene-diene terpolymers, ethylene vinyl acetate, and nitrile rubbers. Various polar elastomers can also be emp The amount of elastomer used is determined by its molecular weight and is limited by the viscosity of the resultant reactant streams. The resultant reactant streams containing elastomer cannot be so viscous that mixing is not possible. Although the elastomer can be dissolved in either one or both of the streams, it is desirable that it be dissolved in both.
In addition to measuring gel and cure times and residual DCPD monomer level, a measurement of swell value was made. The swell value is an indication of the degree of crosslinking in the polymer, i.e., lower swell values indicate higher degree of crosslinking. The general procedure used for swell value determinations is as follows: A 5 gram sample of polymer is removed from its test tube (by breaking the glass) and carefully sliced into 1-2 mm thick sections across the cylindrical axis with a tile cutter. The burrs are removed, each slice weighed to the nearest milligram and strung onto a stainless steel or copper wire taking care to keep them in known sequence. This is done for each sample at a given monomer feed. The wire is made into a closed loop and placed in 50 ml of toluene for each gram of polymer. These flasks are then heated to reflux for 16 hours (overnight) and cooled. Each loop is successively removed from the flask and placed in a small dish of fresh toluene. The slices are removed, patted dry, and weighed individually, again taking care not to disturb their sequence or to tear the swollen samples. The swell values are calculated using the following formula: swell (%)= (w.sub.2 -w.sub.1)/w.sub.1 .times.100%, where w.sub.1 = initial weight of polyDCPD sample and w.sub.2 = weight of solvent swollen polyDCPD sample. Since the swell value is an indication of the degree of crosslinking in the polymer, low values are preferred.
The best mode now contemplated of carrying out this invention will be illustrated with the following examples. The examples are given for the purpose of illustration only and the invention is not to be regarded as limited to any of the specific materials or conditions used in the examples.
In the following examples, in which tungsten complex catalyst components are prepared, tungsten hexachloride (WCl.sub.6) was obtained from GTE Sylvania Chemical Company and used as received. 2,6-diisopropylphenol and 2,6-dichloro-phenol (HOC.sub.6 H.sub.3 -2,6-Cl.sub.2) were purchased from Aldrich Chemical Company and used as received. Hexamethyldisiloxane (Me.sub.3 SiOSiMe.sub.3) (Aldrich) was sparged with dry nitrogen before use.
Cyclopentane, diethyl ether, and pentane were dried over 4A molecular sieves and sparged with nitrogen prior to use. Toluene was placed in contact with 13X molecular sieves and sparged with dry nitrogen before use.
All operations were carried out under a dry nitrogen atmosphere or in vacuum either in a Vacuum Atmospheres Dri Lab (inerted by argon gas) or using Schlenk techniques. All solvent transfers were performed by cannula or syringe techniques to maintain an inert atmosphere.
In the Examples in which polymerization studies are set forth, the following general procedures were followed. All manipulations were performed anaerobically in nitrogen-sparged pop bottles or under an argon atmosphere (Vacuum Atmospheres Dri Lab) or using Schlenk techniques. Tri-n-butyltin hydride (packaged in Sure/Seal bottle) was purchased from Aldrich Chemical Company and stored refrigerated (0.degree. C.). Diglyme was dried by placing it over 3A molecular sieves and sparged with nitrogen before use. Where necessary rate moderators, such as tributylphosphite (Albright and Wilson), were dried over molecular sieves and sparged with dry nitrogen prior to use.
Polymerizations were conducted in nitrogen-sparged test tubes by adding together the catalyst and activator components (2.5 ml of each), mixing on a vortex mixer and then inserting the tube into an oil bath at 80.degree. C. or higher or into a heated block at about 33.degree. C. Gel times were estimated by observing the initial viscosity change and the times were taken when the polymerization increased the exotherm to 100.degree. C. (T.sub.100.degree. C.) or 180.degree. C. (T.sub.180.degree. C.), and to the maximum temperature of the polymerization (T.sub.max). Polymer swells were obtained by refluxing the samples in toluene for 16 hours, cooling for four hours and determining the percentage weight gain.
The tungsten starting material used in all catalyst preparation is tungsten oxytetrachloride complex (WOCl.sub.4). This compound was prepared in the following manner. A solution of hexamethyl-disiloxane (HMDS) (13.40 ml, 0.063 mol) in toluene (100 ml) was added dropwise into a toluene (200 ml) solution of WCl.sub.6 (25 g; 0.063 mol) in a 500 ml round bottomed flask (with stirring) over a 75 minute period. After the HMDS addition was completed, the column was removed and the reaction mixture was allowed to stir overnight under nitrogen. The brown solution was filtered in the dry box to yield a quantity of crude, orange WOCl.sub.4 (19.02 g; 88% yield). Immediately before use, the crude material was sublimed under reduced pressure at 100.degree. C. in small portions to give bright orange crystalline WOCl.sub.4. Pure commercial quantities of WOCl.sub.4 may be substituted in any of the catalyst preparations.

Pure tungsten oxyphenolate complexes as DCPD polymerization catalysts