A novel continuous gas phase polymerization process for producing polyethylene and interpolymers of ethylene and at least one other olefin is provided wherein a non-aromatic halogenated hydrocarbon(s) is used in a specified amount such that the activity of the titanium, zirconium and/or hafnium containing Ziegler-Natta catalyst is increased.

The present invention relates to a continuous gas phase polymerization process for producing polyethylene and interpolymers of ethylene and at least one other olefin comprising introducing into a polymerization medium ethylene or ethylene and other olefin(s), a Ziegler-Natta catalyst comprising at least one transition metal component selected from titanium, zirconium, hafnium, or mixtures thereof, a co-catalyst component, and at least one non-aromatic halogenated hydrocarbon(s) wherein at least one or more non-aromatic halogenated hydrocarbon(s) is added in a molar ratio of non-aromatic halogenated hydrocarbon(s) to the transition metal component of the Ziegler-Natta catalyst from 0.2:1 to about 3:1. More specifically, the present invention relates to a process to enhance the activity of a Ziegler-Natta catalyst by adding at least one non-aromatic halogenated hydrocarbon(s) wherein at least one or more non-aromatic halogenated hydrocarbon(s) is added in a molar ratio of non-aromatic halogenated hydrocarbon(s) to the transition metal component of the Ziegler-Natta catalyst in a range of 0.2:1 to about 3:1; wherein the catalyst activity is increased over the range as compared with the process conducted outside the range.
The use of halogenated hydrocarbons with Ziegler-Natta catalysts for the production of polyethylene is disclosed in U.S. Pat. Nos. 5,863,995; 5,990,251; 4,657,998 and 3,354,139. In general, it is disclosed that the halogenated hydrocarbons may reduce the rate of ethane formation, control the molecular weight of the polyethylene, produce polyethylenes with broad molecular weight distributions, or provide other effects.
In U.S. Pat. No. 5,990,251 it is disclosed that halogenated hydrocarbons are used, in a polymerization process for producing polyethylene utilizing a titanium based Ziegler-Natta catalyst for increasing the catalyst activity in the polymerization. It is further stated that the amount of halogenated hydrocarbon must be present in a molar ratio of halogenated hydrocarbon to titanium of the Ziegler-Natta catalyst from 0.001 to 0.15. Furthermore, it is disclosed that when the molar ratio of halogenated hydrocarbon to titanium is too high, the activity of the catalyst is not appreciably modified or is substantially reduced in a continuous polymerization process. It is also stated that when the molar ratio is too low, the catalyst activity is not substantially modified.
In U.S. Pat. No. 5,863,995, there is reference to catalytic activity in a process for producing polyethylene using a titanium containing Ziegler-Natta catalyst and a halogenated hydrocarbon in a specified amount. The patent states that the halogenated hydrocarbon is present in a molar ratio of halogenated hydrocarbon to the titanium in the catalyst of 0.01 to 1.8. It is further stated that the specified quantity of halogenated hydrocarbon results in no substantial variation of the average activity of the catalyst.
In U.S. Pat. No. 3,354,139, there is disclosed the use of halogenated hydrocarbons with a Ziegler-Natta catalyst to control the molecular weight of polyethylene prepared in a solution or slurry polymerization process.
In U.S. Pat. No. 4,657,998, there is disclosed a catalyst system comprising a titanium containing catalyst component, isoprenylaluminum and a halohydrocarbon for the production of polyethylene having a broad molecular weight distribution.
In this invention, applicants have unexpectedly found that in a continuous gas phase polymerization process for producing polyethylene and interpolymers of ethylene and at least one other olefin comprising introducing into a polymerization medium the ethylene or ethylene and at least one other olefin, a Ziegler-Natta catalyst comprising at least one transition metal component selected from titanium, zirconium, hafnium, or mixtures thereof, a co-catalyst component, and at least one non-aromatic halogenated hydrocarbon(s) wherein at least one or more non-aromatic halogenated hydrocarbon(s) is added in a molar ratio of non-aromatic halogenated hydrocarbon(s) to the transition metal component of the Ziegler-Natta catalyst in a range of about 0.2:1 to about 3:1, the activity of the catalyst is increased as compared with the process conducted outside the range. Applicants have also unexpectedly found that the increase in activity can be preceded by an initial decrease in catalyst activity for a period of time when the continuous process is transitioned to the molar ratio range.
In a first embodiment of this invention, a process for increasing catalyst activity in a continuous gas phase process for polymerizing ethylene or ethylene and at least one or more other olefin(s) is provided. The process comprises contacting, under polymerization conditions, the ethylene or ethylene and at least one or more other olefin(s) with a Ziegler-Natta catalyst comprising at least one transition metal component selected from the group consisting of titanium, zirconium, hafnium and mixtures thereof and a co-catalyst component, and at least one or more non-aromatic halogenated hydrocarbon(s) wherein the at least one or more non-aromatic halogenated hydrocarbon(s) is added in a molar ratio of non-aromatic halogenated hydrocarbon(s) to the transition metal component of the Ziegler-Natta catalyst from 0.2:1 to about 3:1.
In another embodiment of this invention, a process for increasing catalyst activity in a continuous gas phase process for polymerizing ethylene or ethylene and at least one or more other olefin(s) is provided. The process comprises contacting, under polymerization conditions, the ethylene or ethylene and at least one or more other olefin(s) with a Ziegler-Natta catalyst comprising at least one transition metal component selected from the group consisting of titanium, zirconium, hafnium and mixtures thereof, a co-catalyst component, and at least one or more non-aromatic halogenated hydrocarbon(s) wherein at least one or more non-aromatic halogenated hydrocarbon(s) is added in a molar ratio of non-aromatic halogenated hydrocarbon(s) to the transition metal component of the Ziegler-Natta catalyst in a range of 0.2:1 to about 3:1; wherein the catalyst activity is increased over the range as compared with the process conducted outside the range.
These objects, and other objects, will become more apparent to others with ordinary skill in the art after reading this disclosure.
In the two embodiments of this invention, a process is provided for increasing catalyst activity in a continuous gas phase process for polymerizing ethylene or ethylene and at least one or more other olefin(s), the process comprising contacting, under polymerization conditions, the ethylene or ethylene and at least one or more other olefin(s) with a Ziegler-Natta catalyst comprising at least one transition metal component selected from the group consisting of titanium, zirconium, hafnium and mixtures thereof, a co-catalyst component, and at least one or more non-aromatic halogenated hydrocarbon(s); wherein at least one or more non-aromatic halogenated hydrocarbon(s) is added in a molar ratio of non-aromatic halogenated hydrocarbon(s) to the transition metal component of the Ziegler-Natta catalyst from 0.2:1 to about 3:1.
The continuous gas phase polymerization process for producing ethylene and interpolymers of ethylene and at least one other olefin may be carried out using any suitable continuous gas phase polymerization process. These types of processes and means for operating the polymerization reactors are well known and completely described in U.S. Pat. Nos. 3,709,853; 4,003,712; 4,011,382; 4,012,573; 4,302,566; 4,543,399; 4,882,400; 5,352,749 and 5,541,270. These patents disclose gas phase polymerization processes wherein the polymerization zone is either mechanically agitated or fluidized by the continuous flow of the gaseous monomer and diluent. The entire contents of these patents are incorporated herein by reference.
The polymerization process of the present invention is conducted in a continuous gas phase process such as, for example, a gas phase fluid bed process. A fluid bed reactor for use in the process of the present invention typically comprises a reaction zone and a so-called velocity reduction zone. The reaction zone comprises a bed of growing polymer particles, formed polymer particles and a minor amount of catalyst particles fluidized by the continuous flow of the gaseous monomer and diluent to remove heat of polymerization through the reaction zone. Optionally, some of the recirculated gases may be cooled and compressed to form liquids that increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone. A suitable rate of gas flow may be readily determined by simple experiment. Makeup of gaseous monomer to the circulating gas stream is at a rate equal to the rate at which particulate polymer product and monomer associated therewith is withdrawn from the reactor and the composition of the gas passing through the reactor is adjusted to maintain an essentially steady state gaseous composition within the reaction zone. The gas leaving the reaction zone is passed to the velocity reduction zone where entrained particles are removed. Finer entrained particles and dust may be removed in a cyclone and/or fine filter. The gas is compressed in a compressor, passed through a heat exchanger wherein the heat of polymerization and the heat of compression are removed, and then returned to the reaction zone.
In more detail, the reactor temperature of the gas phase process ranges from about 30xc2x0 C. to about 130xc2x0 C. In general, the reactor temperature is operated at the highest temperature that is feasible taking into account the sintering temperatures of the polymer product within the reactor.
The process of the present invention is suitable for the polymerization of ethylene and interpolymers of ethylene with at least one or more other olefins. The other olefins, for example, may contain from 3 to 16 carbon atoms. Included herein are homopolymers of ethylene and interpolymers of ethylene and the other olefin(s). The interpolymers include interpolymers of ethylene and at least one olefin(s) wherein the ethylene content is at least about 50% by weight of the total monomers involved. Exemplary olefins that may be utilized herein are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, 1-hexadecene and the like. Also utilizable herein are non-conjugated dienes and olefins formed in situ in the polymerization medium. When olefins are formed in situ in the polymerization medium, the formation of interpolymers of ethylene containing long chain branching may occur.
The polymerization reaction of the present invention is carried out in the presence of a Ziegler-Natta catalyst comprising at least one transition metal component selected from titanium, zirconium, hafnium, or mixtures thereof, and a co-catalyst. In the process of the invention, the components of the catalyst can be introduced in any manner known in the art. For example, the catalyst components can be introduced directly into the fluidized bed reactor in the form of a solution, a slurry or a dry free flowing powder. The catalyst can also be used in the form of a deactivated catalyst, or in the form of a prepolymer obtained by contacting at least one transition metal component with one or more olefins in the presence of a co-catalyst. The Ziegler-Natta catalyst can optionally contain magnesium and/or chlorine. Such magnesium and chlorine containing catalysts may be prepared by any manner known in the art.
The co-catalyst component of the Ziegler-Natta catalyst used in the process of the present invention can be any organometallic compound, or mixtures thereof, that can activate the titanium, zirconium or hafnium component of the Ziegler-Natta catalyst in the polymerization of ethylene homopolymers and interpolymers. In particular, the organometallic co-catalyst compound that is reacted with the titanium, zirconium or hafnium component contains a metal selected from Groups 1, 2, 11, 12, 13 and/or 14 of the Periodic Table of the Elements as published in xe2x80x9cChemical and Engineering Newsxe2x80x9d, 63(5), 27, 1985. In this format, the groups are numbered 1-18. Exemplary of such metals are lithium, magnesium, copper, zinc, aluminum, silicon and the like, or mixtures thereof.
Preferred for use herein are the organoaluminum compounds such as the trialkylaluminum compounds and dialkylaluminum monohalides. Examples include trimethylaluminum, triethylaluminum, trihexylaluminum, dimethylaluminum chloride, and diethylaluminum chloride.
The titanium, zirconium, hafnium, or mixtures thereof, component(s) of the Ziegler-Natta catalyst, with or without co-catalyst, may be deposited on a carrier. In so doing, there may be used as the carrier any catalyst carrier compound known in the art. Exemplary carriers are magnesium oxides, magnesium oxyhalides and magnesium halides, particularly magnesium chloride. The catalyst, with or without the carrier, may be supported on a solid porous support, such as silica, alumina and the like.
The Ziegler-Natta catalyst may contain conventional components in addition to the titanium, zirconium, hafnium, or mixtures thereof, component(s) and the organometallic co-catalyst component. For example, there may be added any internal or external electron donor(s) known in the art, and the like.
The Ziegler-Natta catalyst may be prepared by any method known in the art. The catalyst can be in the form of a solution, a slurry or a dry free flowing powder. The amount of Ziegler-Natta catalyst used is that which is sufficient to allow production of the desired amount of polymeric material.
The polymerization reaction is carried out in the presence of a non-aromatic halogenated hydrocarbon(s), added in a molar ratio of non-aromatic halogenated hydrocarbon(s) to the titanium, zirconium or hafnium transition metal component(s) of the Ziegler-Natta catalyst, from 0.2:1 to about 3:1. Preferably, the non-aromatic halogenated hydrocarbon(s) is added in a molar ratio ranging from about 0.2:1 to about 2:1. Most preferably, the non-aromatic halogenated hydrocarbon(s) is added in a molar ratio ranging from about 0.5 to about 1.5. Another range in which the non-aromatic halogenated hydrocarbon(s) is added is a molar ratio which comprises all combinations of a lower and an upper range wherein the lower range being any one of the following 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1 and 1.3:1 and the upper range being any one of the following 1.5:1, 1.7:1, 2:1, 2.2:1, 2.4:1, 2.5:1, 2.7:1, 3.0:1, 3.2:1, 3.5:1.
Any non-aromatic halogenated hydrocarbon(s) may be used in the process of the present invention. If desired more than one non-aromatic halogenated hydrocarbon can be used. Typical of such non-aromatic halogenated hydrocarbons are monohalogen and polyhalogen substituted aliphatic and alicyclic hydrocarbons having 1 to 12 carbon atoms. Suitable, non-aromatic halogenated hydrocarbons are fluoromethane; chloromethane; bromomethane; iodomethane; difluromethane; dichloromethane; dibromomethane; diiodomethane; chloroform; bromoform; iodoform; carbon tetrachloride; carbon tetrabromide; carbon tetraiodide; bromofluoromethane; bromochloromethane; bromoiodomethane; chlorofluoromethane; chloroiodomethane; fluoroiodomethane; bromodifluromethane; bromodichloromethane; bromodiiodomethane; chlorodifluromethane; chlorodibromomethane; chlorodiiodomethane; fluorodichloromethane; fluorodibromomethane; fluorodiiodomethane; iododifluromethane; iododichloromethane; iododibromomethane; bromotrifluoromethane; bromotrichloromethane; bromotriiodomethane; chlorotrifluoromethane; chlorotribromomethane; chlorotriiodomethane; fluorotrichloromethane; fluorotribromomethane; fluorotriiodomethane; iodotrifluoromethane; iodotrichloromethane; iodotribromomethane; fluoroethane; chloroethane; bromoethane; iodoethane; 1,1-difluoroethane; 1,1-dichloroethane; 1,1-dibromoethane; 1,1-diiodoethane; 1,2-difluoroethane; 1,2-dichloroethane; 1,2-dibromoethane; 1,2-diiodoethane; 1-bromo-1-fluoroethane; 1-bromo-1-chloroethane; 1-bromo-1-iodoethane; 1-chloro-1-fluoroethane; 1-chloro-1-iodoethane; 1-fluoro-1-iodoethane; 1-bromo-2-fluoroethane; 1-bromo-2-chloroethane; 1-bromo-2-iodoethane; 1-chloro-2-fluoroethane; 1-chloro-2-iodoethane; 1-fluoro-2-iodoethane; 1,1,1-trifluoroethane; 1,1,1-trichloroethane; 1,1,1-tribromoethane; 1,1,1-triiodoethane; 1,1,2-trifluoroethane; 1,1,2-trichloroethane; 1,1,2-tribromoethane; 1,1,2-triiodoethane; 1-bromo-1,1-difluoroethane; 1-bromo-1,1-dichloroethane; 1-bromo-1,1-diiodoethane; 1-chloro-1,1-difluoroethane; 1-chloro-1,1-dibromoethane; 1-chloro-1,1-diiodoethane; 1-fluoro-1,1-dichloroethane; 1-fluoro-1,1-dibromoethane; 1-fluoro-1,1-diiodoethane; 1-iodo-1,1-difluoroethane; 1-iodo-1,1-dichloroethane; 1-iodo-1,1-dibromoethane; 1-bromo-1,2-difluoroethane; 1-bromo-1,2-dichloroethane; 1-bromo-1,2-diiodoethane; 1-chloro-1,2-difluoroethane; 1-chloro-1,2-dibromoethane; 1-chloro-1,2-diiodoethane; 1-fluoro-1,2-dichloroethane; 1-fluoro-1,2-dibromoethane; 1-fluoro-1,2-diiodoethane; 1-iodo-1,2-difluoroethane; 1-iodo-1,2-dichloroethane; 1-iodo-1,2-dibromoethane; 2-bromo-1,1-difluoroethane; 2-bromo-1,1-dichloroethane; 2-bromo-1,1-diiodoethane; 2-chloro-1,1-difluoroethane; 2-chloro-1,1-dibromoethane; 2-chloro-1,1-diiodoethane; 2-fluoro-1,1-dichloroethane; 2-fluoro-1,1-dibromoethane; 2-fluoro-1,1-diiodoethane; 2-iodo-1,1-difluoroethane; 2-iodo-1,1-dichloroethane; 2-iodo-1,1-dibromoethane; 1,1,1,2-tetrafluoroethane; 1,1,1,2-tetrachloroethane; 1,1,1,2-tetrabromoethane; 1,1,1,2-tetraiodoethane; 1,1,2,2-tetrafluoroethane; 1,1,2,2-tetraiodoethane; 2-bromo-1,1,1-trifluoroethane; 2-bromo-1,1,1-trichloroethane; 2-bromo-1,1,1-triiodoethane; 2-chloro-1,1,1-trifluoroethane; 2-chloro-1,1,1-tribromoethane; 2-chloro-1,1,1-triiodoethane; 2-fluoro-1,1,1-trichloroethane; 2-fluoro-1,1,1-tribromoethane; 2-fluoro-1,1,1-triiodoethane; 2-iodo-1,1,1-trifluoroethane; 2-iodo-1,1,1-trichloroethane; 2-iodo-1,1,1-tribromoethane; 1,1-dibromo-2,2-difluoroethane; 1,1-dibromo-2,2-dichloroethane; 1,1-dibromo-2,2-diiodoethane; 1,1-dichloro-2,2-difluoroethane; 1,1-dichloro-2,2-diiodoethane; 1,1-difluoro-2,2-diiodoethane; 1,2-dibromo-1,2-difluoroethane; 1,2-dibromo-1,2-dichloroethane; 1,2-dibromo-1,2-diiodoethane; 1,2-dichloro-1,2-difluoroethane; 1,2-dichloro-1,2-diiodoethane; 1,2-difluoro-1,2-diiodoethane; 2-bromo-2-chloro-1,1,1-trifluoroethane; hexafluoroethane; hexachloroethane; chloropentafluoroethane; iodopentafluoroethane; 1,2-dibromotetrachloroethane; fluoroethylene; chloroethylene; bromoethylene; iodoethylene; 1,1-difluorothylene; 1,1-dichloroethylene; 1,1-dibromoethylene; 1,1-diiodoethylene; 1,1,2-trifluorothylene; 1,1,2-trichloroethylene; 1,1,2-tribromoethylene; 1,1,2-triiodoethylene; 1,1,2,2-tetrafluorothylene; 1,1,2,2-tetrachloroethylene; 1,1,2,2-tetrabromoethylene; 1,1,2,2-tetraiodoethylene; 1-bromo-1,2,2-trifluorothylene; 1-bromo-1,2,2-trichloroethylene; 1-bromo-1,2,2-triiodoethylene; 1-chloro-1,2,2-trifluorothylene; 1-chloro-1,2,2-tribromoethylene; 1-chloro-1,2,2-triiodoethylene; 1-fluoro-1,2,2-trichloroethylene; 1-fluoro-1,2,2-tribromoethylene; 1-fluoro-1,2,2-triiodoethylene; 1-iodo-1,2,2-trifluorothylene, 1-iodo-1,2,2-trichloroethylene; 1-iodo-1,2,2-tribromoethylene; 1,1-dibromo-2,2-difluorothylene; 1,1-dibromo-2,2-dichloroethylene; 1,1-dibromo-2,2-diiodoethylene; 1,1-dichloro-2,2-difluoroethylene; 1,1-dichloro-2,2-diiodoethylene; 1,1-difluoro-2,2-diiodoethylene; 1,2-dibromo-1,2-difluorothylene; 1,2-dibromo-1,2-dichloroethylene; 1,2-dibromo-1,2-diiodoethylene; 1,2-dichloro-1,2-difluoroethylene; 1,2-dichloro-1,2-diiodoethylene; 1,2-difluoro-1,2-diiodoethylene; 1-fluoropropane; 1-bromopropane; 1-chloropropane; 1-iodopropane; 2-fluoropropane; 2-bromopropane; 2-chloropropane; 2-iodopropane; 1,3-difluoropropane; 1,3-dibromopropane; 1,3-dichloropropane; 1,3-diiodopropane; 1-fluorobutane; 1-bromobutane; 1-chlorobutane; 1-iodobutane; 2-fluorobutane; 2-bromobutane; 2-chlorobutane; 2-iodobutane; 1-fluoro-2-methylpropane; 1-bromo-2-methylpropane; 1-chloro-2-methylpropane; 1-iodo-2-methylpropane; 2-fluoro-2-methylpropane; 2-bromo-2-methylpropane; 2-chloro-2-methylpropane; 2-iodo-2-methylpropane; 1-fluoropentane; 1-bromopentane; 1-chloropentane; 1-iodopentane; 2-fluoropentane; 2-bromopentane; 2-chloropentane; 2-iodopentane; 3-fluoropentane; 3-bromopentane; 3-chloropentane; 3-iodopentane; 1-fluoro-2-methyl-butane; 1-bromo-2-methyl-butane; 1-chloro-2-methyl-butane; 1-iodo-2-methyl-butane; 1-fluoro-3-methyl-butane; 1-bromo-3-methyl-butane; 1-chloro-3-methyl-butane; 1-iodo-3-methyl-butane; 2-fluoro-2-methyl-butane; 2-bromo-2-methyl-butane; 2-chloro-2-methyl-butane; 2-iodo-2-methyl-butane; 1-fluoro-2,2-dimethylpropane; 1-bromo-2,2-dimethylpropane; 1-chloro-2,2-dimethylpropane; 1-iodo-2,2-dimethylpropane; hexafluoropropene; hexachloropropene; perfluoro-2-methyl-2-pentene; perfluoropropyl chloride; perfluoroisopropyl chloride; perfluoropropyl iodide; perfluoroisopropyl iodide; 1,2-dibromohexafluoropropane; perfluoropentane; perfluorohexane; chlorocyclopropane; pentachlorocyclopropane; chlorocyclobutane; chlorocyclopentane; chlorocyclohexane; 1,1-dichlorocyclobutane; 1,1-dichlorocyclopentane; 1,1-dichlorocyclohexane; cis-1,2-dichlorocyclobutane; cis-1,2-dichlorocyclopentane; cis-1,2-dichlorocyclohexane; trans-1,2-dichlorocyclobutane; trans-1,2-dichlorocyclopentane; trans-1,2-dichlorocyclohexane; alpha-1,2,3,4,5,6-hexachlorocyclohexane; tetrachlorocyclopropane and the like
Also suitable for use in the process of the present invention are any saturated halogenated hydrocarbon(s) or mixture thereof.
Preferred for use in the process of the present invention are dichloromethane; dibromomethane; chloroform; carbon tetrachloride; bromochloromethane; chlorofluoromethane; bromodichloromethane; chlorodifluromethane; fluorodichloromethane; chlorotrifluoromethane; fluorotrichloromethane; 1,2-dichloroethane; 1,2-dibromoethane; 1-chloro-1-fluoroethane; 1-chloro-1,1-difluoroethane; 1-chloro-1,2-difluoroethane; 2-chloro-1,1-difluoroethane; 1,1,1,2-tetrafluoroethane; 1,1,1,2-tetrachloroethane; 2-chloro-1,1,1-trifluoroethane; 1,1-dichloro-2,2-difluoroethane; 1,2-dichloro-1,2-difluoroethane; hexafluoroethane; hexachloroethane; chloropentafluoroethane and 1,2-dibromotetrachloroethane.
Even more preferred for use in the process of the present invention are dichloromethane; chloroform; carbon tetrachloride; chlorofluoromethane; chlorodifluromethane; dichlorodifluoromethane, fluorodichloromethane; chlorotrifluoromethane; fluorotrichloromethane; 1,2-dichloroethane; 1,2-dibromoethane; 1,1,1,2-tetrachloroethane; 2-chloro-1,1,1-trifluoroethane; 1,1-dichloro-2,2-difluoroethane; 1,2-dichloro-1,2-difluoroethane; hexafluoroethane and hexachloroethane.
Most preferred for use in the process of the present invention is chloroform.
The non-aromatic halogenated hydrocarbons may be used individually or as mixtures thereof.
The non-aromatic halogenated hydrocarbon(s) may be added into the polymerization medium as such, or diluted in a liquid hydrocarbon such as an alkane for example, propane, n-butane, isobutane, n-pentane, isopentane, hexane, cyclohexane, heptane, octane and the like. The non-aromatic halogenated hydrocarbon(s) may be added by any method and at any point to the polymerization medium as such.
In carrying out the polymerization reaction of the present process there may be added other conventional additives generally utilized in processes for polymerizing olefins.
Any conventional additive may be added to the polyethylenes obtained by the present invention. Examples of the additives include nucleating agents, heat stabilizers, antioxidants of phenol type, sulfur type and phosphorus type, lubricants, antistatic agents, dispersants, copper harm inhibitors, neutralizing agents, foaming agents, plasticizers, anti-foaming agents, flame retardants, crosslinking agents, flowability improvers such as peroxides, ultraviolet light absorbers, light stabilizers, weathering stabilizers, weld strength improvers, slip agents, anti-blocking agents, antifogging agents, dyes, pigments, natural oils, synthetic oils, waxes, fillers and rubber ingredients.
The polyethylenes of the present invention may be fabricated into films by any technique known in the art. For example, films may be produced by the well known cast film, blown film and extrusion coating techniques.
Further, the polyethylenes may be fabricated into other articles of manufacture, such as molded articles, by any of the well known techniques.
The invention will be more readily understood by reference to the following examples. There are, of course, many other forms of this invention which will become obvious to one skilled in the art, once the invention has been fully disclosed, and it will accordingly be recognized that these examples are given for the purpose of illustration only, and are not to be construed as limiting the scope of this invention in any way.

Process for the polymerization of ethylene and interpolymers thereof


A vision-based occupant classification method utilizes a static classification routine for achieving highly accurate occupant classification, a dynamic detection routine for quickly responding to changes in occupant position, and a category state change routine for detecting potential changes in occupant category. The static classification routine determines an initial classification of the occupant, after which the dynamic detection routine monitors for changes in occupant position and the category state change routine monitors for a potential change in occupant category. If category state change routine detects a potential change in occupant category, the static classification routine is re-executed to re-classify the occupant. The category state change routine identifies a composite optical flow vector associated with occupant movement, and detects a potential change in occupant category when the composite flow vector crosses one or more pre-defined entry/exit motion gates.

Occupant classification systems are commonly used in motor vehicles for determining if pyrotechnically deployed restraints such as air bags should be deployed in the event of a sufficiently severe crash. Early systems relied exclusively on sensors for measuring physical parameters such as seat force, but vision-based systems have become economically attractive due to the advent of low-cost solid-state imaging chips. However, image processing algorithms for accurately detecting and classifying vehicle occupants can be relatively complex, resulting in slower than desired response to changes in occupant position. The algorithms can be simplified to provide faster dynamic response time, but this typically impairs the classification accuracy. Accordingly, what is needed is a classification method having both high classification accuracy and fast dynamic response.

Method of operation for a vision-based occupant classification system


Disclosed is a method for preparing lactide by using a solvent. According to the method, since an ionic liquid is used as a solvent in a second step in the course of preparing lactide, it is possible to secure mobility of the resulting reactant, and decrease a reaction temperature. In addition, the ionic liquid absorbs moisture generated during the reaction, and thus prevents degradation of lactide which is susceptible to moisture. Furthermore, to the present method allows for the preparation of lactide successively through the continuous supply of lactic acid oligomers. Because the use of an ionic liquid minimizes the contamination of a reactive group with by-products, the use of a solvent for reactor washing is unnecessary. Further, owing to a high boiling point of the ionic liquid, the ionic liquid can be easily harvested and recycled.

(a) Technical Field
The present disclosure relates to a method for preparing lactide, particularly by reacting lactic acid oligomers in the presence of an ionic solvent.
(b) Background Art
The amazing industrialization since the 20th century appears to be largely based on fossil fuel resources, particularly petroleum. With the rapid industrial development and population growth, the petroleum consumption has been increased continuously as well. Petroleum is an unrenewable resource with a limited amount of reserves that will soon be exhausted. Recently, it has been found that the carbon dioxide generated by fossil fuel consumption is one of the main causes of global warming. As such, researchers are striving to improve fuel efficiency so as to reduce carbon dioxide emissions and to reduce dependence on petroleum.
Polymers derived from plants, i.e., biomass polymers, can be prepared by a chemical or biological process from renewable plant resources such as corn, bean, sugar cane, wood, etc. A value of biomass polymers lies in their potential to solve environmental problems through carbon dioxide reduction rather than in biodegradability. Among biomass polymers, polylactic acid is a carbon neutral, environment-friendly, thermoplastic, linear aliphatic polyester, It is derived from corn starch or potato starch through fermentation or it is prepared by polymerizing sugar monomers obtained from saccharification of plant-derived cellulose followed by fermentation.
Despite the various advantages of polylactic acid, however, it does not appear to be suitable for use in automobile parts, because of its low impact resistance, low heat deflection temperature, etc., as compared to the petroleum-based chemical polymers. In particular, polylactic acid has low impact strength due to its brittleness, which thus delimits its application in automobile parts.
For this reason, industrial application of polylactic acid resin is limited due to its inferior physical properties when compared to the general-use polymer materials. In particular, for use in automobile engine and chassis parts requiring high heat resistance and impact resistance, improvement of the physical properties of polylactic acid resin is essential. As a strategy to solve this problem, a technique of preparing a stereo-complex resin by blending the optical isomers of polylactic acid is often used.
Conventionally, a method for manufacturing lactide is composed of polymerizing lactic acid into a low molecular weight oligomer and depolymerizing the low molecular weight oligomer into lactide. In the first step, the oligomer is polymerized under the conditions of 150° C. and 0.3 atm, and moisture generated during this step is removed. In the second step, the synthesis of lactide is carried out in the presence of a catalyst, wherein the catalyst may include tin powder, tin halides or tin carboxylates (EP Patent Nos. 261,572 and 275,581); tin alkoxides (United Kingdom Patent No. 1,007,347); and zinc or tin (EP Patent No 264,926 and U.S. Pat. No. 4,797,468).
In this conventional method, since the polymerization and depolymerization occur simultaneously in the second step of preparing lactides, the molecular weight of lactide obtained thereby is gradually increased. Thus, in order to improve the reaction yield by inducing the synthetic reaction continuously, there is a need to increase a reaction temperature continually. In particular, the synthesis of lactide initiates under the conditions of 170° C. and 0.1 atm in the presence of LiCO as a catalyst. However, the reaction temperature should be increased gradually up to 200° C. or higher so as to increase the reaction yield. It was reported that a yield above 90% was obtained through the reaction at 200° C. for 2 hours based on a 500 cc reactor. Since the synthesis of lactide is carried out at a high reaction temperature, there is a need to wash a reactor by using a solvent, and thus, there is a problem in generating a large quantity of waste liquid caused by the solvent. Further, since the washing step is indispensable, it is very difficult to utilize continuous processing in this conventional method.
As one conventional method for preparing lactide, Korean Patent No. 171,432 describes a method for preparing lactide by treating a aqueous lactic acid feed so as to remove water therefrom, terminating the treatment to produce a crude lactide product, and separating lactides from the crude lactide product.
Japanese Patent Application Publication No. 2004-0149419 describes a method for preparing lactide, which is characterized by azeotropic dehydration of a mixture including water-containing crude lactide and an azeotropic solvent, precipitation of lactide by using the solvent after the azeotropic dehydration, solid/liquid separation of the solvent into a solid phase and an azeotropic solvent phase, and collection of lactide from the solid phase.
Japanese Patent Application Publication No. 1999-0209370 describes a method for preparing lactide, which includes the steps of: synthesizing a composition including polylactic acid alone or polylactic acid and lactide through dealcoholization by heating lactic acid ester in the presence of a monobutyltin compound, and synthesizing lactide by heating the composition polylactic acid alone or polylactic acid and lactide obtained in the above step in the presence of a monobutyltin compound.
Korean Patent Application Publication No. 2010-0005820 describes a method for preparing optically pure lactide, including: (A) dissolving lactic acid in an organic solvent; (B) adding an enzyme to the organic solvent solution of lactic acid and stirring the resulting mixture; and (C) separating optically pure lactide from the resulting mixture.
However, none of the preparation methods describes in the above patents can overcome the problems of the prior art as mentioned above.
The above information disclosed in this Background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known in this country to a person of ordinary skill in the art.

Method for preparing lactide using an ionic solvent


A coloured porous material comprising in its pores an effectively colouring amount of an organic pigment which is obtainable by fragmenting a meltable or solvent-soluble pigment precursor, and a process for its preparation. The instant coloured porous material powders are used as pigments for high molecular weight organic materials.

The present application relates to porous materials given coloured pigmentation with organic pigments localized in their pores and to a process for their preparation.
Porous materials are commonly coloured with dyes that are applied, for example, as stains. In order to achieve satisfactory colouring results with this method a requirement is that the porous material to be coloured has a high and uniform affinity for the dye; this requirement, however, is seldom met. Porous materials coloured with dyes possess, moreover, an undesirably low light stability, and in contact with water or organic liquids (beverages, for example) marks may be formed on articles that are in contact with the materials, since the dyes are in some cases leached out again.
Another method of imparting a coloured appearance to porous materials is to provide them with a pigmented coating. This method, however, has the disadvantage that the pores become sealed by the pigmented coating material, with the result that it becomes difficult if not impossible to perceive visually the nature of the porous material. This is a great disadvantage, especially with natural porous materials, since it is their properties, especially their natural appearance and their permeability, that are the most prized. The properties of the porous material, however, are impaired by a pigmented coating.
EP 648 770 and EP 648 817 disclose carbamate-functional, soluble chromophors which can be converted to the corresponding pigments by heating them to relatively high temperatures, with the ensuing elimination of the carbamate radicals. These compounds are suitable for the mass colouring of polymers and, according to EP 654 711, for the colouring of resists and of polymer coats to which they are applied. Compounds of the same type but with improved properties are known from EP 742 556 and U.S. application Ser. No. 09/013,659.
U.S. Pat. No. 5,243,052 discloses carbonates of quinophthalones, which are of limited solubility and can be used in heat-sensitive recording systems. The leuco dye is embedded within a polymer, preferably in polyethyloxazoline.
Soluble derivatives of triphenylmethane dyes are known from U.S. Pat. No. 4,826,976. They are likewise used in heat-sensitive recording systems, together with a binder such as cellulose acetate-butyrate, polyvinylpyrrolidone or copolymerized ethylene/maleic anhydride.
EP 742 556, furthermore, describes textured pigmentary coatings which are prepared from soluble or meltable precursors and which cover all or part of a substrate surface. The substrates mentioned include fibres and fabrics. It has been found, however, that these pigmentary coatings fail to meet high requirements in terms, in particular, of their rub fastness.
Also known, finally, are numerous heat-sensitive recording systems in which colourless precursors of colorantsxe2x80x94as solids, in the form, for example, of aqueous suspensions, together with binders and with or without fillersxe2x80x94are incorporated as the recording layer. For example, JP 04/123,175 describes leucoindigoid derivatives. Colorants in solid form, however, like conventional pigments, for example, make hardly any entry into the pores but for the most part remain, undesirably, on the surface.
It has now surprisingly been found that porous materials can be coloured without impairing their properties, and especially without clogging the pores, if fragmentable pigment precursors in melted or dissolved form are introduced into the pores and then converted to their pigmentary form.
Depending on the solvent, pressure, temperature and treatment time it is possible, surprisingly, to influence the depth of penetration of the pigment precursor and so with great advantage to obtainxe2x80x94in a targeted manner, for examplexe2x80x94colorations wherein the pigment is very close to the surface. Since in this case the entirety of the pigment contributes to colouring, it is possible with advantage to reduce its amount to the minimum necessary for coloration, and the colour of the material core remains unaltered.
It is, however, also possible to obtain very high colour saturations (chroma) by using high pigment concentrations. Thus, pigmented porous materials of fine particle size can be used as pigments for colouring high molecular mass organic material. The results are excellent with respect to hue and chroma as well as also to the transparency, when the porous material has a refraction index similar to that of the substrate into which it is incorporated. Very advantageously, these products are less dusting and more easily incorporated into substrates than usual transparent pigments, and rheology problems can be avoided.
Under appropriate conditions it is also possible, however, to provide porous materials with uniform colouring right through, hence allowing them with little or no change in colour to be processed, for example cut, milled, sanded, bent or joinedxe2x80x94by gluing, for instance. Consequently, either finished articles or raw material, as desired, can be coloured prior to its processing or shaping.
A particularly advantageous result of this is an increase in production flexibility, and possibilities for making savings, when producing articles from coloured porous materials.
The resulting colorations are surprisingly strong in colour, fast to weathering, light and heat, rubbing, water and solvent, and are also highly uniform optically provided the material itself is uniform in its porosity. With particular advantage this permits the use of materials whose quality would not enable any satisfactory results to be obtained on conventional colouring, a feature which, especially in the case of naturally occurring organic porous materials of complex structure, such as wood, leather or hair, for example, paves the way for ecologically significant, improved utilization of natural resources. A further great advantage is that following the colouring of the porous material its nature is, surprisingly, still apparent to the eye.
The present invention accordingly provides a coloured porous material comprising in its pores an effectively colouring amount of an organic pigment which is obtainable by fragmenting a meltable or solvent-soluble pigment precursor.
Porous materials can be mineral or organic, natural, refined or synthetic. The material may, for example, be chalk, pumice, fired clay, unglazed porcelain, gypsum, concrete, kieselguhr, silica gel, zeolites, wood, paper, leather, imitation leather or hair, in whatever form, or products derived from these. It is preferably a material composed of refined or unrefined organic components of natural origin or, with particular preference, is a refined or unrefined natural organic material. In particular, it can be either hard wood or soft wood.
In another preferred embodiment, however, the material consists of fine particles, most preferably inorganic particles, such as chalk, pumice, fired clay, unglazed porcelain, gypsum, kieselguhr, silica gel or zeolite powders. The particle size is preferably from 0.1 to 10 xcexcm, most preferably from 1 to 3 xcexcm. The organic pigment""s concentration may be low or high, depending of the desired colour saturation. A low concentration of the organic pigment in the powdered inorganic material leads to pastel tints, while a high concentration of the organic pigment in the powdered inorganic material leads to higher saturations.
Examples of high molecular mass organic materials which can be coloured or pigmented with the instant pigmented porous material powders are cellulose ethers, cellulose esters, such as ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate, natural resins or synthetic resins, such as addition polymerization resins or condensation polymerization resins, such as amino resins, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenolic resins, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyesters, ABS, polyphenylene oxides, rubber, casein, silicone and silicone resins, individually or in mixtures.
The abovementioned high molecular mass organic compounds can be present, individually or in mixtures, as plastic masses, as melts or in the form of spinning solutions, varnishes, coating materials or printing inks. Organic high molecular mass materials coloured with the instant pigmented porous material powders possess outstanding colour properties. This invention therefore also provides a composition comprising a high molecular mass organic material and an effective pigmenting amount of an instant pigmented porous material powder.
The instant pigmented porous material powders are preferably employed in an amount of from 0.1 to 50% by weight, most preferably from 1 to 30% by weight, based on the high molecular mass organic material to be pigmented.
The pigmenting of the high molecular mass organic substances with the instant pigmented porous material powders is carried out, for example, by mixing such solid solutions, in the form of masterbatches if desired, into these substrates using roller assemblies, mixers or milling apparatus. The pigmented material is subsequently brought into the desired final form by methods known per se, such as calandering, compression moulding, extrusion, coating, casting or injection moulding. So as to produce non-rigid mouldings, or to reduce their brittleness, it is often desirable to incorporate plasticizers into the high molecular mass compounds prior to their forming. Examples of compounds which can be used as such plasticizers are esters of phosphoric acid, phthalic acid or sebacic acid. The plasticizers can be incorporated into the polymers before or after the incorporation of the instant pigmented porous material powders. In order to achieve different colour effects, it is also possible to add to the high molecular mass organic substances not only the instant pigmented porous material powders but also fillers, reflecting metallic or inorganic particles, for example aluminium flakes or mica, and/or other colour-imparting constituents, such as white, coloured or black pigments, in any desired quantities.
For the pigmentation of varnishes, coating materials and printing inks, the high molecular mass organic materials and the instant pigmented porous material powders, together if desired with additives such as fillers, other pigments, siccatives or plasticizers, are finely dispersed or dissolved in an organic solvent or solvent mixture for them both. In this context it is possible to follow a procedure in which the individual components are dispersed or dissolved individually or else two or more of them are dispersed or dissolved together and only then to combine all of the components.
The instant pigmented porous material powders are particularly suitable for colouring plastics, especially polyvinyl chloride and polyolefins, and for colouring paints, preferably automotive or metallic finishes, for example those containing metal particles or mica particles.
A feature of porous materials is the presence of pores, by which are meant cavities within the physical shell of the material, which may be partly or totally filled with a gas, for example air, or with a liquid, for example water. Preferably, the pores extend at least in part to the surface of the material. The volume of the pores is preferably at least 5% relative to the volume of the geometric shell of the material. With particular preference the volume of the pores is from 20 to 90% relative to the volume of the geometric shell of the material. Preferably, the cross-section of the pores is so fine that by virtue of capillary force an aqueous liquid does not flow out under gravity. With particular preference the average cross-section of the pores is from 1xc2x710xe2x88x9216 to 10xe2x88x926 m2, determined at a transverse section through the material, by dividing the total pore area by the number of pores.
Introducing the pigment precursor into the pores of the porous material is effected by applying a solution or melt of the pigment precursor to the porous material using any desired, known method, for example by spraying or impregnation in a bath. The methods of and conditions for treatment of certain materials are known in the technical literature, to which express reference is hereby made. For example, the methods of and conditions for treating wood and wood products with solutions are described in detail in Ullmann""s Encyclopaedia of Industrial Chemistry, Vol. A28, 305-393 (5th Edition 1996) and Kirk-Othmer Encyclopaedia of Chemical Technology, Vol. 24, 579-611 (3rd Edition 1978). The application temperature can be an elevated temperature but is judiciously kept low enough for the dissolved or melted pigment precursor not to undergo any, or any significant, decomposition during the minimum time required for the application. If desired, the solution or melt of the pigment precursor may be augmented with further substances known for treating the material, examples being fungicides, antibiotics, flame retardants or moisture repellents.
Suitable solvents are water or, preferably, any desired protic or aprotic solvents, examples being hydrocarbons, alcohols, amides, nitriles, nitro compounds, N-heterocycles, ethers, ketones and esters which may also be either mono- or polyunsaturated or chlorinated: examples are methanol, ethanol, isopropanol, diethyl ether, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, 2-methoxyethanol, ethyl acetate, tetrahydrofuran, dioxane, acetonitrile, benzonitrile, nitrobenzene, N,N-dimethylformamide, N,N-dimethylacet-amide, dimethyl sulfoxide, N-methylpyrrolidone, pyridine, picoline, quinoline, trichloroethane, benzene, toluene, xylene, anisole and chlorobenzene. Further examples of solvents are described in numerous tabular and reference works. Instead of a single solvent it is also possible to employ mixtures of two or more solvents.
Preference is given to those solvents which do not corrode the substrate that is to be coloured, or do so only very slowly, and which have a boiling point of between 40xc2x0 C. and 170xc2x0 C., especially to aromatic hydrocarbons, alcohols, ethers, ketones and esters. Particular preference is given to toluene, methanol, ethanol, isopropanol, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran and dioxane, and mixtures thereof.
The concentration of the pigment precursor in water or a solvent is usually from 0.01% by weight, based on the weight of the solution, to approximately 99% by weight of the saturation concentration, it also being possible in certain cases to employ supersaturated solutions without premature precipitation of the solvate. For many pigment precursors the optimum concentration is around xcx9c0.1-50% by weight, often around 1-20% by weight, based on the weight of the solution.
Conversion of the pigment precursor into the pigmentary form takes place by fragmentation under known conditions, for example thermally. in the presence or absence of a catalyst, such as an acid or a cationic photoinitiator which can be introduced into the pores of the porous material before, at the same time as or after the pigment precursor.
Fragmentation can be carried out individually, or simultaneously with any further known, subsequent treatment; for example, in the course of curing an additional transparent coating film.
By an effectively colouring amount is meant that amount which is sufficient to bring about a colour difference xcex94E*(CIE-L*a*b*) of xe2x89xa72 when the coloured material is compared with the uncoloured material under the standard illuminant D65 and at a viewing angle of 10xc2x0. This amount is preferably from 0.01 to 30% by weight, most preferably from 0.1 to 15% by weight, based on the weight of the coloured material.
Judicious fragmentable pigment precursors are those whose structure includes a complete pigment framework substituted on at least one heteroatom N, O or S. The substituent involved is preferably an oxycarbonyl radical. Where the heteroatom is part of the chromophor or bonded directly to the chromophor, in the course of fragmentation the oxycarbonyl radical is generally eliminated and replaced by a hydrogen atom, so that the structure of the resulting pigment corresponds to that of the unsubstituted pigment framework. Where, on the other hand, the heteroatom is bonded to a substituent of the chromophor, then the fragmentation process is sometimes more complex, and the precise structure of the resulting pigment cannot always be clearly ascertained.
The pigment precursors can be employed individually or else in mixtures with other pigment precursors or with colorantsxe2x80x94for example, dyes customary for the corresponding application. Where the pigment precursors are employed in mixtures, the components of the mixture are preferably those whose colour in the pigmentary form is red, yellow, blue, brown or black. From these it is possible to produce brown shades having a particularly natural occurrence. Any dyes added are likewise preferably red, yellow, blue, brown or black.
Preferred pigment precursors are, for example, compounds of the formula (I)
A(B)xxe2x80x83xe2x80x83(I),
in which x is an integer from 1 to 8,
A is the radical of a chromophor of the quinacridone, anthraquinone, perylene, indigo, quinophthalone, indanthrone, isoindolinone, isoindoline, dioxazine, azo, phthalocyanine or diketopyrrolopyrrole series which is attached to x groups B via one or more heteroatoms selected from the group consisting of N, O and S and forming part of the radical A,
B is hydrogen or a group of the formula
where at least one group B is not hydrogen and, if x is from 2 to 8, the groups B can be identical or different, and
L is any suitable solubilizing group, for example tert.-butyl or tert.-amyl. Many other groups suitable for solubilizing pigments are known, for example, from the publications referred to above.
Except in the case of phthalocyanines, A preferably contains at least one directly adjacent or conjugated carbonyl group at each heteroatom attached to x groups B.
A is the radical of known chromophores having the basic structure
A(H)x,
examples being
and all known derivatives thereof.
Preferred compounds of the formula I are:
a) perylenecarboximides of the formula
in which D is hydrogen, C1-C6alkyl, unsubstituted or halo- or C1-C6alkyl-substituted phenyl, benzyl or phenethyl or B,
b) quinacridones of the formula
in which R1 and R2 independently of one another are hydrogen, halogen, C1-C24alkyl, C1-C6alkoxy or phenyl,
c) dioxazines of the formula
in which R3 is hydrogen, halogen or C1-C24alkyl,
or of the formula
in which R4, R5 and R6 independently of one another are hydrogen, C1-C4alkyl, C1-C4alkoxy, NECOC1-C4alkyl, NECOphenyl or N(E)2 where at least one of the radicals R4, R5 and R6 is NECOC1-C4alkyl, NECOphenyl or N(E)2,
d) isoindolines of the formulae
in which R7 is a group
R8 is hydrogen, C1-C24alkyl, benzyl or a group
R9 is hydrogen, E or R7,
R10, R11, R12 and R13 independently of one another are hydrogen, C1-C24alkyl, C1-C6alkoxy, halogen or trifluoromethyl,
e) isoindolinones of the formula
in which R14 and R15 independently of one another are hydrogen, halogen or C1-C4alkyl,
f) anthraquinonoid compounds of the formula
in which R16 is hydrogen or halogen,
g) phthalocyanines of the formula
in which
M is H2, a divalent metal selected from the group consisting of Cu(II), Zn(II), Fe(II), Ni(II), Ru(II), Rh(II), Pd(II), Pt(II), Mn(II), Mg(II), Be(II), Ca(II), Ba(II), Cd(II), Hg(II), Sn(II), Co(II) and Pb(II), preferably Cu(II), Zn(II), Fe(II), Ni(II) or Pd(II), or a divalent oxo metal selected from the group consisting of V(O), Mn(O) and TiO,
T1 is xe2x80x94CHR18xe2x80x94, xe2x80x94COxe2x80x94 or xe2x80x94SO2xe2x80x94,
R17 is hydrogen, C1-C6alkyl, xe2x80x94N(E)R18, N(E)2, xe2x80x94NECOR19, xe2x80x94COR19 or
R18 is hydrogen or C1-C6alkyl, R19 is C1-C6alkyl and
R20 is hydrogen, halogen, C1-C6alkyl or C1-C6alkoxy,
z is zero or 1 and y is a number from 1 to 8,
h) pyrrolo[3,4-c]pyrroles of the formula
in which G1 and G2 independently of one another are a group of the formula
in which
R21 and R22 independently of one another are hydrogen, halogen, C1-C24alkyl, C1-C6alkoxy, C1-C18alkylthio, C1-C18alkylamino, xe2x80x94CN, xe2x80x94NO2, -phenyl, trifluoromethyl, C5-C6cycloalkyl
xe2x80x94Cxe2x95x90Nxe2x80x94(C1-C24alkyl),
xe2x80x83imidazolyl, pyrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, piperidinyl or pyrrolidinyl,
T2 is xe2x80x94CH2xe2x80x94, xe2x80x94CH(CH3)xe2x80x94, xe2x80x94C(CH3)2xe2x80x94, xe2x80x94CHxe2x95x90Nxe2x80x94, xe2x80x94Nxe2x95x90Nxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94 or xe2x80x94NR2Txe2x80x94,
R23 and R24 independently of one another are hydrogen, halogen, C1-C6alkyl, C1-C6alkoxy or xe2x80x94CN, R25 and R26 independently of one another are hydrogen, halogen or C1-C6alkyl and R27 is hydrogen or C1-C6-alkyl,
i) quinophthalones of the formula
in which R27 is H or Oxe2x80x94E,
R28 to R31 independently of one another are hydrogen, halogen, xe2x80x94COOxe2x80x94C1-C6alkyl or xe2x80x94CONExe2x80x94C1-C6alkyl,
j) azo compounds of the formula
in which R32 to R36 independently of one another are hydrogen, halogen, C1-C6alkyl,
C1-C6alkoxy, nitro, acetyl or SO2NEC1-C6alkyl, and
R37 is hydrogen, halogen, C1-C6alkyl or C1-C6alkoxy,
k) anthraquinones of the formula
in which R38 and R39 independently of one another are hydrogen, C1-C12alkyl, or C6-C12aryl which is unsubstituted or substituted by halogen, C1-C6alkyl, C1-C6alkoxy, nitro, acetyl, SO2NEC1-C6alkyl or SO2NE2,
R40 and R41 independently of one another are hydrogen, halogen, C1-C6alkyl, C1-C6alkoxy, nitro, cyano, CONE2, SO2NEC1-C6alkyl, SO2NE2, SO3E, SO3Na or C6-C12aryl w unsubstituted or substituted by halogen, C1-C6alkyl, C1-C6alkoxy, nitro, acetyl, SO2NEC1-C6alkyl or SO2NE2, and
R42 is hydrogen, halogen, nitro, cyano, hydroxyl or C1-C6alkoxy, and
l) indigo derivatives of the formula
in which R43 is hydrogen, CN, C1-C6alkyl, C1-C6alkoxy or halogen,
where in each case in the abovementioned formulae each E independently of the others is hydrogen or B, with the proviso that in each formula E is B on at least one occasion, and B is as defined above.
Preferred quinacridones are those in which in formula III R1 and R2 independently of one another are hydrogen, chlorine or methyl.
Preferred pyrrolo[3,4-c]pyrroles are those in which in formula XIII G1 and G2 are the same and are a group of the formula
where R21 and R22 independently of one another are hydrogen, chlorine, bromine, C1-C4alkyl, C1-C6alkoxy, C1-C6alkylamino, CN or phenyl,
T2 is xe2x80x94Oxe2x80x94, xe2x80x94NR27xe2x80x94, xe2x80x94Nxe2x95x90Nxe2x80x94 or xe2x80x94SO2xe2x80x94, and
R27 is hydrogen, methyl or ethyl.
Preferred azo compounds are those in which in the formulae XVa to XVf R32 to R36 independently of one another are hydrogen, halogen, methyl, methoxy, nitro, acetyl or SO2NECH3, and R37 is halogen or methoxy.
Particularly preferred are quinacridones of the formula
in which E is hydrogen or B, with the proviso that in each formula E is B on at least one occasion, and B is as defined above,
dioxazines of the formula
in which R44 and R45 independently of one another are C1-C4alkyl, and E is hydrogen or B,
with the proviso that E is B on at least one occasion, and B is as defined above,
pyrrolopyrroles of the formula
in which R46 and R47 independently of one another are hydrogen, methyl, tert-butyl, chlorine, bromine, CN or phenyl, and E is hydrogen or B, with the proviso that E is B on at least one occasion, and B is as defined above,
phthalocyanines of the formula (XII) in which M is Cu(II) and R16 is hydrogen or E, and z is 1 and y is a number from 1 to 4, with the proviso that E is B on at least one occasion, and B is as defined above,
isoindolinones of the formula
in which R48 is hydrogen or C1-C4alkyl, and E is hydrogen or B, with the proviso that E is B on at least one occasion, and B is as defined above,
indanthrones of the formula
in which E is hydrogen or B, with the proviso that E is B on at least one occasion, and B is as defined above, and
azo compounds of the formula XVa, XVb, XVe or XVf, in which
R32 to R36 independently of one another are hydrogen, chlorine, methoxy, nitro, acetyl or SO2NECH3, and R37 is halogen or methoxy, with the proviso that in each formula E is B on at least one occasion, and B is as defined above.
Particularly noteworthy soluble chromophores are those which can be prepared from Colour Index Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 83, Pigment Yellow 109, Pigment Yellow 139, Pigment Orange 71, Pigment Orange 73, Pigment Red 122, Pigment Red 185, Pigment Red 202, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Blue 25, Pigment Blue 26, Pigment Blue 60, Pigment Blue 64, Pigment Violet 19, Pigment Violet 29 and Pigment Violet 37.
The compounds of the formulae I to XXI are known or can be prepared in analogy to methods known per se, as described, for example, in EP 648 770, EP 648 817 and EP 742 556.
Preferably xe2x80x94L is a group of the formula
in which R49, R50 and R51 independently of one another are C1-C6alkyl,
R52 and R53 independently of one another are C1-C6alkyl, O, S or N(R60)2-interrupted C1-C6alkyl, unsubstituted or C1-C6alkyl-, C1-C6alkoxy-, halo-, cyano- or nitro-substituted phenyl or biphenylyl,
R54, R55 and R56 independently of one another are hydrogen or C1-C6alkyl,
R57 is hydrogen, C1-C6alkyl or a group of the formula
R58 and R59 independently of one another are hydrogen, C1-C6alkyl, C1-C6alkoxy, halogen, cyano, nitro, N(R60)2, unsubstituted or halo-, cyano-, nitro-, C1-C6alkyl- or C1-C6alkoxy -substituted phenyl,
R60 and R61 are C1-C6alkyl, R62 is hydrogen or C1-C6alkyl and R63 is hydrogen, C1-C6alkyl unsubstituted or C1-C6alkyl-substituted phenyl,
Q is p,q-C2-C6alkylene which is unsubstituted or substituted one or more times by C1-C6alkoxy, C1-C6alkylthio or C2-C12dialkylamino, p and q being different numeric locants,
X is a heteroatom selected from the group consisting of N, O and S, where m is 0 if X is O or S and is 1 if X is N, and
L1 and L2 independently of one another are unsubstituted or mono- or poly-C1-C12alkoxy-, xe2x80x94C1-C12alkylthio-, xe2x80x94C2-C24dialkylamino-, xe2x80x94C6-C12aryloxy-, xe2x80x94C6-C12arylthio-, xe2x80x94C7-C24alkylarylamino- or xe2x80x94C12-C24diarylamino-substituted C1-C6alkyl or [xe2x80x94(pxe2x80x2,qxe2x80x2xe2x80x94C2-C6alkylene)xe2x80x94Zxe2x80x94]nxe2x80x94C1-C6alkyl, where n is a number from 1 to 1000, pxe2x80x2 and qxe2x80x2 are different numeric locants, each Z independently of the others is a heteroatom O, S or C1-C12alkyl-substituted N, and C2-C6alkylene in the repeating units [xe2x80x94C2-C6alkylene-Z xe2x80x94] can be identical or different,
and L1 and L2 can be saturated or mono- to deca-unsaturated, uninterrupted or interrupted in any desired points by from 1 to 10 groups selected from the group consisting of xe2x80x94(Cxe2x95x90O)xe2x80x94 and xe2x80x94C6H4xe2x80x94, and may carry no or 1 to 10 further substituents selected from the group consisting of halogen, cyano and nitro.
Of particular interest are compounds of the formula (I) in which L is C1-C6alkyl or
in which Q is C2-C4alkylene and L1 and L2 are [xe2x80x94C2-C12alkylenexe2x80x94Zxe2x80x94]nxe2x80x94C1-C12alkyl or are C1-C12alkyl which is substituted one or more times by C1-C12alkoxy, C1-C12alkylthio or C2-C24dialkylamino, and m and n are as defined above.
Of very particular interest are compounds of the formula (I) in which L is C4-C5alkyl (especially tert.-butyl or tert.-amyl) or
in which Q is C2-C4alkylene, X is O and m is zero, and L2 is [xe2x80x94C2-C12alkylene xe2x80x94Oxe2x80x94]nxe2x80x94C1-C12alkyl or is C1-C12alkyl which is substituted one or more times by C1-C12alkoxy, especially those in which xe2x80x94Oxe2x80x94Xxe2x80x94 is a group of the formula xe2x80x94C(CH3)2xe2x80x94CH2xe2x80x94Oxe2x80x94.
Alkyl or alkylene can be straight-chain, branched, monocyclic or polycyclic.
Thus C1-C12alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, trimethylcyclohexyl, decyl, menthyl, thujyl, bornyl, 1-adamantyl, 2-adamantyl or dodecyl.
If C2-C12alkyl is mono- or polyunsaturated it is C2-C12alkenyl, C2-C12alkynyl, C2-C12alkapolyenyl or C2-C12alkapolyynyl in which two or more double bonds may if appropriate be isolated or conjugated, examples being vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-cyclobuten-1-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-thujen-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcaradien-3-yl or the various isomers of hexenyl, octenyl, nonenyl, decenyl or dodecenyl.
C2-C4alkylene is, for example, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene, 1,4-butylene or 2-methyl-1,2-propylene. C5-C12alkylene is, for example, an isomer of pentylene, hexylene, octylene, decylene or dodecylene.
C1-C12alkoxy is Oxe2x80x94C1-C12alkyl, preferably Oxe2x80x94C1-C4alkyl.
C6-C12aryloxy is Oxe2x80x94C6-C12aryl, for example phenoxy or naphthoxy, preferably phenoxy.
C1-C12alkylthio is Sxe2x80x94C1-C12alkyl, preferably Sxe2x80x94C1-C4alkyl.
C6-C12arylthio is Sxe2x80x94C6-C12aryl, for example phenylthio or naphthylthio, preferably phenylthio.
C2-C24dialkylamino is N(alkyl1)(alkyl2), where the sum of the carbon atoms in the two groups alkyl1 and alkyl2 is from 2 to 24, preferably N(C1-C4alkyl)-C1-C4alkyl.
C7-C24alkylarylamino is N(alkyl1)(aryl2), where the sum of the carbon atoms in the two groups alkyl1 and aryl2 is from 7 to 24, for example methylphenylamino, ethyinaphthylamino or butylphenanthrylamino, preferably methylphenylamino or ethylphenylamino.
C12-C24diarylamino is N(aryl1)(aryl2), where the sum of the carbon atoms in the two groups aryl1 and aryl2 is from 12 to 24, for example diphenylamino or phenylnaphthylamino, preferably diphenylamino.
Halogen is chlorine, bromine, fluorine or iodine, preferably fluorine or chlorine.
n is preferably a number from 1 to 100, with particular preference a number from 2 to 12.
In addition to the pigment, the porous material may also contain other compounds in its pores, for example binders or surfactants known in the art to improve the pigment""s dispersibility. It has however surprisingly been found, that improved results are obtained when the porous material is treated with a silane or siloxane compound, particularly when the porous material is inorganic, for example silica gel. The amount of silane or siloxane compound is preferably from 1 to 100% by weight, most preferably from 5 to 20% by weight, based on the weight of the organic pigment.
The silane or siloxane compound is preferably of structure
wherein R64 to R67 are independently OH,
or phenyl or OC1-C16alkyl which are unsubstituted or substituted by OH, OC1-C16alkyl,
Most preferred silane or siloxane compounds are diphenylsilanediol, diphenylmethoxysilane, glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
The invention also provides a process for preparing a coloured porous material of the invention whose pores comprise an effectively colouring amount of an organic pigment, comprising
(a) the treatment of the porous material with a solution or melt of a pigment precursor such that at least part of the pigment precursor enters the pores of the material, and
(b) the fragmentation of the pigment precursor that has entered the pores of the material in accordance with treatment (a), to form a pigment, by means of heating or irradiation.
Heating or irradiation step be carried out by any desired means; for example, by treatment in a thermal oven or by electromagnetic radiation, for example visible light, UV or IR radiation, or microwaves, in the presence or absence of a catalyst. The conditions required for fragmentation are known per se for each class of pigment precursors.
Of course, it is judicial to choose pigment precursors the fragmentation temperature of which is lower than the decomposition point of the porous material to be pigmented, so that fragmentation can be accomplished without altering the material""s properties. Thus, step (b) is usually accomplished by heating to a temperature of from 100 to 250xc2x0 C., preferably from 150 to 200xc2x0 C., particularly preferably from 160 to 200xc2x0 C., or by irradiating with an amount of energy sufficient for said pigment precursor to be heated to said temperature. It is known that the fragmentation temperature may be lowered by using a catalyst, for example an acid.
The heating time is not critical, as long as care is taken that it is sufficiently long for the fragmentation to be completed. Typically, it ranges from several seconds to several hours, preferably from about 1 to about 30 minutes. The required heating time can be decreased by elevating the temperature.
In addition to the steps (a) and (b), the process may of course comprise additional steps which are known per se, for example a prior bleaching and/or a subsequent overcoating with, for example, a colourless nitrocellulose lacquer.
When the porous material also contains other compounds in its pores, it is preferred to add the latter at the latest before step (b), most preferred before step (a).
The examples which follow illustrate the invention:


A printer includes a printing portion, a cover including a first roller, a peeling mechanism including a second roller, and a first guide portion including a moving portion and a first restricting portion. The peeling mechanism is switched among three states. In a first state, the second roller is separated from the first roller. In a third state, the second roller is in contact with the first roller. In a second state, the distance between the first roller and the second roller is less than the distance between the first roller and the second roller in the first state. The moving portion switches the peeling mechanism from the first state to the second state as the cover changes from an open state to a closed state. The first restricting portion restricts the switching of the peeling mechanism from the third state to the second state.

The present disclosure relates to a printer that is provided with a peeling mechanism that peels a printed label off of a release paper.
A printer is known that is able to switch between two different operating modes of normal printing and peel-off printing. Normal printing is an operating mode in which a printed label is discharged in a state in which it is affixed to a release paper. Peel-off printing is an operating mode in which the printed label is discharged in a state in which it has been peeled off of the release paper. A label printer that is a printer that is able to switch between normal printing and peel-off printing is provided with a peeling unit that includes a pinch roller and a torsion spring. The peeling unit is able to move such that the pinch roller is separated from a platen roller during normal printing and is in contact with the platen roller during peel-off printing. During peel-off printing, the pinch roller is pressed against the platen roller by the energizing force of the torsion spring. The platen roller and the pinch roller rotate in a state in which the release paper is pinched between the platen roller and the pinch roller, and they bend the release paper such that the side of the release paper to which the label is not affixed faces each other. By bending the release paper, the peeling unit peels the printed label off of the release paper. Note that in order for the printed label to be peeled off of the release paper properly, it is preferable for the pinch roller to make proper contact with the platen roller.


A pickup for a stringed musical instrument, including at least one magnet and at least one pressure sensitive element arranged in contact with the at least one magnet.

A pickup is a transducer that captures or senses mechanical vibrations produced by musical instruments, particularly stringed instruments, and converts them to an electrical signal. The electrical signal is in turn amplified using an instrument amplifier to produce musical sounds through a speaker. Pickup assemblies enable quiet or relatively quiet instruments such as the electric guitar, electric bass guitar, Chapman Stick or electric violin to be audible when played with other louder musical instruments or to larger audiences. Existing pickup assemblies are primarily of three types, namely body pickups, accelerometer pickups and string pickups.
For example, with reference to an electric guitar, body pickups may be directly attached to an inside part of a top of the electric guitar, and behind a bridge of the electric guitar. The body pickups are typically made of a piezoelectric sensor material such as piezoelectric crystal or film or from electret film material. The accelerometer pickups are typically mounted to measure the movement of a top or body of an instrument, which directly correlates to the sound of the instrument. The string pickups typically detect vibrations from the strings. Most electric guitars and electric bass guitars use magnetic pickups.
Magnetic pickups convert vibrations of guitar strings through electromagnetic induction into electrical signals, which may be amplified or modified so as to provide desired volume and/or sound effects. Traditional magnetic pickups typically detect vibrations or movements of strings in an electromagnetic field to induce electrical current in a coil. The traditional single coil magnetic pickups are prone to capture noise from electromagnetic fields due to mains electricity, wiring, power transformers, fluorescent light ballasts etc. in the vicinity and produce electrical interference. This in turn creates noise disturbances in the sound when amplified.
Therefore, in light of the foregoing discussion, there exists a need to overcome the aforementioned drawbacks in existing pickups due to electrical interference that causes undesirable noise.


A foundation pile includes a first flange section, a second flange section, and a web section. The first flange section, second flange section, and web section are formed from a single length of material and each comprises at least two layers of the material. A second end of the length of material is wrapped 180-degrees around a first end of the length of material to form a wrapped-around portion in the length of material and a three-layered overlapping region in the first flange section. One or more tabs protrude perpendicularly from the first end of the length of material, such that the tabs are not bent relative to the first end. The one or more tabs extend into respective one or more slots in the length of material adjacent the second end of the length of material. The respective one or more slots are formed in the wrapped-around portion.

Piles are often implemented to establish and stabilize foundations for structures that are designed to maintain heavy loads, or for structures that are constructed in loose or unstable ground. For example, foundation piles can be used in the construction of bridges, docks, and other structures that require a footing in sandy and/or muddy terrain. Foundation piles can further be used to reinforce conventional foundations against anticipated earthquakes, floods, tornadoes, and other natural disasters. Still further, foundation piles are often used to provide a stable foundation for sky-scrapers, towers, and other large buildings that require a substantial footing.
While foundation piles can be constructed according to various techniques and can have various structural configurations, some foundation piles often resemble I-beams that are frequently used in construction to support large loads while spanning large horizontal distances. Conventional metal foundation piles and metal I-beams are often constructed using a metal rolling technique (e.g., hot rolling and cold rolling techniques). Conventional metal rolling techniques, however, are often only capable of efficiently producing flat sheets that are welded together to form foundation piles and I-beams with the traditional I-shaped cross-sections. In other words, foundation piles constructed using conventional metal rolling techniques are limited in their flange configurations and often have flanges that are double layered. While traditional flange configurations and double-layered flanges may be acceptable in certain implementations, the limitations of conventional foundation piles and the associated manufacturing methods render certain foundation pile applications expensive and/or inefficient to implement.


A system for determining abandonment of a child or infant in a vehicle. The system features a remote key in communication with sensors operatively connected to seatbelts in a vehicle. If a user presses the lock button on the remote key the sensors determine if any seatbelt has been left engaged. If a seatbelt is engaged an alarm is activated on the remote key. If no seatbelt is left engaged, the vehicle doors become locked. To override the alarm, and override button must be pushed on the remote key. An unlock button on the remote key unlocks the vehicle doors and the system is reset.

Many infants and children have suffered painful an unnecessary deaths due to being left in a vehicle. The present invention features a system for determining abandonment of a child or infant in a vehicle. The system incorporates sensors in the seatbelts that determine whether the seatbelts are locked at the time a user locks the vehicle from the outside (e.g., via a remote key). If a seatbelt is locked, an alarm is activated after a certain length of time (e.g., 3 seconds), alerting the user that he/she needs to check the interior of the vehicle. If the vehicle is empty, the user can press a button to override the alarm, thereby locking the vehicle.
Any feature or combination of features described herein are included within the scope of the present invention provided that the features included in any such combination are not mutually inconsistent as will be apparent from the context, this specification, and the knowledge of one of ordinary skill in the art. Additional advantages and aspects of the present invention are apparent in the following detailed description and claims.

System for determining abandonment of child in unattended vehicle


Carbon-based materials, and associated methods and articles, are generally provided. In some embodiments, a carbon-based material comprises a carbon-based portion and a functional group bonded to the carbon-based portion. The functional group may be capable of forming a reversible covalent bond with a species. Carbon may make up greater than or equal to 30 wt % of the carbon-based portion. The carbon-based portion may comprise graphene, and a ratio of a total number of functional groups in a plurality of functional groups bonded to the graphene to a total number of carbon atoms in the plurality of carbon atoms of the graphene may be greater than or equal to 1:50. The carbon-based portion may comprise graphene, and greater than or equal to 70% of the graphene sheets may be spaced apart from their nearest neighbors by a distance of greater than or equal to 10 Å. A method may comprise applying a voltage to a carbon-based material. The voltage may be applied in the presence of a combination of solvents comprising a dissolved species. The combination of solvents may comprise a solvent stable at voltages of greater than or equal to −3.15 V and less than or equal to −2.2 V and/or may comprise a solvent with a surface tension within 25% of a surface tension of the carbon-based material. The voltage may be a decreasing voltage that decreases at a rate of greater than or equal to 2 μV/s and less than or equal to 40 μV/s and has a value of greater than or equal to −2.2 V and less than or equal to −3.15 V at at least one point in time.

Carbon-based materials may be beneficially employed in a variety of applications. However, it is often challenging to obtain carbon-based materials in a desirable state. For instance, it may be difficult to obtain fully exfoliated, unaggregated graphene from graphite and to obtain graphene with desirable chemical functionalization.
Accordingly, improved articles and methods are needed.


A lever-type cam follower for a valve drive of an internal combustion engine for operating at least one gas exchange valve, includes a main body exhibiting a substantially U-shaped configuration and comprised of two spaced-apart side walls extending in a longitudinal direction and a cross member interconnecting the side walls. The cross member defines a valve-proximate side which includes a substantially planar bearing surface for receiving a gas exchange valve. In addition, the cross member is provided with a passageway for conduction of lubricant to a contact zone of the gas exchange valve upon the bearing surface, whereby the passageway is disposed outside the contact zone but in immediate proximity thereto.

The present invention relates to a lever-type cam follower for a valve drive of an internal combustion engine for operating at least one gas exchange valve.
U.S. Pat. No. 5,016,582, issued May 21, 1991 discloses a cam follower which is of substantially U-shaped cross section and includes two longitudinal side walls which are interconnected by a cross member. The cross member defines a valve-proximate side which has an end portion formed with a bearing surface for a gas exchange valve. An opening is formed through the cross member for passage of lubricant to the contact zone of the gas exchange valve upon the bearing surface. This conventional cam follower suffers the drawback that the bearing surface for the gas exchange valve is formed as a ball-shaped recess that increases the complexity of manufacture. Moreover, the opening for transmission of lubricant is disposed exactly in the contact zone between the gas exchange valve and the bearing surface. Thus, increased wear is experienced in this zone so that the recessed region must be reinforced.

Lever-type cam follower for a valve drive of an internal combustion engine


A method of modeling dynamic system performance includes enabling a user to create a user-defined static behavior model of a user-defined system of computers, networks and/or bridges. A library of blocks is provided that each represent a computer, a network and/or a bridge for the user to use in defining a user-defined static behavior model, at least some of the blocks in the library of blocks may include one or more block parameters that are user definable. The static behavior model is automatically converted into a dynamic behavior model that is compatible with a simulator and is read into the simulator. A plurality of Monte-Carlo simulations are run on the dynamic behavior model to produce a plurality of simulation outputs, which are analyzed and the analyzed results are outputted.

Computer networks can include a number of servers and connections between servers. When designing a computer network, or modifying an existing computer network, it is desirable to analyze the computer network to look for bottlenecks in the computer network and/or components that have excessive capacity. A bottleneck can, for example, be a point (such as a particular computer server, network section or bridge) at which demand for a resource exceeds the available supply of the resource. Analyzing such computer networks can be done by creating and then simulating a dynamic behavioral model of the computer network. However, creating such dynamic behavioral models can be complex, and often requires specialized coding knowledge in the particular computer language understandable by the simulator. This is often beyond the ability of a casual computer network analyst.
What would be desirable is a system that allows a user to easily create a static behavior model of the computer network that is similar to a standard computer network topology diagram, automatically convert the static behavior model into a dynamic behavior model suitable for simulating on a dynamic simulator, and then automatically simulating the dynamic behavior model using automatically generated randomized loads.

Determining dynamic system performance from a static behavior model


A machine that can pass, reflect, filter, or block light along multiple paths. The specific portions of light that can be passed, reflected, blocked, or filtered, are controlled by an optical routing subassembly. This optical routing subassembly can be manipulated to direct specific portions of light to specific paths.

There is a need for mechanisms that provide for high resolution imaging and tracking. There is also a need for mechanisms that provide for optical routing and switching. Additionally, there is a need for mechanisms that facilitate optical computation.
Relevant prior art includes:
U.S. Pat. No. 3861788January, 1975Webster359/889U.S. Pat. No. 4084909April, 1978Mathisen356/332U.S. Pat. No. 4176916December, 1979Carpenter359/589U.S. Pat. No. 4448500May, 1984Marling359/503U.S. Pat. No. 4738535April, 1988Webster356/418U.S. Pat. No. 4930883June, 1990Salzman359/419U.S. Pat. No. 5335082August, 1994Sable347/232U.S. Pat. No. 5371543December, 1994Anderson348/270U.S. Pat. No. 5508844September, 1994Blake359/503U.S. Pat. No. 5748812May, 1998Buchin385/018U.S. Pat. No. 6498682December, 2002Glance359/578U.S. Pat. No. 6567225May, 2003Derian359/892Other Publications:    Ron Wodaski, The New CCD Astronomy, 2002, The New Astronomy Press, pp. 78-80, 322-323, 328-330    Julian Brown, The Quest for the Quantum Computer, 2000, Touchstone, pp. 61-71Prior art suffers from a number of disadvantages:            (a) different devices are required to be used to perform all of the desired functions;        (b) cost is increased when requiring several devices to perform the desired functions;        (c) an increased number of devices in an optical system can cause an increased and unwanted amount of flexure in the optical system;        (d) an increased number of devices in an optical system can cause an unwanted lengthening of the light path in the optical system;        (e) on-axis optical guiding is not achieved;        (f) simultaneous imaging and optical guiding from the whole field is not achieved;        (g) switching from imaging mode to viewing mode may require a component of the device to be physically moved;        (h) existing optical switches are not highly configurable;        (i) optical logic gates with reversible and conservative properties are not yet commercially practical; and        (j) electronic logic gates are susceptible to electromagnetic radiation interference.

Combined optical fiber wheel, beamsplitter, switch, and logic gate


A method for encoding depth map image involves dividing the image into blocks. These blocks are then classified into smooth blocks without large depth discontinuities and discontinuous blocks with large depth discontinuities. In the discontinuous blocks, depth discontinuities are represented by line segments and partitions. Interpolation-based intra prediction is used to approximate and compress the depth values in the smooth blocks and partitions. Further compression can be achieved with of depth-aware quantization, adaptive de-blocking filtering, scale adaptive block size, and resolution decimation schemes.

Most of the visual content today is still in two dimensional (2D) images or videos which are in form of a sequence of images. Generally, the conventional images and videos do not support changes of viewpoints other than just magnification/scaling or simple shifting. With the advent of stereo or three dimensional display technologies, active shutter and passive polarized eye glasses are now commonly available. More recently, high resolution autostereoscopic displays, which do not require eye glasses, have become available. The input to such autostereoscopic displays is usually i) a video plus a depth map which describes the depth of each pixel in the video or ii) a set of videos at adjacent viewpoints, sometimes called multi-view videos, which are multiplexed on an image frame in a certain format. A lenticular lens or parallax barrier of the autostereoscopic displays perform a spatial filtering so that a user at a certain viewing position will be able to see two different images in his/her left and right eyes, respectively, thus creating a 3D perception.
As noted, depth maps are images (or videos if taken at regular time interval) that record the distances of observable scene points from the optical point of a camera. It provides additional information to the associated color pixels in the color image or video taken at the same position by specifying their depths in the scene. One application of depth maps is to synthesize new views of the scene from the color image or videos (also referred to as texture). Depth maps can also be taken at adjacent spatial locations to form multi-view depth images or videos.
Efficient compression methods for depth map images and videos are therefore important for the efficient storage and transmission of such images. Intra coding plays an important role in hybrid video coding schemes, especially in applications such as effect access, references for prediction, error resilience, bit rate control, low-complexity encoding, etc. See, G. J. Sullivan et al, "Overview of the High Efficiency Video Coding (HEVC) Standard," IEEE Trans. Circuits and Systems for Video Technology, vol. 22, pp. 1649-1668, (2012); G. Tech et al., "3D-HEVC draft text 1," in Proceedings of the 5th Meeting of Joint Collaborative Team on 3D Video Coding Extensions (JCT-3V), Document JCT3V-E1001, Vienna, Austria, (August 2013); and J. Lainema et al., "Intra Coding of the HEVC standard," IEEE Trans. Circuits and Systems for Video Technology, vol. 22, pp. 1792-1801, (2012), all of which are incorporated herein by reference in their entirety. Intra coding is performed relative to information that is contained only within the current frame and not relative to any other frames in the video sequence.
The intra coding of state-of-the-art depth compression algorithms is usually based on spatial sample prediction followed by discrete cosine transform (DCT)-based coding. However, these methods may not be efficient due to the piecewise smooth nature of depth maps. The conventional DCT-based intra coding methods need to use a considerable number of bits to cope with depth discontinuities in depth maps. At high compression ratio, the DCT-based intra coding usually generates artifacts at the discontinuities and degrades the coding quality. Hence, more efficient intra coding for depth compression is in demand.

Depth discontinuity-based method for efficient intra coding for depth videos


A boring tool is proposed which has a cutting portion at one end thereof, a driver engaging portion at the other end thereof, a shank arranged between the cutting portion and the driver engaging portion. The shank is formed with a helical groove for discharging cuttings. The driver engaging portion has a hexagonal outer shape and is formed with a hexagonal hole and a recess at bottom of the hexagonal hole for receiving the tip of a driver. The cutting portion has a pointed tip and a substantially conical shape, a first recess formed by cutting off substantially a 180xc2x0 section of the cutting portion as seen axially from the pointed tip with an edge in the rotational direction forming a cutting edge, and a second recess formed by cutting off substantially a 90xc2x0 section of the remaining 180xc2x0 section. The second recess is separated from the first recess by a thin-walled partitioning wall.

The present invention relates to a boring tool used to form a bore when a plug, an anchor or the like used to mount an instrument is inserted into a brittle wall substrate such as a plaster board.
Heretofore, as such a boring tool, a drill is used which is to be mounted on an electric drill and has a shank portion having a helical shape except its mounting portion, and a cutting edge having a pointed tip.
Also, as one for a manual driver, JP utility model publication 6-32325 proposes such a boring tool.
But when various kinds of instruments are mounted to a brittle wall surface substrate such as a plasterboard, troublesome work was needed. Namely, after boring has been made in the wall surface substrate with a drill mounted to an electric power tool, the drill is removed from the power tool and a driver bit or a hexagonal socket has to be mounted on the power tool to thread a screw or a bolt into a plug or anchor inserted through an instrument into the wall surface substrate. Otherwise, it was necessary to prepare another power tool to which is mounted a driver bit or a hexagonal socket in addition to a power tool to which is mounted a drill.
Also, in order to solve this problem, JP utility model publication 6-32325 for a manual driver was proposed. But since the driver bit is fitted in the boring tool only at its tip, rattling will develop, thus making accurate boring difficult. Also, if it is used with an electric power tool, there was a problem that the fitting portion tends to get damaged soon.
According to this invention, there is provided a boring tool comprising a cutting portion at one end thereof, a driver engaging portion at the other end thereof, a shank arranged between the cutting portion and the driver engaging portion, the driver engaging portion being formed with a hexagonal hole and a cross recess at bottom of the hexagonal hole for receiving the tip of a cross head driver or driver bit.
According to the present invention, there is also provided a boring tool comprising a cutting portion at one end thereof, a driver engaging portion at the other end thereof, a shank 6 arranged between the cutting portion and the driver engaging portion, the shank being formed with a helical groove for discharging cuttings, the driver engaging portion having a hexagonal outer shape and formed with a hexagonal hole and a recess at bottom of the hexagonal hole for receiving the tip of a driver, a circular flange provided between the driver engaging portion and the shank and having a larger diameter than the outer diameter of the shank, the cutting portion having a pointed tip and a substantially conical shape spreading from the pointed tip toward the outer periphery of the shank, a first recess formed by cutting off substantially a 180xc2x0 section of the cutting portion as seen axially from the pointed tip with an edge in the rotational direction forming a cutting edge, and a second recess formed by cutting off substantially a 90xc2x0 section of the remaining 180xc2x0 section, the second recess being separated from the first recess by a thin-walled partitioning wall.
Other features and objects of the present invention will become apparent from the following description made with reference to the accompanying drawings, in which:


A ring saw is described which has a novel construction for centering the cutting ring. The ring saw is characterized by a groove in the inner annular surface of the cutting ring. A plurality of rollers are provided which engage the groove in the inner annular surface. The rollers serve to center the cutting ring relative to the saw body while withstanding axial and radial loads placed upon the cutting ring. The construction, as described, serves to increase the capacity of the cutting ring to withstand radial and axial loading.

Ring saws have a circular disc-shaped saw body with a circumferential edge. A cutting ring is mounted for rotation about the circumferential edge. The cutting ring has all inner annular surface with gear teeth. At least one drive gear is rotatably mounted in the saw body. The drive gear engages the gear teeth on the inner annular surface to rotate the cutting ring.
Ring saws used in the forestry industry for cutting down trees are subjected to significant radial and axial loading. Radial loading occurs as the cutting ring engages the tree. Axial loading occurs as cutting progresses and the weight of the tree bears upon the cutting ring.
Canadian Patent 1,291,396 discloses an improved ring saw which addresses the "difficulty in mounting the ring saw on the saw body to take stresses such as those applied by a tree resting on the saw". This ring saw has a track in which the cutting ring rotates. The track has a number of arcuate "bearing grooves" arranged in end to end relation in which are received "bearing strips". The bearing strips are described as being "made from a suitable plastic material having a low coefficient of friction". The cutting ring has an inwardly projecting annular flange. Three idler gears cooperate with the inwardly projecting flange to help center the cutting ring during rotation and cutting operations. The inwardly projecting flange is sandwiched between the bearing strips to withstand axial loading.
There are a number of problems with the teachings of Canadian Patent 1,291,396. Firstly, the engagement between the bearing strips and the inwardly projecting annular flange on the cutting ring is intended to serve a dual purpose of a bearing surface and a sealing surface. However, the plastic bearing material of the bearing strips will invariably experience deterioration under heavy axial loading which reduces its ability to function as a sealing surface. Without effective sealing dirt and debris enter into the gears and decrease the operational life of the gears. Secondly, the number of rotations per minute of the cutting ring is limited by the friction properties of the plastic bearing material of the bearing strips. Thirdly, when the gears perform a centering function they are subjected to radial loads, which reduces the operational life of the gears.