Methods for the production of 1,1,1-trihalogeno-2-nitroethanes from 1,1-dihalogenoethylene by using nitric acid or its salt and hydrogen chloride or hydrogen bromide or its salt, and for the production of .alpha.-unsaturated amines from the 1,1,1-trihalogeno-2-nitroethanes which are useful as insecticides.

1. Field of the Invention
The present invention relates to a process for the production of .alpha.-unsaturated amines. More particularly, it relates to an improved process for the production of .alpha.-unsaturated amines useful as insecticides and their intermediates of 1,1,1-trihalogeno-2-nitroethanes.
2. Description of the Prior Art
.alpha.-Unsaturated-amines of the formula (V) shown hereinbelow or their salts are excellent insecticidal compounds [cf. EP-302389A]. As intermediates for production of the same, 1,1,1-trihalogeno-2nitroethanes are known to be prepared by the methods of the following formulas [1] and [2]. ##STR1## [cf. Izvest. Akad. Nauk S.S.S.R., Otdel. Khim. Nauk, 1958, 841 (C.A., 53, 1111i (1959))]. ##STR2##
However, the method of the formula [1] mentioned above which reacts 1,1-dichloroethylene with nitryl chloride shows the disadvantages that nitryl chloride is explosive [cf. Ber. 75 B, 1323(1942)]; its generation must use fuming nitric acid and chlorosulfonic acid which are dangerous and difficult to handle; a large amount of waste sulfuric acid must be disposed of and the yield of the object compound is low. The method of the formula [2] has many problems that very toxic dinitrogen tetroxide and chlorine gas must be used and the yield of the object compound is also low.
Also, the method of the formula [3] is known as the reaction of 1,1-dihalogenoethylene with nitric acid. ##STR3## [cf. Probl. Organ. Sinteza. Akad. Nauk. S.S.S.R., Otd. Obshchi. Tekhn. Khim. 1965. 60 (CA. 64, 8023b (1966))]. However, it is reported that the yield of this reaction is extremely low, i.e., 10.6% of 1,1-dichloro-2-nitroethylene and 37% of nitroacetyl chloride, respectively.
On the other hand, the methods of the formulas [4] and [5] are known to introduce a nitro group and fluorine atom into 1,1-dihalogenoethylene (the latter is supposed to show reactivity entirely different from chlorine and bromine atoms). ##STR4## [Izv. Akad. Nauk SSSR, Set. Kim., 1963, 1946(cf. CA. 60, 5325 g)] ##STR5## [Dokl. Akad. Nauk SSSR, 149, 330-333 (1963) (cf. CA. 59, 6215 g)]
Also, improvements on the above methods [4] and [5] are disclosed in DE 3,305,201 and DE 3,305,202, which however do not afford 1,1,1-trichloro or tribromo-2-nitroethane as the object compound and further do not suggest or teach to react olefins with hydrogen chloride or hydrogen bromide and nitric acid to introduce chlorine or bromine atom as well as nitro group.
The reaction of halogenated olefins with hydrogen chloride or hydrogen bromide requires use of a catalyst such as a metal chloride or active carbon, because their reactivity is less due to a reverse inductive effect (-I effect) of the halogen atom in the halogenated olefins. For instance, anhydrous ferric chloride is used in the reaction of 1,1-dichloroethylene with hydrogen chloride (cf. U.S. Pat. No. 2,209,000).
On the other hand, the reactivity of hydrogen fluoride is different from that of other hydrogen halides. For instance, hydrogen fluoride is required to react with common olefins under pressure, although they tend to react with hydrogen chloride or hydrogen bromide at room temperature [cf., J. Org. Chem., 3, 26(1938)]. Also, hydrogen fluoride is highly reactive with halogenated olefins, depending upon their structures [cf., J. Phys. Chem., 44, 275(1940)]. Specifically, it reacts easily, e.g. with 1,1-dichloroethylene at 65.degree. C. [cf., J. Am. Chem. Soc., 65, 1271(1943)]. Further, hydrogen halide [HX; X=F, Cl, Br or I] is generally known as an electrophilic reagent. It is considered that in the addition reaction of olefin with hydrogen halide, ionized H.sup.+ initially attacks olefin and then X.sup.- reacts with carbonium cation formed as the intermediate. Hydrogen fluoride however reacts with a polyhalogenated olefin, with predominant nucleophilic attack of F.sup.-, thereby affording the desired product in good yield [J. Am. Chem. Soc., 82, 3091(1960)] . However, such nucleophilic reaction is not known for hydrogen chloride and hydrogen bromide. Accordingly, the reaction of 1,1-dihalogenoethylene with hydrogen chloride or hydrogen bromide whose reactivity is different from hydrogen fluoride is not suggested or predicted by the fact that 1,1-dihalogenoethylene as a kind of polyhalogenoolefin reacts easily with hydrogen fluoride.
Under these circumstances, the inventors of this invention have made various studies and have found unexpectedly the fact that when a 1,1-dihalogenoethylene is reacted with nitric acid or its salt and hydrogen chloride or hydrogen bromide or its salt, it provides at a high yield 1,1,1-trihalogeno-2-nitroethane (or 1-nitro-2,2,2-trihalogenoethane) in which a nitro group and a halogen atom are introduced at the same time and at the specific positions.
3. Summary of the Invention
This invention provides
1) a process for the production of 1,1,1-trihalogeno-2-nitroethanes which comprises reacting a 1,1-dihalogenoethylene of the formula (I): ##STR6## wherein X.sup.1 and X.sup.2 are the same or different and represent a fluorine, chlorine, bromine or iodine atom, with nitric acid or its salt and hydrogen chloride or hydrogen bromide or its salt to obtain a compound of the formula (II): ##STR7## wherein X.sup.1 and X.sup.2 have the same meanings as defined in the formula (I), and X.sup.3 is chlorine or bromine atom; PA1 2) a process for the production of .alpha.-unsaturated amines which comprises reacting a 1,1,1-trihalogeno-2-nitroethane of the formula (II) mentioned in the above 1) with an amino compound of the formula (III): EQU R.sup.1 --NH--C.sub.n H.sub.2n --A (III) PA1 3) a process for the production of .alpha.-unsaturated-amines which comprises treating a 1,1,1-trihalogeno-2-nitroethane of the formula (II) mentioned in the above 1) with a base to obtain a 1,1-dihalogeno-2-nitroethylene of the formula (VI): ##STR10## wherein X.sup.4 and X.sup.5 are the same or different and represent a fluorine, chlorine, bromine or iodine atom, and then reacting it with an amino compound of the formula (III): EQU R.sup.1 --NH--C.sub.n H.sub.2n --A (III) PA1 wherein R.sup.1, A and n have the same meanings as defined in the above 2), or its salt and an amino compound of the formula (IV): ##STR11## wherein R.sup.2 and R.sup.3 have the same meanings as defined in the above 2), or its salt to obtain a compound of the formula (V): ##STR12## wherein R.sup.1, R.sup.2, R.sup.3 A and n have the same meanings as mentioned above or its salt; PA1 3. Preferred Embodiments of the Invention
wherein R.sup.1 is a hydrogen atom, an C.sub.1-4 alkyl, halo-C.sub.1-4 alkyl, mono- or di-C.sub.1-4 alkoxy-C.sub.1-4 alkyl, C.sub.7-9 aralkyl, optionally substituted phenyl, mono- or di-C.sub.1-4 alkylamino or C.sub.1-4 alkoxy group, A is a 3- or 4-pyridyl, pyrazinyl, 2-, 4- or 5-thiazolyl or phenyl group which may be substituted by a halogen atom or a C.sub.1-4 alkyl, C.sub.1-4 alkylthio or C.sub.1-4 alkoxy group, and n is 0, 1 or 2, or its salt and an amino compound of the formula (IV): ##STR8## wherein R.sub.2 is a hydrogen atom, or a C.sub.1-4 alkyl or C.sub.7-9 aralkyl group, R.sub.3 is a hydrogen atom, a C.sub.1-5 alkyl, halo-C.sub.1-4 alkyl, hydroxy-C.sub.1-4 alkyl, mono- or di-C.sub.1-4 alkoxy-C.sub.1-4 alkyl, mono- or di-C.sub.1-4 alkylthio-C.sub.1-4 alkyl, di-C.sub.1-4 alkylamino-C.sub.1-4 alkyl, tri-C.sub.1-4 -alkylsilyl-C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.7-9 aralkyl, optionally substituted phenyl, amino, di-C.sub.1-4 alkylamino, pyridyl-C.sub.1-2 alkyl or thiazolyl-C.sub.1-2 alkyl group (pyridyl and thiazolyl ring may be substituted by a halogen atom), or R.sup.2 and R.sup.3 together with the adjacent nitrogen atom may form a 5 or 6-membered heterocylic ring which may contain an oxygen atom or another nitrogen atom, or its salt, to obtain a compound of the formula (V): ##STR9## wherein R.sup.1, R.sup.2, R.sup.3, A and n have the same meanings as defined above or its salt; and
With respect to R.sub.1 of the above mentioned formulas,
the C.sub.1-4 alkyl may be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl, among which methyl, ethyl or n-propyl is preferable; PA0 the halo-C.sub.1-4 alkyl may be monochloromethyl, dichloromethyl, trichloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl or 1,1,2,2-tetrafluoroethyl; PA0 the mono- or di-C.sub.1-4 alkoxy-C.sub.1-4 alkyl group may be methoxymethyl, dimethoxymethyl, ethoxymethyl, 1- or 2-methoxyethyl, 2,2-dimethoxyethyl, 3-methoxypropyl or 3,3-dimethoxypropyl, among which methoxymethyl, dimethoxymethyl, 2-methoxyethyl or 2,2-dimethoxyethyl is preferable; PA0 the C.sub.7-9 aralkyl group may be benzyl, 4-chlorobenzyl, 4-bromobenzyl, 4-methylbenzyl, phenethyl or 4-methylphenethyl; PA0 the optionally substituted phenyl group may be phenyl or a phenyl substituted by one to four substituents of a halogen (e.g., fluorine, chlorine, bromine or iodine), C.sub.1-3 alkyl (e.g., methyl, ethyl or propyl), C.sub.1-3 alkoxy (e.g., methoxy, ethoxy or propoxy), amino, hydroxy, carboxy or sulfo; PA0 the mono- di-C.sub.1-4 alkylamino group may be methylamino, ethylamino, n-propylamino, i-propylamino or n-butylamino, or dimethylamino, methylethylamino, diethylamino or di-n-propylamino; PA0 the C.sub.1-4 alkoxy group may be methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy or i-butoxy. PA0 the halo C.sub.1-4 alkyl, mono- or di-C.sub.1-4 alkoxyalkyl, C.sub.7-9 aralkyl, optionally substituted phenyl and di-C.sub.1-4 alkylamino groups include the same ones examplified in R.sup.1 ; PA0 the hydroxy C.sub.1-4 alkyl group may be hydroxymethyl, 1- or 2-hydroxyethyl, or 3-hydroxypropyl; PA0 the mono- or di-C.sub.1-4 alkylthio-C.sub.1-4 alkyl group may be methylthioethyl, ethylthioethyl, n-propylthioethyl methylthiopropyl, dimethylthiomethyl, diethylthiomethyl, dimethylthioethyl or dimethylthiopropyl; PA0 the di-C.sub.1-4 alkylamino-C.sub.1-4 alkyl group may be dimethylaminoethyl, diethylaminomethyl or dimethyl aminopropyl; PA0 the tri-C.sub.1-4 alkylsilyl-C.sub.1-4 alkyl group may be trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylpropyl, triethylsilylmethyl or tri-n-propylsilylmethyl; PA0 the C.sub.2-4 alkenyl group may be vinyl, allyl or isopropenyl; PA0 the pyridyl-C.sub.1-2 alkyl group may be substituted by one to three halogens (e.g., Cl, Br or F) on the pyridine ring and includes e.g., (3-pyridyl)methyl, (6-chloro-3-pyridyl)methyl, (6-fluoro-3-pyridyl)methyl, (6-bromo-3-pyridyl)methyl and 1-(3-pyridyl)ethyl; PA0 the thiazolyl-C.sub.1-2 alkyl group may be substituted by one to three halogens (e.g., Cl, Br or F) on the thiazole ring and includes e.g., (2-thiazolyl)methyl, (5-thiazolyl)methyl, (2-chloro-5-thiazolyl)methyl, (2-bromo-5-thiazolyl)methyl, (4-thiazolyl)methyl and 1-(5-thiazolyl)ethyl. Preferable examples of R.sup.3 are hydrogen, or a C.sub.1-4 alkyl such as methyl, ethyl or propyl.
Preferable examples of R.sup.1 are hydrogen atom and a C.sub.1-4 alkyl group such as methyl, ethyl or propyl.
With respect to R.sup.2, the C.sub.1-4 alkyl group and C.sub.7-9 aralkyl group mentioned in R.sup.1 are applicable to these groups of R.sup.2. Preferable examples of R.sup.2 are hydrogen atom and a C.sub.1-4 alkyl group such as methyl, ethyl or propyl.
With respect to R.sup.3, the C.sub.1-5 alkyl group includes the C.sub.1-4 alkyl groups examplified in R.sup.1 and also amyl;
The 5- or 6-membered heterocyclic group which may contain an oxygen atom and another nitrogen atom (in addition to the adjacent nitrogen atom to R.sub.2 and R.sub.3) may be pyrrolidino, piperidino, morpholino, or 4-methylpiperazino.
With respect to A, the 3- or 4-pyridyl, pyrazinyl, 2-, 4- or 5-thiazolyl or phenyl group may be substituted by one to four substituents of a halogen, C.sub.1-4 alkyl, C.sub.1-4 alkylthio or C.sub.1-4 alkoxy. Here, the halogen may be fluorine, chlorine, bromine or iodine, the C.sub.1-4 alkyl or C.sub.1-4 alkoxy includes the same groups exemplified in R.sup.1 and the C.sub.1-4 alkylthio may be methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio or i-butylthio. Examples of the 3- or 4-pyridyl groups which may be substituted are 3-pyridyl, 2- or 6-chloro-3-pyridyl, 5- or 6-bromo-3-pyridyl, 6-fluoro-3-pyridyl, 6-methoxy-3-pyridyl, 6-methyl-3-pyridyl, 5- or 6-trifluoromethyl-3-pyridyl, 2-methylthio-3-pyridyl, 2,6- or 5,6-dichloro-3-pyridyl, 4-pyridyl and 2,6-dichloro-4-pyridyl. Examples of the 2,4- or 5-thiazolyl groups which may be substituted are 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-chloro-5-thiazolyl, 2-bromo-5-thiazolyl, 2-fluoro-5-thiazolyl, 2-methyl-5-thiazolyl, 2-trifluoromethyl-5-thiazolyl, 2,4-dichloro-5-thiazolyl and 2-phenyl-5-thiazolyl. Examples of the pyrazinyl groups which may be substituted are 2-pyrazinyl, 5-chloro-2-pyrazinyl 5-bromo-2-pyrazinyl, 5-fluoro-2-pyrazinyl 5-methoxy-2-pyrazinyl and 5-methyl-2-pyrazinyl Examples of the phenyl groups which may be substituted are phenyl, p-chlorophenyl, p-bromophenyl, p-fluorophenyl, p-tolyl and p-methoxyphenyl.
Preferable examples of A are 2-halogeno-5-thiazolyl such as 2-chloro-5-thiazolyl and 6-halogeno-3-pyridyl such as 6-chloro-3-pyridyl.
A preferable example of C.sub.n H.sub.2n is CH.sub.2.
Specific examples of the 1,1-dihalogenoethylenes (I) which are the starting material of this invention are 1,1-difluoroethylene, 1,1-dichloroethylene, 1,1-dibromoethylene, 1,1-diiodoethylene, 1-chloro-1-fluoroethylene, 1-bromo-1-fluoroethylene, 1-fluoro-1-iodoethylene, 1-bromo-1-chloroethylene, 1-chloro-1-iodoethylene and 1-bromo-1-iodoethylene, among which 1,1-dichloroethylene is useful because it is commercially available at a low price.
According to this invention, a 1,1-dihalogenoethylene (I) is reacted with nitric acid or its salt and hydrogen chloride or hydrogen bromide (hereinafter sometimes referred to as hydrogen halide) or its salt to obtain a 1,1,1-trihalogeno-2-nitroethane (II). Each of nitric acid and hydrogen halide is generally used in 0.5 to 5 equivalents, preferably 1.0 to 2.0 equivalents, more preferably 1.2 to 1.5 equivalents to the compound (I). In case of using a salt of hydrogen halide, further addition of nitric acid enough to generate the hydrogen halide is desirable to give a good result. Similarly, when a salt of nitric acid is used, further addition of hydrogen halide which is necessary for generating nitric acid will achieve a good result. Examples of the salts of the hydrogen halides or nitric acid are the alkaline metal salts, alkaline earth metal salts, and ammonium salt. Needless to say, it is possible to use the mixture of nitric acid and its salt or the hydrogen halide and its salt. The hydrogen halide can be used as it is but is conveniently used as its aqueous solution which is easy to handle, i.e., as hydrohalogenic acid. The concentration of each of nitric acid and the hydrogen halide to be used in the reaction is suitably selected, as far as it does not impede the reaction. As nitric acid, 60% to 70% nitric acid which is available on the market or a fuming nitric acid can be used. About 35% hydrochloric acid and about 47% hydrobromic acid which are available on the market can be used as hydrogen chloride and hydrogen bromide, respectively. These hydrohalogenic acids and nitric acid can be used by diluting with water, although it may cause the delay of the reaction speed. The preferred initial concentration of each of the hydrogen halide and nitric acid to be added in the reaction system is about 40% to 60%.
The reaction is usually carried out in an aqueous system, to which an inert organic solvent may be added. Examples of the organic solvents are those which are not easily mixable with water, such as hydrocarbons (e.g., hexane, petroleum ether, ligroin, cyclohexane, benzene, toluene, or xylene), ethers (e.g., diethyl ether or diisopropyl ether), esters (e.g., ethyl acetate) or halogenated hydrocarbons (e.g., chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane or 1,1-dihaloethylene as the starting material); those which are homogenerously mixable with water, such as nitriles (e.g., acetonitrile), tetrahydrofuran (hereinafter referred to as "THF") or dioxane.
The reaction can be conducted at 0.degree.-100.degree. C. in a sealed vessel but be conducted at 0.degree.-40.degree. C., preferably 10.degree.-35.degree. C. in an open system. The reaction time is 5 minutes or more, preferably 0.5 to 48 hours. However, the reaction time of 5 minutes or more, preferably 0.5 to 5 hours is sufficient in case where the preferred concentrations of the hydrogen halide and nitric acid and the preferred reaction temperature are selected.
The order of addition of the raw materials, i.e., the compound (I), nitric acid or its salt and the hydrogen halide or its salt in the reaction system can be optionally determined. That is, to the mixture of two optional kinds of the raw materials can be added the remaining raw material, or to one optional raw material can be added the remaining two raw materials at the same time. Alternatively, the three raw materials can be simultaneously mixed. We found the fact that nitric acid is reacted with the 1,1-dihalogenoethylene to produce the 1,1,1-trihalogeno- 2-nitroethane. For instance, when 1,1-dichloroethylene is reacted with 70% nitric acid, it affords the mixture of 1,1,1-trichloro-2-nitroethane and 1,1,1,2-tetrachloroethane as main products, which however is not satisfactory for yield. On the other hand, hydrochloric acid or hydrobromic acid is hardly reacted with the 1,1-dihalogenoethylene under the condition of the present invention. Thus, it will be understood that in accordance with the reaction of the present invention, the coexistence of nitric acid and the hydrogen halide is required to prepare the 1,1,1-trihalogeno-2-nitroethane (II) in high yield from the 1,1-dihalogenoethylene.
The completion of the reaction can be detected by the stop of an exothermic reaction, or the conventional analysis with an instrument such as gas chromatography, NMR, etc. The object compound (II) can be isolated by the conventional methods such as liquid separation, extraction and evaporation.
Examples of 1,1,1-trihalogeno-2-nitroethanes (II) thus obtained are 1,1,1-trichloro-2-nitroethane, 1-bromo-1,1-dichloro-2-nitroethane, 1,1-dibromo-1-chloro-2-nitroethane, 1-chloro-1,1-diiodo-2-nitroethane, 1,1-dichloro-1-fluoro-2-nitroethane, 1-chloro-1,1-difluoro-2-nitroethane, 1,1-dibromo-1-iodo-2-nitroethane, 1-bromo-1,1-diiodo-2-nitroethane, 1,1-dibromo-1-fluoro-2-nitroethane, 1-bromo-1,1-difluoro-2-nitroethane and 1,1,1-tribromo-2-nitroethane, among which especially 1,1,1-trichloro-2-nitroethane is industrially useful.
The 1,1,1-trihalogeno-2-nitroethane (II) is reacted with an amino compound of the formula (III): EQU R.sup.1 --NH--C.sub.n H.sub.2n --A (III)
wherein R.sup.1, A and n have the same meanings as defined above, or its salt and an amino compound of the formula (IV): ##STR13## wherein R.sup.2 and R.sup.3 have the same meanings as defined above, or its salt to provide an .alpha.-unsaturated amine of the formula (V): ##STR14## wherein R.sup.1, R.sup.2, R.sup.3, A and n have the same meanings as defined above or its salt.
The reaction is preferably conducted in the presence of a base, in order to avoid a consumption of the amino compound by a hydrogen halide which is produced as by-product of this reaction. Although there is no limitation of the order of addition of the two amino compounds (III) and (IV), it is preferable to conduct at first the reaction of a secondary amine in case of the combination of primary and secondary amines. Accordingly, it is possible to react the compound (II) with the compound (III), subsequently with the compound (IV), and alternatively to react the compound (II) with the compound (IV) followed by reacting with the compound (III).
Suitable examples of the bases to be employed in the reaction are organic bases such as triethylamine, tri-n-propylamine, pyridine, collidine, quinoline, dimethylaniline, methyldicyclohexylamine, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]-octane, 1,8-diazabicyclo[5.4.0]-7-undecene and 3,4-dihydro-2H-pyrido[1,2-a]-pyrimidin-2-one; inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide; salts of carboxylic acids such as sodium acetate and potassium acetate. It is also possible to use as the base the amino compounds themselves which are used as the raw materials. The base is preferably used in 3 or more equivalents, to the compound (II), and there is no particular limitation in the timing of addition thereof as far as it does not impede the reacion.
The reaction is usually carried out in a solvent which does not impede the reaction. Suitable examples of the solvents are water; aliphatic hydrocarbons such as hexane, petroleum ether, ligroin and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and 1,2-dichloroethane, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; amides such as dimethylformamide and dimethylacetamide; esters such as methyl acetate, ethyl acetate and butyl acetate, and sulfoxides such as dimethyl sulfoxide.
The reaction temperature can be selected from the range of -80.degree. C. or higher, but is generally -40.degree. C. or higher, preferably -40.degree. C. to 120.degree. C., more preferably -20.degree. C. to 50.degree. C. The reaction will be completed within a relatively short time of 5 minutes to 5 hours. The object compound (V) after completion of the reaction can be isolated by the conventional methods such as filtration, concentration, extraction and column chromatography.
Also, the .alpha.-unsaturated amine (V) or its salt can be obtained by treating a 1,1,1-trihalogeno-2-nitroethane (II) with a base to obtain a 1,1-dihalogeno-2-nitroethylene (VI) and then reacting the compound (VI) with or without isolation with the amino compounds (III) and (IV) or salts thereof. ##STR15##
The first reaction for obtaining the compound (VI) from the compound (II) and the base can be conducted with or without solvent. Suitable examples of the solvents to be employed are water; aliphatic hydrocarbons such as hexane, petroleum ether, ligroin and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; amides such as dimethylformamide and dimethylacetamide; esters such as methyl acetate, ethyl acetate and butyl acetate; and sulfoxides such as dimethyl sulfoxide.
Examples of the bases to be employed in the reaction are organic bases such as triethylamine, tri-n-propylamine, pyridine, collidine, quinoline, dimethylaniline, methyldicyclohexylamine, 1,5-diazabicyclo[4.3.0]-non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene and 3,4-dihydro-2H-pyrido[1.2-a]pyrimidin-2-one; inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide; salts of carboxylic acid salts such as sodium acetate and potassium acetate. Such bases are used in 1 to 5 equivalents, preferably 1 to 2 equivalents, to the compound (II). The reaction temperature can be selected in the range of -80.degree. C. or higher, but is generally -40.degree. C. or higher, preferably -40.degree. C. to 120.degree. C., more preferably -20.degree. C. to 50.degree. C.
The completion of the reaction can be detected, e.g. by gas chromatography, NMR, etc. The reaction will be completed within a relatively short time such as 15 minutes to 5 hours. For the isolation of the resulting product (VI), the conventional method such as extraction, filtration, concentration or evaporation is suitably utilized.
In the second reaction for obtaining the compound (V) from the compound (VI), the order of the reaction of two kinds of the amino compounds (III) and (IV) can be freely selected and, in case of the combination of a primary amine and a secondary amine, it is preferable to allow to firstly react the secondary amine. Any one of the compounds (III) and (IV) can be firstly used to react.
The reaction is preferably conducted in a solvent, to which those exemplified in the above mentioned first reaction are applicable. The reaction is preferably conducted in the presence of such base, to which those mentioned in the above mentioned first reaction are applicable. The base is used in 2 to 5 equivalents, preferably 2 to 3 equivalents, to the compound (VI). As occasion demands, it is also possible to use as such base the amino compound itself which is employed as the raw material. The reaction temperature can be chosen from the range of -80.degree. C. or higher, preferably -40.degree. C. to 120.degree. C. but is generally -40.degree. C. or higher, especially -20.degree. C. to 50.degree. C. The reaction time is relatively short and is 5 minutes to 5 hours.
The isolation of the resulting compound (V) after completion of the reaction can be carried out by the conventional method such as filtration, concentration, extraction and column chromatography.
In the above reactions, it is especially preferable to use secondary amines or salts thereof as either one or both of two kinds of the amino compounds (III) and (IV).
Examples of salts of the amino compounds (III) and (IV) are the salts with an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid; an organic acid such as benzenesulfonic acid; and a base such as sodium, potassium or lithium (e.g., C.sub.1-4 alkyl-N-(Na)C.sub.n H.sub.2n --A).
The amino compounds (III) and (IV) can be easily produced by the known methods, as described, e.g. in Organic Functional Group Preparations, Academic Press Vol 1, Chapter 13 (1968) and Vol 3, Chapter 10 (1972); survey of Organic Syntheses, Wiley-Inter-Science (1970), Chapter 8, or analogous methods thereto. Specific examples of the .alpha.-unsaturated-amines (V) as produced are shown in the Table 1.
TABLE 1 __________________________________________________________________________ ##STR16## Compound Melting No. R.sup.1 R.sup.2 R.sup.3 C.sub.n H.sub.2n A point __________________________________________________________________________ 1 H H Me CH.sub.2 ##STR17## 159-160 2 H H Et CH.sub.2 ##STR18## 161-162 3 H H i-Pr CH.sub.2 ##STR19## 148-150 4 H H n-Bu CH.sub.2 ##STR20## 110-112 5 H H Allyl CH.sub.2 ##STR21## 114-115 6 H H n-C.sub.5 H.sub.13 CH.sub.2 ##STR22## 97-98 7 H H ##STR23## CH.sub.2 ##STR24## 217-218 8 H H H CH.sub.2 ##STR25## 177-178 9 H H n-PrS(CH.sub.2).sub.2 CH.sub.2 ##STR26## 93-94 10 H H Me.sub.2 N(CH.sub.2).sub.2 CH.sub.2 ##STR27## 110-111 11 H H HO(CH.sub.2).sub.2 CH.sub.2 ##STR28## 161-163 12 H H MeO(CH.sub.2).sub.2 CH.sub.2 ##STR29## 108-109 13 H H (MeO).sub.2 CHCH.sub.2 CH.sub.2 ##STR30## 96-98 14 H H CF.sub.3 CH.sub.2 CH.sub.2 ##STR31## 164-165 15 H H Me.sub.3 SiCH.sub.2 CH.sub.2 ##STR32## 156-157 16 H H NH.sub.2 CH.sub.2 ##STR33## 176-177 decomposition 17 H Me Me CH.sub.2 ##STR34## 68-70 18 H (CH.sub.2).sub.4 CH.sub.2 ##STR35## 103-105 19 H ##STR36## CH.sub.2 ##STR37## oily form 20 H (CH.sub.2).sub.2O(CH.sub.2).sub.2 CH.sub.2 ##STR38## 102-103 21 H (CH.sub.2).sub.5 CH.sub.2 ##STR39## 106-108 22 H H Me.sub.2 N CH.sub.2 ##STR40## 158-159 23 Me H H CH.sub.2 ##STR41## 158-159 24 Me H Me CH.sub.2 ##STR42## 86-87 25 H H Me CH.sub.2 ##STR43## 181-183 26 Me H Me CH.sub.2 ##STR44## 103-104 27 Et H Me CH.sub.2 ##STR45## oily form 28 (MeO).sub.2 CHCH.sub.2 H Me CH.sub.2 ##STR46## oily form 29 Me H Et CH.sub.2 ##STR47## oily form 30 Me H n-Bu CH.sub.2 ##STR48## oily form 31 MeO(CH.sub.2).sub.2 H Me CH.sub.2 ##STR49## oily form 32 Me H Allyl CH.sub.2 ##STR50## oily form 33 Me H i-Pr CH.sub.2 ##STR51## 119-121 34 Me H ##STR52## CH.sub.2 ##STR53## oily form 35 Me H Me CH.sub.2 ##STR54## 145-147 36 Me H Me Me CH ##STR55## oily form 37 Me.sub.2 N H Me CH.sub.2 ##STR56## 109-110 38 n-Pr H Me CH.sub.2 ##STR57## oily form 39 n-Bu H Me CH.sub.2 ##STR58## oily form 40 ##STR59## H Me CH.sub.2 ##STR60## 118-119 41 Me H H CH.sub.2 ##STR61## 206-207 42 H Me Me CH.sub.2 ##STR62## 124-125 43 H H Me CH.sub.2 ##STR63## 211-213 decomposition 44 Me H H CH.sub.2 ##STR64## 214-215 decomposition 45 i-Pr H H CH.sub.2 ##STR65## powder 46 H Me Et CH.sub.2 ##STR66## 87-88 47 H H NH.sub.2 CH.sub.2 ##STR67## 188-190 decomposition 48 H H Me.sub.2 N CH.sub.2 ##STR68## 170-172 49 Me H Me CH.sub.2 CH.sub.2 ##STR69## oily form 50 Me Me Me CH.sub.2 ##STR70## 103-105 51 Me Me ##STR71## CH.sub.2 ##STR72## oily form 52 Me Me Me CH.sub.2 ##STR73## 110-112 53 Et H H CH.sub.2 ##STR74## 159-161 54 Et H Me CH.sub.2 ##STR75## 83-84 55 Me H Me CH.sub.2 ##STR76## 77-78 56 Me H Me CH.sub.2 ##STR77## 145-146 57 Me H Me CH.sub.2 ##STR78## 96-97 58 MeO H Me CH.sub.2 ##STR79## 100-101 59 Me H MeO(CH.sub.2).sub.2 CH.sub.2 ##STR80## 55-57 60 Me H Me CH.sub.2 ##STR81## 98-99 61 H H H CH.sub.2 ##STR82## 215-216 decomposition 62 H H Me CH.sub.2 ##STR83## 219-220 decomposition 63 H Me Me CH.sub.2 ##STR84## 133-135 64 Me H Me CH.sub.2 ##STR85## 132-133 65 Me H Me.sub.2 N CH.sub.2 ##STR86## 80-82 66 n-Pr H H CH.sub.2 ##STR87## 185-186 decomposition 67 n-Pr H Me CH.sub.2 ##STR88## 102-103 68 i-Pr H Me CH.sub.2 ##STR89## 119-120 69 Me H Me -- ##STR90## 108-109 70 Me H Me -- ##STR91## 113-114 71 Me H Et CH.sub.2 ##STR92## 132-133 72 Me H Me CH.sub.2 ##STR93## 131-133 73 Me H Me CH.sub.2 ##STR94## 106-113 74 Me H Me -- ##STR95## 155-156 75 Me H Me -- ##STR96## 120-121 76 Me H Et -- ##STR97## 118-119 77 Me H Me CH.sub.2 ##STR98## 116-117 78 Me H Me CH.sub.2 ##STR99## 131-132 79 Me H Me CH.sub.2 ##STR100## 155-156 80 H H ##STR101## CH.sub.2 ##STR102## 238-240 decomposition 81 Et H Me -- ##STR103## 95-95 82 n-Pr H Me -- ##STR104## 94-95 83 n-Bu H Me -- ##STR105## 87-88 84 Et H Et -- ##STR106## 105 85 Me H Me -- ##STR107## 114-115 86 Me H n-Pr -- ##STR108## oily form 87 H H Me -- ##STR109## 185 decomposition 88 Me H Me CH.sub.2 ##STR110## 102-103 89 Me H Me CH.sub.2 ##STR111## 100-100.5 90 Et H Me CH.sub.2 ##STR112## oily form 91 Me H Me CH.sub.2 ##STR113## 130-131 92 Et H Me CH.sub.2 ##STR114## 79-80 93 Me H Me CH.sub.2 ##STR115## 131-133 94 Et H Me CH.sub.2 ##STR116## 110-112 95 H Me Me CH.sub.2 ##STR117## 101-102 96 H H ##STR118## CH.sub.2 ##STR119## 211 decomposition 97 H H Me CH.sub.2 ##STR120## 181 decomposition 98 H Me Me -- ##STR121## 122-123 99 Me H Me -- ##STR122## 131-132 100 H H Me CH.sub.2 ##STR123## 184-186 decomposition 101 H Me Me CH.sub.2 ##STR124## 158-159 102 Me H H CH.sub.2 ##STR125## 206-207 103 CF.sub.3 CH.sub. 2 H Me CH.sub.2 ##STR126## 110-111 104 H H Me CH.sub.2 ##STR127## 182-184 decomposition 105 H H Me CH.sub.2 ##STR128## 167-169 decomposition 106 H Me Me CH.sub.2 ##STR129## 125 decomposition 107 Et Me Me CH.sub.2 ##STR130## oily form 108 CH.sub.2 FCH.sub.2 H Me CH.sub.2 ##STR131## 78-79 109 CH.sub.2 FCH.sub.2 Me Me CH.sub.2 ##STR132## 90-91 110 CH.sub. 2 FCH.sub.2 H Me CH.sub.2 ##STR133## 111 CH.sub.2 FCH.sub.2 Me Me CH.sub.2 ##STR134## 112 CH.sub.2 FCH.sub.2 H Me CH.sub.2 ##STR135## 113 Me Me Me CH.sub.2 ##STR136## 114 Et Me Me CH.sub.2 ##STR137## 115 Me H Me CH.sub.2 ##STR138## 116 Et H Me CH.sub.2 ##STR139## 117 CH.sub.2 FCH.sub.2 Me Me CH.sub.2 ##STR140## 118 Me Me Me CH.sub.2 ##STR141## 119 Et Me Me CH.sub.2 ##STR142## 120 ClCH.sub.2 H Me CH.sub.2 ##STR143## 121 ClCH.sub.2 H Me CH.sub.2 ##STR144## 122 ClCH.sub.2 H Me CH.sub.2 ##STR145## 123 CH.sub.2 FCH.sub.2 H Me CH.sub.2 ##STR146## 124 CH.sub.2 FCH.sub.2 Me Me CH.sub.2 ##STR147## 125 CF.sub.3 CH.sub.2 H Me CH.sub.2 ##STR148## 126 CF.sub.3 CH.sub.2 Me Me CH.sub.2 ##STR149## 127 Me Me Me CH.sub.2 ##STR150## 128 Et Me Me CH.sub.2 ##STR151## 129 H H Me CH.sub.2 ##STR152## 130 H Me Me CH.sub.2 ##STR153## 131 Me Me Me CH.sub.2 ##STR154## 132 Et Me Me CH.sub.2 ##STR155## 133 Et (CH.sub.2).sub.4 CH.sub.2 ##STR156## 110-111 134 Et Et Et CH.sub.2 ##STR157## 105-106 135 Et H i-Pr CH.sub.2 ##STR158## 126-127.5 136 Et H t-Bu CH.sub.2 ##STR159## 151-152 137 CH.sub.2 FCH.sub.2 H H CH.sub.2 ##STR160## 152-153 138 Et H Et CH.sub.2 ##STR161## 123-125 139 Et H ##STR162## CH.sub.2 ##STR163## 74-75 140 Et MeO Me CH.sub.2 ##STR164## oily form 141 Et MeO H CH.sub.2 ##STR165## oily form 142 Et Me Et CH.sub.2 ##STR166## oily form 143 Et H Me.sub.2 N CH.sub.2 ##STR167## oily form 144 ##STR168## H Me CH.sub.2 ##STR169## 115-116 145 ##STR170## H H CH.sub.2 ##STR171## oily form 146 ##STR172## H H CH.sub.2 ##STR173## 128-129 147 ##STR174## Me Me CH.sub.2 ##STR175## oily form 148 ##STR176## Me Me CH.sub.2 ##STR177## 73-75 149 Et H Me CH.sub. 2 ##STR178## 108-109 __________________________________________________________________________ ##STR179## ##STR180##
In the above table, Me, Et, n-Pr, i-Pr and n-Bu represent CH.sub.3 --, CH.sub.3 CH.sub.2 --, CH.sub.3 CH.sub.2 CH.sub.2 --, ##STR181##
When the compound (V) is obtained in the free form, it may be converted into its salt form by the conventional method and, on the contrary, the salt when obtained may be converted into the corresponding free form by the conventional method. That is, when the compound (V) has a basic group or moiety in the parts of R.sup.1, R.sup.3 and A, it may form the acid addition salt, e.g., the hydrochloride, hydrobromide, hydroiodide, nitrate, sulfate, phosphate, acetate, benzoate, maleate, fumalate, succinate, tartarate, citrate, oxalate, glyoxylate, aspartate, methanesulfonate, methanedisulfonate, 1,2-ethanedisulfonate or benzenesulfonate. Also, the compound (V) may form an inner salt which is also included in this invention.
The compounds (V) can exist as stereoisomers and tautomers, and such isomers and mixtures thereof are also included in this invention.
The compounds (V) or their salts are effective in preventing sanitary or horticultural insect pests and animal and plant parasites and can exert potent insecticidal activities when they are directly contacted with insects, e.g., by applying to their living animals or plants. An interesting characteristic property of the compounds (V) or their salts is found in that potent insecticidal activities can be achieved by once absorbing the compounds in plants through their root, leaves or stem which are then sucked or bitten by insects or contacted with insects. Such property is Advantageous for preventing suctorial type or mandible type insecticides. Moreover, the compounds (V) and their salts possess safe and advantageous properties as agents for preventing agricultural injurious insects, such as no substantial damage on plants and less toxicity against fishes.
Specifically, the preparations containing the compounds (V) or their salts are especially effective in preventing Hemiptera injurious insects such as Eurydema rugosum, Scotinophara lurida, Riptortus clavatus, Stephanitis nashi, Laodelphax striatellus, Nalaparvate lugens, Nephotettix cincticeps, Unaspis yanonensis, Aphis glycines, Lipaphis erysimi, Brevicoryne brassicae, Aphis gissypii, Sogattela furcifera, Nezara viridula, Trialeurodes vaporariorum, Myzus persicae, Pseudococcus comstocki, Aphis promi Nezara spp, Cimex lectularius and Psylla spp; Lepidoptera injurious insects such as Spodoptera litura, Plutella xylostella, Pieris rapae crucivora, Chilo suppressalis, Autographa nigrisigna, Helicoverpa assulta, Pseudaletia separata, Mamestra brassicae, Adoxophyes orana fasciata, Notarcha derogata, Cnaphalocrocis medinalis and Phthorimaea operculella; Coleoptera injurious insects such as Epilachna vigintioctopunctata, Aulacophora, femoralis, Phyllotreta striotata, Oulema oryzae and Echinocnemus squameus; Diptera injurious insects such as Musca domestica, Culex pipiens pallens, Tabanus trigonus, Delia antiqua and Delia platura; Orthoptera injurious insects such as Locusta migratoria and Gryllotalpa africana; Dictyoptera injurious insects such as Blattella germanica and Periplaneta fuliginosa; Tetranychidaes such as Tetranychus urticae, Panonychus citri, Tetranychus kanzawai, Tetranychus cinnabarinus, Panonychus ulmi and Aculops pelekassi; and Nematodes such as Aphelenchoides besseyi.
The compounds (V) or their salts can be used as insecticides or miticides in any application form suited for general agricultural chemicals. That is, one, two, or more than two kinds of the compounds (V) or their salts are used in the form of preparation such as emulsifiable concentrates, oil solutions, wettable powders, dusts, granules, tablets, sprays or ointments, according to the purpose of use, by dissolving or dispersing them in suitable liquid carriers, or mixing them with or absorbing them on suitable solid carriers. These preparations may contain, if necessary, emulsifying agent, suspending agent, spreading agent, penetrating agent, wetting agent, thickening agent or stabilizer, and can be prepared by any conventional method known per se.
The rate of the compound (V) or a salt thereof contained in an insecticidal preparation is suitably about 10 to 90% by weight in the case of emulsifiable concentrates or wettable powders, about 0.1 to 10% by weight in the case of oil solution or dust and about 1 to 20% by weight in the case of granules. However, such concentration may be changed properly, depending on the purpose of use. Emulsifiable concentrates, wettable powders or the like are suitably diluted or extended (for example, to 10 to 100000 times) with water or the like, on the occasion or use, and then scattered.
Suitable examples of the liquid carriers (solvents) include solvents such as water, alcohols (for example, methanol, ethanol, n-propanol, isopropanol or ethylene glycol), ketones (for example, acetone or methyl ethyl ketone), ethers (for example, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, di-ethylene glycol monomethyl ether or propylene glycol monomethyl ether), aliphatic hydrocarbons (for example, kerosine, kerosene oil, fuel oil or machine oil), aromatic hydrocarbons (for example, benzene, toluene, xylene, solvent naphtha or methylnaphthalene), halogenated hydrocarbons (for example, dichloromethane, chloroform or carbon tetrachloride), acid amides (for example, dimethylformamid or dimethyl acetamide), esters (for example, ethyl acetate, butyl acetate or fatty acid glycerol ester )or nitriles (for example, acetonitrile or propionitrile). These solvents are used individually or as a suitable mixture of two, or more, of them.
Suitable examples of the solid carriers (diluents or dust carrier) include vegetable powder (for example, soybean meal, tobacco meal, wheat flour or wood flour), mineral powders (for example, clays such as kaolin, bentonite, or acid clay, talcs such as talc powder or pyrophyllite powder), silicas (for example, diatomaceous earth or mica powder), aluminas, sulfur powder or active carbon. They are used individually or as a suitable mixture of two, or more, of them.
Also, suitable examples of bases for ointments include polyethylene glycol, pectin, polyalcohol esters of higher aliphatic acids (for example, glycerin mono-stearate), cellulose derivatives (for example, methyl cellulose), sodium alginate, bentonite, higher alcohols, polyalcohos (for example, glycerin), vaseline, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hard oil or resins. They are used individually, or as a suitable mixture of two, or more, of them or together with surface active agents mentioned below.
As surface active agents used as the emulsifying agent, spreading agent, penetrating agent or dispersing agent, nonionic or anionic surface active agents such as soaps; polyoxyethylene alkyl aryl ethers (e.g., Noigen.RTM. and E.A 142.RTM. from Dai-ichi Kogyo Seiyaku K.K., Japan, and Nonal.RTM. from Toho Chemical, Japan); alkyl sulfates (e.g., Emal 10.RTM. and Emal 40.RTM. from Kao K.K., Japan); alkyl sulfonates (e.g., Neogen.RTM. and Neogen T.RTM. from Dai-ichi Kogyo Seiyaku K.K. and Neopellex.RTM. from Kao K.K.); polyethylene glycol ethers (e.g., Nonipol 85.RTM., Nonipol 100.RTM., Nonipol 160.RTM. from Sanyo Kasei K.K., Japan); or polyhydric alcohol esters (e.g., Tween 20.RTM. and Tween 80.RTM. from Kao K.K.) are used, if necessary.
The compounds (V) or their salts can also be used, as occasion demands, in combination with or as an admixture with other insecticides (for example, pyrethroid insecticides, organophosphorus insecticides, carbamate insecticides or natural insecticides), acaricides, nematocides, herbicides, plant hormones, plant growth regulators, fungicides (for example, copper fungicides, organic chlorine fungicides, organic sulfur fungicides or phenol fungicides), synergistic agents, attractants, repellents, pigments and/or fertilizers.
The insecticidal or miticidal composition comprising the compound (V) or its salt of the present invention is an excellent agricultural product having fairly low toxicity and good safety. It can be used in a similar way to the conventional insecticidal or miticidal composition and can exert excellent effects in comparison with the conventional compositions. For example, the insecticidal or miticidal compositions of the present invention can be applied to the target insects, by treatment in nursery box, application for stem and leaf of crop, spraying for insects, application in water of a paddy field or soil treatment of a paddy field. The amount of application may broadly vary depending on the season, place and method of application, and so forth. However, the active ingredient (the compound (V) or its salt) is used in general, in an amount of 0.3 g to 3,000 g, preferably 50 g to 1,000 g per hectare. When the insecticidal composition of the present invention is in a wettable powder, it can be used by diluting it so as to be 0.1- 1000 ppm, preferably 10-500 ppm as the final concentration of the active ingredient.
Activity
As will be clear from the following tests, the compounds (I) and salts thereof possess excellent insecticidal activities.


Described are hybrid articles comprising at least one hard non-oxide or oxide ceramic component of at least 95% of theoretical density directly bonded to, and different from, a hard non-oxide or oxide ceramic composite component comprising a tribology enhancing component. The at least one hard non-oxide or oxide ceramic component comprises a member of the group consisting of silicon carbide, pressureless sintered silicon carbide, liquid phase sintered silicon carbide, reaction bonded silicon carbide, tungsten carbide, aluminum oxide, and silicon nitride. The at least one hard non-oxide or oxide ceramic composite component comprises a member of the group consisting of silicon carbide, pressureless sintered silicon carbide, liquid phase sintered silicon carbide, reaction bonded silicon carbide, tungsten carbide, aluminum oxide, and silicon nitride.

Hard non-oxide or oxide ceramic materials are commonly used in applications requiring materials with a high hardness, superior strength, good corrosion resistance, and high thermal conductivity, such as the materials used in acidic, caustic, corrosive, abrasive, high speed, or high temperature environments. These types of applications include rotating equipment, pump seals and bearings, gas turbine components, mixing nozzles, and flame holders. Examples of these hard non-oxide or oxide ceramic materials include but are not limited to silicon carbide, pressureless sintered silicon carbide, liquid phase sintered silicon carbide, reaction bonded silicon carbide, tungsten carbide, aluminum oxide, and silicon nitride.
A drawback to these hard non-oxide or oxide ceramic materials is the lack of self-lubricity when used alone. A self-lubricating solid is one having low friction in the absence of an adequate lubricant. For example, in applications having a high PV (pressure-sliding velocity) or marginal lubrication conditions, parts, such as seals or bearings, having a hard non-oxide or oxide ceramic material surface adjoining with relative motion against another surface made of the same or other hard non-oxide or oxide ceramic material, other silicon carbide materials, other ceramics, or steel will wear excessively due to the forces generated by the high friction. In marginal lubrication conditions with mating surfaces, special wear surfaces must be provided on at least one of the bodies.
Graphite is a known lubricant and has been incorporated into carbon and silicon carbide materials to impart a self-lubricating property to the material. For example, U.S. Pat. Nos. 5,580,834, 5,656,563, and 5,968,653, the contents of which are incorporated herein by reference, teach the use of a carbon graphite/silicon carbide composite material. Other inclusions, such as tribology enhancing additives, porosity, boron carbide, etc., can also improve the tribology of the material. The composite materials have wear resistance superior to hard non-oxide or oxide ceramic materials, in that the material of the present invention can run against itself or other hard non-oxide or oxide ceramic, non-self-lubricating materials in sliding face applications, such as for mechanical seals and pump bearings, in marginal lubrication conditions. Composite materials also have thermal shock resistance superior to hard non-oxide or oxide ceramic materials. In catastrophic failure or dry run conditions, such as when fluid is lost in pump applications, seals and bearings made of the composite material have enhanced survivability and can maintain their integrity, while seals and bearings made of hard non-oxide or oxide ceramic materials can fail almost immediately. However, a drawback to the use of composite materials alone is that the composite material does not exhibit the same level of superior hardness, corrosion resistance, thermal conductivity, and strength that are enhanced physical properties of hard non-oxide or oxide ceramic materials.
Accordingly, there is a need to combine the superior physical properties of hard non-oxide or oxide ceramic materials with the enhanced tribological capability of composite versions of these hard non-oxide or oxide ceramic materials.

Hard non-oxide or oxide ceramic / hard non-oxide or oxide ceramic composite hybrid article

Morgan Advanced Materials and Technology Inc.


A computer implemented method for migrating streaming applications from on-premise non-cloud infrastructure to target clouds. The method may include receiving at the message connector a source message from an on-premise application. The method may further include analyzing the source message to assess feasibility of migrating the on-premise application to the target cloud wherein analysis includes extracting communication data from the source message and meta data from the source message. The method may also include converting the source message to a format native to the target cloud application, wherein the conversion by the message connector includes a cognitive engine to match a selected target cloud to the on premise application.

The present invention generally relates to communication services and transmitting data from communication services to a cloud platform.
Mobile based communication applications produce messages for transmission between consumers looking to communicate with one another. Software vendors for mobile based communications application can be faced with challenges when attempting to migrate their message streaming applications to the cloud in order to employ cloud services. In some instances, software venders experience data loss when migrating data, as well as having to deal with format changes, such as code changes etc. For example, a number of applications are based on-premise and they have one or more streaming components. These streaming components could potentially be either messages or events. These messages or events can be generated by producers and consumed by consumers through message queues. Enabling on-premise applications to be migrated to the cloud can include managing cloud native services for the data being migrated, e.g., the events/message data. However, there are multiple formats of data to be migrated between the on premise and cloud platforms, and there are numerous implementations of message queues, which can complicate migration of the data.

Message connector as a service to migrate streaming applications into cloud nativity


This disclosure discloses a non-transitory computer-readable recording medium, storing a fixed form print information processing program for executing steps on a control device. The steps comprises a fixed form print producing step for producing fixed form print information, a margin area deleting step for deleting a width direction margin area of the width direction margin area and a longitudinal direction margin area respectively set on each side of both ends in a tape width direction as well as each side of both ends in a tape longitudinal direction of font data corresponding to a character string included in the fixed form print information, a fixed form print displaying step for displaying on the display device the fixed form print information from which the margin area has been deleted, and a fixed form print transferring step for transferring the fixed form print information to the print label producing apparatus.

1. Field
The present disclosure relates to a recording medium on which a fixed form print information processing program used by an operation terminal connected to a print label producing apparatus is recorded.
2. Description of the Related Art
There are already known systems wherein an operation terminal (computer device) and print label producing apparatus (tape printer) are connected, making it possible for an operator to produce a print label (printed tape) by operating the print label producing apparatus via the operation terminal According to this prior art, the print label producing apparatus is capable of using fixed form print information (a so-called template), making it possible for an operator to simply produce a print label of a desired mode. Further, a predetermined application program (editor) for producing fixed form print information is preinstalled in computing device of the operation terminal, making it possible for the operator to edit the contents of the fixed form print information as desired. The operator can verify the contents of the edited fixed form print information via a display by display device, and then transfer the fixed form print information to the print label producing apparatus.
The prior art has the following problems. That is, the fixed form print information includes, for example, a diagram section of frames, ruled lines, and the like, and a character string section suitably disposed in a position associated with that diagram section. The operation terminal comprises a PC, etc., and thus, from the operator viewpoints of visibility and aesthetics, fonts are normally prepared for a character string that comprise both a width direction margin on both tape width direction end sides and a longitudinal direction margin on both tape longitudinal direction end sides of the character string. On the other hand, the print label producing apparatus forms print on a printed tape restricted in size in the tape width direction and thus, unlike the above, often has fonts prepared for a character string that do not have a width direction margin on both tape width direction end sides of the character string.
Accordingly, when fixed form print information edited by the operator as previously described is transferred to a print label producing apparatus and a print label is produced using that fixed form print information, the difference between whether or not the font margin described above is present may cause the mode of the character string formed into print on the print label to differ from the mode intended by the operator when the operator edited the fixed form print information.


The present disclosure relates to a technical field of fluid delivering. An electromagnetic pump is provided. The electromagnetic pump includes a drive mechanism and a magnetic assembly, where the magnetic assembly is configured to be driven by the drive mechanism to generate a varying magnetic field.

An electromagnetic pump is a pump in which an energized fluid in a magnetic field flows in a certain direction under the influence of electromagnetism. The electromagnetic pump is an apparatus that utilizes interaction of the magnetic field and a current in a conductive fluid to cause the fluid to be subjected to electromagnetism to generate a pressure gradient, thereby promoting motion of the fluid. In practice, electromagnetic pumps are mostly used to pump liquid metal, so they are also called electromagnetic pumps for liquid metal.
The electromagnetic pump generates an alternating magnetic field by introducing an alternating current into a coil, and the liquid metal is driven by the alternating magnetic field generated by the coil to flow in an expected direction. This type of electromagnetic pump has higher requirements on current and voltage and presents safety hazards.


An adhesive tape product incorporating foam that is stitch-bonded with a stitching yarn to provide substantial dimensional stability in the machine direction without sacrificing the sound dampening and insulation properties of the foam. A pressure sensitive adhesive is disposed in overlying relation to at least one face of the foam. One or more fibrous layers may be positioned between the foam and the adhesive.

Tape products incorporating foam layers in combination with pressure sensitive adhesive (PSA) are known. Such tape products provide noise dampening and sound insulation properties as may be desirable in automotive applications such as wrapping electrical cables and the like. However, low density foam may tend to elongate and/or break when placed under machine directional tension during coating and winding onto rolls. While these deficiencies may be addressed to some degree by using thicker and/or heavier foam layers, such approaches necessarily add cost and weight to the products. Thus, the use of foam layers in tape products currently faces inherent limitations. Accordingly, a tape product that incorporates a thin, low density foam layer that can be processed without undue elongation and deformation while still retaining the benefits of the foam would represent a useful advancement over the current art.

Stitch bonded foam tape product and method


A handheld device comprising a motor for generating an airflow through the device, the motor including: a frame for supporting a rotor assembly and a stator assembly, the frame including an inner wall and an outer wall and a plurality of diffuser vanes extending between the inner wall and outer wall; a rotor assembly including a shaft, a magnet, a bearing assembly and an impeller; and a stator assembly including a bobbin, a stator core and a winding wound around the bobbin; the frame being formed of zinc and the impeller being formed of aluminium.

When developing a handheld product, it is important to consider a number of factors that will affect the end-user. For example, the size and weight of the product must be kept down in order that a user is able to handle the product easily, and that the product does not cause discomfort to the user during use. Another important consideration is that of noise. It is preferable that a handheld product does not produce a level of noise that is unpleasant and/or uncomfortable during use. What is more, excessive noise could potentially be damaging to a user's hearing if the product is used regularly over a long period of time. It is often the case that additional soundproofing, for example foam, is included in a product in order to maintain an acceptable level of noise generated by the product. Alternatively, the motor can be run at a lower power to reduce the level of noise that it generates. Of course, neither of these solutions are particularly desirable. Additional components or materials such as foam will increase the cost of the product, and running the motor at a lower power will negatively affect the performance of the product.
In handheld products which contain motors, it is often the motor that contributes the most towards the weight of the overall product and also towards the noise of the product during use. In smaller, handheld products, it is usual for many components of the motor to be formed of plastics which are more lightweight than other alternative materials.

Motor and a handheld device having a motor


A method comprises providing a non-transitory, machine-readable storage medium storing a partial netlist of at least a portion of a previously taped-out integrated circuit (IC) layout, representing a set of photomasks for fabricating an IC having the IC layout such that the IC meets a first specification value. A computer identifies a proper subset of a plurality of first devices in the IC layout, such that replacement of the proper subset of the first devices by second devices in a revised IC layout satisfies a second specification value different from the first specification value. At least one layout mask is generated and stored in at least one non-transitory machine readable storage medium, accessible by a tool for forming at least one additional photomask, such that the set of photomasks and the at least one additional photomask are usable to fabricate an IC according to the revised IC layout.

Semiconductor foundries and standard cell library vendors are continuously improving the designs of standard cells and reusable components.
Modern design processes for integrated circuits make extensive use of modular components. Circuit designers produce design descriptions, typically at a register-transfer level (RTL). The RTL source description (e.g., Verilog code) is compiled into instances of "cells.". The cells are basic building blocks of circuits, such as gates or memory bit cells. Cells implement logic or other electronic functions. Various foundries and independent cell library vendors provide standard cell libraries. The cells in these libraries have been modeled and qualified, for use with a particular integrated circuit technology. Electronic Design Automation (EDA) tools place the selected standard cells at appropriate locations in the IC floor plan, and route the interconnections between the various cells to generate an IC layout. After a layout is generated, a series of verification and acceptance procedures are performed, including design rule checks (DRC) and layout versus schematic (LVS) checks. When a design has passed its verification procedures, signoff and tapeout occur. The layout is released to a foundry using a standard format, such as GDSII or Oasis.
An IC designer designs circuits using the standard cell libraries that are available at the time a given IC is designed. After the initial release of a given IC, foundries and cell library vendors continue to enhance their cell libraries with new cell designs. It would be costly for IC designers to redesign their ICs to take advantage of later developed cell designs.

This patent is subject to a terminal disclaimer.

Taiwan Semiconductor Manufacturing Co., Ltd.


A method of determining a road surface condition for a vehicle driving on a road. Probabilities associated with a plurality of road surface conditions based on an image of a capture scene are determined by a first probability module. Probabilities associated with the plurality of road surface conditions based on vehicle operating data are determined by a second probability module. The probabilities determined by the first and second probability modules are input to a data fusion unit for fusing the probabilities and determining a road surface condition. A refined probability is output from the data fusion unit that is a function of the fused first and second probabilities. The refined probability from the data fusion unit is provided to an adaptive learning unit. The adaptive learning unit generates output commands that refine tunable parameters of at least the first probability and second probability modules for determining the respective probabilities.

An embodiment relates to detection of a road surface condition using adaptive learning techniques.
Precipitation on driving surface causes several different issues for a vehicle. For example, water or snow on a road reduces the coefficient of friction between the tires of the vehicle and the surface of the road resulting in vehicle stability issues.
Various techniques are known for attempting to determine what the environmental condition of the road surface is. An example of one such technique is a vehicle model that senses vehicle operating conditions to obtain data for classifying a road surface condition. The model has set parameters and without any updates, the model would yield the same results for a given input. Therefore, if the model misdiagnoses the road surface condition, then the output will continuously generate the same incorrect result.
Other approaches, such as an image-based approach, utilize a classifier to determine the road surface condition. However, if the classifier is not updated, then the classifier will output the same result even if it is incorrect.
In such cases, the road surface detection system is entirely dependent on the classifier or model stored in the vehicle when the vehicle was manufactured or brought in for a service update.

Road surface condition detection with recursive adaptive learning and validation


A method of producing lactic acid by separating lactic acid produced in a culture solution by microbial fermentation, comprising: a step (A) of filtering the culture solution through a nano-filtration membrane; and a step (B) of distilling a lactic-acid-containing solution produced in step (A) under a pressure of 1 Pa to atmospheric pressure (inclusive) at a temperature of 25 to 200° C. (inclusive) to recover lactic acid.

Lactic acid is widely applied even in an industrial use as a monomer raw material of biodegradable plastics other than a use for food, medicine and the like, and the demand is increasing. It is known that 2-hydroxypropionic acid, i.e., lactic acid is produced by a microbial fermentation, and the microorganism converts a substrate containing carbohydrate typified by glucose into lactic acid. Lactic acid is classified into optical isomers of (L)-isomer and (D)-isomer based on the configuration of a hydroxyl group bonded to a carbonyl carbon of α-position. Microbial fermentation can produce lactic acid of (L)-isomer or (D)-isomer selectively, or of a mixture (racemic body) of (L)-isomer and (D)-isomer by suitably choosing a microorganism.
The production of lactic acid by microbial fermentation is generally conducted while being maintained at an optimum pH for microbial fermentation by adding an alkaline substance to a culture solution. Lactic acid, an acidic substance produced by microbial fermentation, is mostly present as lactate in a culture solution by being added with an alkaline substance. In this case, free lactic acid is obtained by adding an acidic substance to a culture solution after completion of fermentation. Specifically, as one example of the alkaline substance to be added to a culture solution, calcium hydroxide is used, in this case, lactic acid produced by microbial fermentation is present as calcium lactate in a culture solution. Thereafter, by adding an acidic substance (for example, sulfuric acid) to a culture solution after completion of culture, a solution of free lactic acid can be obtained, but a calcium salt (for example, calcium sulfate) is produced as a by-product.
As a method for separating lactic acid by removing the calcium salt produced, in the case that a calcium salt is a poorly-soluble and precipitates like calcium sulfate, a method of filtering out through qualitative filter paper or the like is used. However, in the case of this method, a calcium salt that precipitates as a solid is removed, but a small amount of calcium salt dissolved in a solution is not removed, thus, it will remain in a lactic acid-containing solution. In the case that lactic acid is produced by microbial fermentation, various inorganic salts other than target lactic acid are produced as by-products, of which ones dissolved in a culture solution cannot be filtered out through qualitative filter paper or the like. Therefore, for example, when this filtrate containing lactic acid is subjected to a concentration procedure in the subsequent purification process, there arises a problem that calcium salt and other inorganic salts separate out (precipitation) again in a solution containing free lactic acid. When a lactic acid-containing solution is heated in operations such as distillation in a state that inorganic ions are not sufficiently removed, it is known that racemization and oligomerization of lactic acid proceed by the influence of inorganic ions. Therefore, a method for effectively removing a small amount of inorganic ion components remained in a lactic acid-containing solution is desirable.
As a method for removing a small amount of inorganic ion components from a lactic acid-containing solution, a method using an ion-exchange resin is disclosed (for example, see Japanese translation of PCT Publication No. 2001-506274). However, for maintaining ion-exchange performance of an ion-exchange resin, it is necessary to regenerate the ion-exchange resin periodically. In such regeneration of the ion-exchange resin, it is carried out using a large amount of sodium chloride aqueous solution, there is a problem that a lot of waste liquid is discharged being accompanied with regeneration, so that waste liquid treatment costs a lot. Further, there has been a problem that when an ion-exchange resin is regenerated repeatedly, the regeneration rate of an ion-exchange resin is lowered, in addition thereto, the ion-exchange performance is lowered, and the removal rate of inorganic salts is lowered.
There is also the known method that a small amount of inorganic ion components such as calcium component is removed from a lactic acid-containing solution by a bipolar membrane using an electrodialyzer (for example, see Japanese Unexamined Patent Publication No. 2005-270025). However, there has been a problem that the bipolar membrane used in this method is expensive, in addition thereto, the removal efficiency of inorganic salts such as calcium salt is by no means high.
In addition, a method of separation and recovery of organic acid using a separation membrane is known, and a method of separating para-pyruvic acid from a pyruvic acid solution through a reverse osmosis membrane is disclosed (see Japanese Unexamined Patent Publication No. 6-306011), but in that case, the removal rate of inorganic salts is not disclosed. Japanese Unexamined Patent Publication No. 6-306011 relates to a method of separation and recovery of pyruvic acid, but since pyruvic acid is not an optically-active material, problems in separation and recovery of lactic acid from a lactic acid-containing solution, namely, racemization and oligomerization have not been solved yet.
Further, a method of removing inorganic salts from a lactic acid-containing solution using a nano-filtration membrane is disclosed (for example, see U.S. Pat. Nos. 5,503,750, 5,681,728 and US 2004/0033573), but there is no disclosure on a process for recovery of lactic acid by distilling a lactic acid-containing solution obtained by filtrating a fermentation culture solution of a microorganism through a nano-filtration membrane, and on the influence that distillation affects the yield of lactic acid, so that the object of recovering lactic acid in a high yield by distillation has not been solved.
It could therefore be helpful to provide a method of effectively separating and recovering lactic acid in a culture solution while suppressing racemization and oligomerization.


A printing condition setting apparatus having a setting parameter data storage unit for storing a plurality of setting parameter data each including at least one setting parameter registered by the user's operation among a plurality of setting parameters specifying printing conditions; a setting parameter data reception unit for receiving the user's selection of one setting parameter data among a plurality of setting parameter data stored in said setting parameter data storage unit; and a setting parameter data call unit for calling up said one setting parameter data selected by the user to display the setting parameters included in said setting parameter data on a specific operating screen.

1. Technical Field
The invention relates to a printing condition setting apparatus, a printing condition setting method, and a computer readable recording medium stored with a printing condition setting program. The invention particularly relates to a printing condition setting apparatus, a printing condition setting method, and a computer readable recording medium stored with a printing condition setting program for setting up the printing condition for printing functions of a printing apparatus.
2. Description of Related Art
For a printing job executed on a printer, various setting parameters of printing conditions such as page allocation, color selection, printing type, and the likes can be applied. The user can set up various setting parameters applied to a printing job to preferred setting values using a control program called a printer driver on a PC (personal computer). There are many setting parameters provided by the printer driver, and the number of setting parameters has even been on a rise in recent years. A plurality of setting parameters are classified in accordance with related functions and displayed on an operating screen, which is selectable on a GUI screen window by selecting a tab. Therefore, in order for a user to set up a desired printing condition, the user must first switch the operating screen by selecting a tab to display a desired setting parameter, and then modify the setting value (in other words, the setting item) of the setting parameter, thus making the printing condition setting work more complex.
As a means of solving this problem, an art has been proposed in which all those setting parameters for which the setting values are frequently modified by the user are displayed aggregately on a specific operating screen.
Refer to the printer driver of PostScript 3 Printer Controller provided by EFI, Image Controller IC-406, available on the World Wide Web at "konicaminolta.jp/business/download/copiers/efi/detail.html".
According to this non-patent document technology, all those setting parameters for which the setting values are frequently modified by the user can be displayed aggregately on a specific operating screen by the user adding or removing setting parameters to or from an operating screen that can be edited by the user.
However, even for the same user, the setting parameters that need to be modified frequently may change depending on the printing scene. Therefore, even if the user has edited the operating screen to display the desired setting parameters, there may be a case for the same user to switch the operating screen by selecting a tab to modify the setting value of a certain setting parameter when the printing scene changes.

Printing condition setting apparatus, printing condition setting method, and computer readable recording medium stored with printing condition setting program

Konica Minolta Business Technologies, Inc.


A sanitizer includes a shell defining first and second chamber portions, and having an opening into the first portion. A cover has a closed position over the opening for preventing access to the chamber, and an open position for permitting access to the chamber. A tray is moveable between an access position in the first portion, for placement and retrieval of an article within the tray, and a sanitizing position in the second portion, for exposing the article to sanitizing electromagnetic radiation from an emitter mounted in the second portion. A controller controls an actuator coupled to the tray to move the tray to the sanitizing position when the cover is closed, and to return the tray to the access position when a return condition is satisfied. A radiation barrier is configured to substantially prevent radiation from reaching the opening when the tray is in the access position.

The surfaces of portable articles such as smartphones can carry various infectious agents, such as bacteria and viruses. There are many known devices for sanitizing such articles. Most conventional sanitizing devices make use of these ultraviolet bulbs emitting light in the 254 nm wavelength range. For example, the PhoneSoap® is a consumer product used to disinfect smartphones (for example while charging the smartphone overnight). A user places their smartphone inside the single compartment of the PhoneSoap, and an ultraviolet bulb then disinfects the surfaces of the device over a period of time (e.g. 5 minutes).
Conventional sanitizing devices such as those mentioned above may not be suitable for some applications, such as scenarios in which larger numbers of articles are treated in a given time period, because their sanitation cycles impose excessive wear on the ultraviolet bulbs.

Sanitizing device and method for sanitizing articles


A cable linkage comprising a cable partially housed within a sheath and a fitting for securement to a linkage member, a length of cable between the fitting and the sheath being exposed when the cable is extended in use, wherein the fitting has a guide follower arranged to follow a guide so as to substantially inhibit kinking of the exposed length of cable.

This application claims priority to British Application No. GB 0110457.9 filed Apr. 28, 2001.
The present invention relates to a cable linkage. More particularly, the present invention relates to a cable linkage having a guide to inhibit the kinking of the cable when a compression load is applied thereto.
The use of cables to enable the remote actuation of devices such as latches and locks on vehicle doors, for example, is well known.
In order to simplify the design and installation of cables within doors, it is desirable that sheathed multi-strand flexible cable with a reduced internal friction is used so that the cable may be routed easily around obstacles within the door. Additionally, the use of flexible cables is desirable as slack can be provided along the cable run. This means that in the event of an impact which deforms the door, the deformation is unlikely to cause unwanted actuation due to a tightening of the cable, which would lead to the door becoming unlatched.
While flexible cables are effective when required to exert a tensile load, the reduced internal friction of flexible cables results in an intrinsic tendency to kink when called upon to exert a compression load and are unconstrained by an outer sheath, thus preventing actuation of devices connected thereto in this direction.
One solution that has been previously proposed in order to overcome this problem provides a rigid end piece to the cable that extends into the cable sheath so that none of the flexible cable is exposed. Thus, this arrangement substantially mitigates the tendency to kink. However, the installation and/or use of such an arrangement is not possible when the end of the cable proximate the device to be actuated has to be routed through a tight angle in order to avoid obstructions, for example, due to the inflexibility of this end of the cable. Furthermore, such an arrangement generally requires an enlarged end to the sheath to accommodate the rigid end piece, which may be undesirable when space is restricted.
The present invention seeks to overcome, or at least mitigate, the problems of the prior art.
An aspect of the present invention provides a cable linkage comprising a cable partially housed within a sheath and a fitting for securement to a linkage member, a length of cable between the fitting and the sheath being exposed when the cable is extended in use, wherein the fitting has a guide follower arranged to follow a guide means so as to substantially inhibit kinking of the exposed length of cable.

Meritor Light Vehicle System (UK) Limited


We report an electro-deionization (EDI) device having split flow arrangement for the purification of second pass RO permeate water with high flow rate in which the feed water is fed through the center port and is diverted into each section of dilute chamber with equal flow rate, producing two product streams. The EDI device has concentrate chambers adjacent to dilute chambers in two sections of the stack, allowing independent flow through the separate sections. The split flow design reduces resin bed depth requirement for processing of second pass RO permeate water. This results in higher flow rate through the stack, elimination of the pressure drop limitation, and reduction of power consumption per unit volume of water.

1. Field of the Invention
Embodiments of the invention relate to electro-deionization methods and apparatus.
2. Background of the Related Art
An Electro-Deionization apparatus (EDI) is a device that removes the dissolved impurities of reverse osmosis ("RO") permeate water with the help of resin media, ion exchange membrane and DC current. The EDI process is a continuous process as it does not need chemicals such as acid and caustic for regeneration of resin media and membranes. The resin media is regenerated during the purification of water due to continuous water splitting occurring inside the EDI apparatus. Splitting of H+ and OH− ions happens due to the electric potential generated within the dilute compartment from the H2O molecules which regenerates the corresponding resin ions continuously.
An EDI apparatus is generally used for the purification of reverse osmosis permeate water up to a level of 0.055 μS/cm conductivity and makes it suitable for various industrial applications including but not limited to boiler feed/steam generation, microelectronics/semiconductor makeup or rinse water, and purified USP grade water.
An EDI apparatus is typically made up of ion exchange resin, ion exchange membranes, electrodes for DC supply and hardware components for water flow distribution. The arrangement of ion exchange membranes, anion exchange membranes and cation exchange membrane, are very important in an EDI apparatus. They are generally arranged in alternate manner with respect to anode and cathode electrodes. The ion exchange resin media are filled in the chambers/compartments which are formed due the arrangement of anion and cation exchange membranes. This leads to the formation of dilute chambers and concentrate chambers.
The dilute chambers are those in which the feed water (RO permeate) gets purified and become ultra pure water whereas the concentrate chambers are adjacent alternate positioned to dilute in which the removed ions from the dilute chambers are collected and flushed out from the apparatus with the help of separate water stream. A small portion of the water is also used for flushing and cooling the cathode and anode electrodes, called Electrode Rinse stream and the chamber is called the Electrode Rinse Chamber.
The efficiency and commercial utilization of any EDI apparatus depends upon the quantity of product water produced per unit area of membrane, per unit volume of ion exchange media or per cell pair of membranes. There are many commercial EDI apparatus are available in market which can be easily divided into three categories—
1) Low Flow Rate EDI Apparatus:
This type of EDI apparatus are generally thin cell plate and frame EDI having product flow rate range of 1.5 m3/hr and 2.0 m3/hr with 30 or more cell pair. The output product flow of each dilute chamber is generally in the range of 50 to 60 LPH or less.
2) Medium Flow Rate EDI Apparatus:
The second category EDI apparatus are generally thick cell plate and frame EDI having product flow rate of 2.5 m3/hr-5.0 m3/hr with 30 cell pair or more. The output product flow of each dilute chamber is generally in the range of 80 to 170 LPH or less.
In both the first and the second category the pressure drop across dilute chamber (feed to product) is typically around 20 to 30 psi for nominal flow rate. For maximum flow rate it typically increases up to 40-60 psi. The effective length of dilute chambers of such EDI apparatus vary from 350 mm to 450 mm and width vary from 100 mm to 200 mm. The resin volume inside the dilute chambers of these EDI apparatus does not allow increase in the flow rate due to high pressure drops, mechanical leaks or mechanical strength of the apparatus.
The typical flow configuration of both category EDI apparatus is shown in FIG. 1. A third category of EDI apparatus is also used.
3) High Flow EDI Apparatus:
To achieve high product flow rate, more than 5.0 m3/hr, a third category of EDI apparatus is also used, which is generally the combination of multiple EDI apparatus, connected together in parallel with 40 to 60 number of cell pairs per unit, for producing high product flow rate from the stacks. The product flow rate per dilute chamber of this type EDI apparatus is similar to medium flow rate EDI apparatus. The high product flow through these EDI apparatus is only due to the increased area of dilute chambers.
For the production of ultra pure water, an EDI apparatus generally is used to purify either permeate water of single pass RO, where the feed ion load is high with challenging scaling ions, or permeate water of second pass RO permeate, where the feed ions load are very less with negligible amount of scaling ions.
The scaling ions (like Ca2+, Mg2+, CO3, SiO2, etc) have big role to play in any EDI operation and have been the cause for limiting conditions requiring additional pretreatment that may be uneconomical in many cases. Some solutions to this problem have been proposed. For example, the fractional deionization process reported in U.S. Pat. No. 6,896,814, incorporated by reference herein, uses a dual voltage process for the removal of higher load of scaling ions without scaling in EDI apparatus.
EDI design for certain flow depends upon the feed condition and the product quality requirement. For harsher feed condition such as single pass RO permeate water with challenging scaling ions, the product flow is typically reduced. This makes the system costly and therefore unattractive for use.
The typical product flow rate of an EDI apparatus at different feed hardness (as CaCO3) and feed conductivity equivalent (FCE) loads are summarized as,                a. Product flow rate=2.4 m3/hr when feed hardness (as CaCO3) is 3 ppm and total FCE load is 25-30 μS/cm for the product quality requirement of more than 10 to 16 MOhms        b. Product flow rate=3.5 m3/hr when feed hardness (as CaCO3) is 1 ppm and total FCE load is 15-20 μS/cm for the product quality requirement of more than 10 to 16 MOhms        c. Product flow rate=4.5 m3/hr when feed hardness (as CaCO3) is 0.1 ppm and total FCE load is <10 μS/cm for the product quality requirement of more than 10 to 16 MOhms
When the feed hardness (as CaCO3) is less than 0.1 ppm like in second pass RO permeate water, the EDI behavior is quite different. Scaling is not a major concern, and the rate of effective in-situ media regeneration is the main criterion to govern the process and higher product quality can be easily achievable even with high flow rate but the main limitation is the higher pressure drop across the dilute chamber in regular flow mode.
The previously mentioned fractional deionization process of U.S. Pat. No. 6,896,814 B2 is a two stage process that deals with hardness and silica removal in separate zones because of their different current requirement. The design of an apparatus for this reason has two stages and is able to produce product flow rate up to 5.0 m3/hr with its regular flow mode. This process/apparatus when used for double pass RO grade water with novel split flow design is able to treat as high as 8 to 10 m3/hr of product water against normally product flow rate which is 3 to 5 m3/hr. Single stack with 8 to 10 m3/hr reduces the line connections, minimize pressure drop across dilute chamber, reduce power consumption per unit volume of water and makes a economical and viable proposition for the user.

Split flow EDI apparatus for treating second pass RO permeate water with high flow rate


An item is determined to exist in a dataset by arranging the dataset into a plurality of subsets, each bounded by the minimum amount of memory that may be transferred between levels of memory in a memory configuration. The item and the subsets have attributes that allow for a determination of which subset the item would exist in if the item were in the dataset. A singular subset is transferred between levels of memory to determine whether the item exists in the transferred subset. If the item does not exist in the transferred subset, it is determined that the item does not exist in the dataset.

A financial instrument trading system, such as a futures exchange, referred to herein also as an "Exchange", such as the Chicago Mercantile Exchange Inc. (CME), provides a contract market where financial instruments, for example futures and options on futures, are traded. Futures is a term used to designate all contracts for the purchase or sale of financial instruments or physical commodities for future delivery or cash settlement on a commodity futures exchange. A futures contract is a legally binding agreement to buy or sell a commodity at a specified price at a predetermined future time. An option is the right, but not the obligation, to sell or buy the underlying instrument (in this case, a futures contract) at a specified price within a specified time. The commodity to be delivered in fulfillment of the contract, or alternatively the commodity for which the cash market price shall determine the final settlement price of the futures contract, is known as the contract's underlying reference or "underlier." The terms and conditions of each futures contract are standardized as to the specification of the contract's underlying reference commodity, the quality of such commodity, quantity, delivery date, and means of contract settlement. Cash Settlement is a method of settling a futures contract whereby the parties effect final settlement when the contract expires by paying/receiving the loss/gain related to the contract in cash, rather than by effecting physical sale and purchase of the underlying reference commodity at a price determined by the futures contract, price.
Typically, the Exchange provides for a centralized "clearing house" through which all trades made must be confirmed, matched, and settled each day until offset or delivered. The clearing house is an adjunct to the Exchange, and may be an operating division of the Exchange, which is responsible for settling trading accounts, clearing trades, collecting and maintaining performance bond funds, regulating delivery, and reporting trading data. The essential role of the clearing house is to mitigate credit risk. Clearing is the procedure through which the Clearing House becomes buyer to each seller of a futures contract, and seller to each buyer, also referred to as a novation, and assumes responsibility for protecting buyers and sellers from financial loss due to breach of contract, by assuring performance on each contract. A clearing member is a firm qualified to clear trades through the Clearing House.
Current financial instrument trading systems allow traders to submit orders to buy or sell contracts to an order book database maintained and managed by an exchange which contains data indicative of previously received, but unsatisfied, referred to as "resting", orders. A match engine is used by the exchange to, for a particular incoming order, search the order book database to identify a suitable counter order, e.g. for the same financial instrument and same or better price as the incoming order, with which to match the incoming order. Stated a different way, a dataset may involve previously received unsatisfied orders, or resting orders. An incoming order is received and the dataset of resting orders is searched for data that would match the incoming order to a resting order, or what may be known as intersecting data. For example a resting buy order and an incoming sell order may be of the same quantity or price of an underlier, and thus have matching or intersecting data. The process by which it is determined if one or more items of one dataset exist in a second dataset may be referred to as determining the intersection of two sets. Mathematically, the intersection of two sets A and B is the set of elements common to A and B.
Set intersection is a basic problem in computer science, and has a variety of applications. For example, Index-ANDing in database query evaluation calculates set intersection of property index tables. There are several established methods for computing set intersection, for example sort based methods, hash based methods, or search tree methods may be used.
In dataset intersection determination, items in a dataset may be compared. These comparisons involve transferring memory into different memory locations and levels. Because of these transfers, and the large amounts of data that may be involved in storing large datasets, numerous transfers may be required to determine all dataset intersections. For example, multiple data transfers may be required to search for an individual value of one item in a dataset, in another dataset. Therefore, if the datasets have thousands, or millions, of items, the determination of dataset intersection may be very computationally intensive.
Typically computers contain on-board RAM memory such as banks of SRAM and DRAM. Typically, the on-board memory forms a memory hierarchy, for instance where SRAM is smaller in capacity but faster to access, and DRAM is larger in capacity but has longer access times. This type of memory hierarchy may exist through multiple levels of storage, RAM and main computer memories. Also, each level of memory may have a minimum amount of memory required to be transferred between levels of memory in a memory transfer. In cache memory, this minimum amount of memory is known as a cache line or block. A cache line, or block, is generally fixed in size typically ranging from 16 to 256 bytes, but may be any size suitable for a particular hardware configuration or application.


An ac electric drive system includes a bidirectional power semiconductor interface between a battery, or an auxiliary energy storage device, and a power inverter for boosting an input dc voltage and for decoupling the dc link voltage from the input dc voltage such that the dc link voltage is substantially independent of the input dc voltage and the parameters of the battery or energy storage device. The input dc voltage is controlled to maximize efficiency along predetermined torque envelopes.

Today's electric vehicle drives require increasing levels of torque and power to meet aggressive vehicle acceleration and grade-climbing requirements. To be practical, commercial electric vehicle drives require minimized cost, size, and weight. During the last decade, as higher voltage semiconductor devices have become available, industry has increased drive system power density by increasing the system voltage (i.e., dc link voltage) from approximately 100 V to 300 V, thereby allowing higher voltage-rated, but lower current-rated, power semiconductors to be used in the inverter. This trade-off advantageously minimizes the size and cost of electric drive systems. Except for the battery, the inverter is the most expensive subsystem in the total electric drive system, and the power semiconductor switches are generally the most expensive components in the inverter. For typical voltage levels of these drives, power semiconductor cost increases more rapidly as a function of current rather than voltage.
Increasing the dc system voltage has resulted in significant performance improvements while reducing costs. However, increasing the dc system voltage also requires the battery to be designed for relatively high voltage (typically 300 V nominal), which is accomplished by both designing lower current capacity cells and connecting larger numbers of small cells (e.g., 2 V) in series, disadvantageously reducing battery reliability and life due to cell-to-cell capacity mismatch. The larger number of cells that are connected in series, the greater the probability of cell-to-cell variations. Battery weight constraints also limit the number of series strings of cells that can be connected in parallel, further reducing reliability.
Accordingly, it is desirable to provide a solution to the high-voltage battery reliability problem and to increase efficiency in ac electric drive systems by decoupling the energy storage system from the dc link voltage.

Technique for decoupling the energy storage system voltage from the DC link voltage in AC electric drive systems