A resin composition comprising the following components (A), (B) and (C), wherein the content of component (A) is from 10 to 90 wt %, component (B):component (C)=from 10:1 to 1:5 (weight ratio), the intrinsic viscosity [xcex7] is in the range from 0.17 to 0.40 m3/kg, and the density is in the range from 935 to 968 kg/m3:

1. Field of the Invention
The present invention relates to a resin composition comprising ethylene-based polymers excellent in environmental stress cracking resistance (hereinafter referred to as ESCR) and stiffness without imperfections or gel, excellent in moldability, and suitable for blow molding to produce e.g. cans and bottles, and for extrusion molding to produce pipes, and a process for its production.
2. Discussion of Background
In recent years, higher performance has become required for polyethylene as its application and demand increases. For example, physical properties required for polyethylene for blow molding or for extrusion molding may be good ESCR, high stiffness due to high density, good moldability, etc.
Generally speaking, the polyethylene having lower density, or higher intrinsic viscosity and higher molecular weight leads better ESCR property of the resin composition. However, when the value of polymer density is lowered, the mechanical strength of the composition is lowered as well as stiffness. When the polyethylene has high value of intrinsic viscosity or high molecular weight, the composition is poorly flowable to cause the problem of molding. Thus, improving ESCR of the resin composition in control of the density of the polymers and increasing the stiffness of resin composition, are against each other. Likewise, improving ESCR of the composition in control of the molecular weight of the polymers and improving the moldability of the composition, are against each other.
Heretofore, as a method of producing a polyethylene having a broad molecular weight distribution to be used for blow molding, a method of producing a polyethylene having a high molecular weight and a polyethylene having a low molecular weight in more than two consecutive polymerization steps has been considered, and various methods have been proposed as multi-step polymerization methods. Generally speaking, a polyethylene obtained by a two-step polymerization method is excellent in the balance of stiffness and ESCR, as compared with a polyethylene obtained by a single step polymerization method. For example, according to the method described in JP-A-64-79204 or JP-A-2-155906, it is disclosed that an xcex1-olefin is copolymerized in order to control the stiffness of the polyethylene, and the balance between the stiffness and environmental stress cracking resistance (ESCR) can be remarkably improved by incorporating the xcex1-olefin so that the content of the xcex1-olefin in the higher molecular weight polymer is higher than the content of the xcex1-olefin in the lower molecular weight polymer.
However, the product obtained by such a two-step polymerization method has disadvantages that generally, the bonding strength at a pinch-off portion of the blow molded articles is small, and the swelling ratio is small. As a means to overcome such disadvantages of the two-step polymerization method, a three-step polymerization method has been proposed in, for example, JP-A-58-138719, JP-A-59-227913, JP-A-64-79204, JP-B-59-10724, JP-B-62-61057, JP-B-3-29805 and JP-B-4-14686. In the method described in these publications, three components having different molecular weights are produced in each step. However, as pointed out in JP-B-4-14686, there is a problem that the balance of stiffness and ESCR tends to be poor, although the swelling ratio of the obtained polyethylene can be improved. Further, in the three-step polymerization method as proposed by such prior art, generally in addition to the lower molecular weight component and the high molecular weight component produced by normal two-step polymerization, a small amount of an ultrahigh molecular weight component is produced as a third component, and consequently, a polyethylene containing a small amount of a polymer having such a very high molecular weight tends to form imperfections or gel.
Therefore, it is an object of the present invention to provide a resin composition comprising ethylene-based polymers excellent in ESCR and stiffness without imperfections or gel, and excellent in moldability, and a process for producing such a resin composition.
The present inventors have conducted extensive studies to solve the above-mentioned difficult problems and establish a resin composition comprising ethylene-based polymers suitable for blow molding or extrusion molding, and a process for its production, and, as a result, have found that by combining three types of polymers having specific structures which are not ultrahigh molecular weight components, at specific contents, and further by setting the difference in molecular weight (evaluated by an intrinsic viscosity) between component (B) and component (C) among the three types not to be so large, and differentiating the contents of xcex1-olefins in the two components, all of the above-mentioned requirements can be satisfied and the object of the present invention can be realized. The present invention has been accomplished on the basis of these discoveries.
Thus, the present invention provides a resin composition comprising the following components (A), (B) and (C), wherein the content of component (A) is from 10 to 90 wt %, component (B):component (C)=from 10:1 to 1:5 (weight ratio), the intrinsic viscosity [xcex7] is in the range from 0.17 to 0.40 m3/kg, and the density is in the range from 935 to 968 kg/m3:
Component (A): a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.035 to 0.17 m3/kg,
Component (B): a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, and
Component (C): a copolymer of ethylene having an xcex1-olefin content of from 0.7 to 15 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg.
The present invention also provides a process for producing a resin composition comprising ethylene-based polymers, which comprises carrying out
step (a): a step of producing from 10 to 90 wt %, based on the total amount of polymerized polymers, of a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.035 to 0.17 m3/kg, at a temperature of from 70 to 110xc2x0 C.,
step (b): a step of producing a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, at a temperature of from 40 to 90xc2x0 C., and
step (c): a step of producing a copolymer of ethylene having an xcex1-olefin content of from 0.7 to 15 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, at a temperature of from 30 to 80xc2x0 C., in an optional order, by using a catalyst which comprises a solid catalyst component (E) containing at least titanium, magnesium and a halogen, and an organic aluminum compound, wherein the three-step polymerization is carried out so that the ratio of amount of polymerized polymers in steps (b) and (c) becomes step (b):step (c)=from 10:1 to 1:5 (weight ratio), to produce a resin composition having an intrinsic viscosity [xcex7] of from 0.17 to 0.4 m3/kg and a density of from 935 to 968 kg/m3.
The present invention further provides a process for producing a resin composition comprising ethylene-based polymers, which comprises carrying out
step (a): a step of producing from 10 to 90 wt %, based on the total amount of polymerized polymers, of a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.035 to 0.17 m3/kg, at a temperature of from 70 to 100xc2x0 C.,
step (b): a step of producing a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, at a temperature of from 40 to 90xc2x0 C.,
step (c): a step of producing a copolymer of ethylene having an xcex1-olefin content of from 0.7 to 15 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, at a temperature of from 30 to 80xc2x0 C., in an optional order, by using a catalyst which comprises a solid catalyst component (F) containing a metallocene compound and an aluminoxane, and an organic aluminum compound, wherein the three-step polymerization is carried out so that the ratio of amount of polymerized polymers in steps (b) and (c) becomes step (b):step (c)=from 10:1 to 1:5 (weight ratio), to produce a resin composition having an intrinsic viscosity [xcex7] of from 0.17 to 0.4 m3/kg and a density of from 935 to 968 kg/m3.
Now, the present invention will be described in detail with reference to the preferred embodiments.
The xcex1-olefin as a comonomer for the copolymer of ethylene constituting the resin composition comprising ethylene-based polymers of the present invention, means an xcex1-olefin other than ethylene. As such an xcex1-olefin, one having from 4 to 20 carbons is preferably used. Particularly, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene or 1-icocene, may, for example, be mentioned. Among these, 1-butene, 1-hexene and 1-octene are particularly preferred.
The resin composition comprising ethylene-based polymers of the present invention comprises three components (A), (B) and (C). Among them, component (A) is a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt % and an intrinsic viscosity [xcex7] of from 0.035 to 0.17 m3/kg. It is preferably a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.3 wt % and an intrinsic viscosity [xcex7] of from 0.04 to 0.15 m3/kg. When the content of the xcex1-olefin in component (A) exceeds 0.5 wt %, the stiffness and ESCR of the resin composition tend to be low. And, when the intrinsic viscosity [xcex7] is less than 0.035 m3/kg, the bonding strength at a pinch-off portion of the blow molded articles tends to be insufficient, and if it exceeds 0.17 m3/kg, ESCR of the composition tends to be low.
Component (B) of the resin composition is a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.5 wt % and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg. Preferably, it is a homopolymer of ethylene or a copolymer of ethylene having an xcex1-olefin content of from 0 to 0.3 wt % and an intrinsic viscosity [xcex7] of from 0.25 to 0.8 m3/kg. In component (B), when the xcex1-olefin content exceeds 0.5 wt %, the stiffness and ESCR of the resin composition tends to be low. Further, when the intrinsic viscosity [xcex7] of component (B) is less than 0.2 m3/kg, the impact resistance of the resin composition tends to be insufficient, and when it exceeds 1.0 m3/kg, the fluidity of the resin composition deteriorates and a gel, imperfections or fish-eyes tend to be formed in the molded articles.
Further, component (C) of the resin composition is a copolymer of ethylene having an xcex1-olefin content of from 0.7 to 1.5 wt % and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg. Preferably, it is an ethylene copolymer having an xcex1-olefin content of from 1.0 to 1.3 wt % and an intrinsic viscosity [xcex7] of from 0.25 to 0.8 m3/kg. In component (C), if the xcex1-olefin content is less than 0.7 wt %, ESCR of the composition tends to be too low, and if it exceeds 15 wt %, the stiffness of the composition deteriorates. Further, when the intrinsic viscosity [xcex7] of component (C) is less than 0.2 m3/kg, the impact resistance of the resin composition tends to be insufficient, and when it exceeds 1.0 m3/kg, the fluidity of the resin composition deteriorates and a gel, imperfections or fish-eyes tend to be formed in the molded articles.
The composition ratio of these three components is such that the content of component (A) is from 10 to 90 wt %, preferably from 30 to 80 wt %, based on the total amount of the composition, and the contents of component (B) and (C) are such that the weight ratio of component (B):component (C) is from 10:1 to 1:5, preferably from 5:1 to 1:4.
Here, when the content of component (A) based on the total amount of the resin composition is less than 10 wt %, the fluidity of the resin composition tends to be low, and the moldability of the resin composition in blow molding or extrusion molding is poor. On the other hand, if it exceeds 90 wt %, a gel or fish-eyes tend to increase. Further, in the weight ratio of component (B) and (C), when the amount of component (C) is too small, ESCR of the resin composition tends to be low, and when it is too much, the stiffness of the resin composition tends to be low.
The physical properties of the entire composition comprising components (A), (B) and (C), and constituted by the above-mentioned ratio, are such that the intrinsic viscosity [xcex7] is from 0.17 to 0.40 m3/kg, preferably from 0.18 to 0.35 m3/kg, and the density is from 935 to 968 kg/m3, preferably from 940 to 965 kg/m3.
When the intrinsic viscosity [xcex7] of the entire composition is less than 0.17 m3/kg, ESCR or the impact resistance tends to be low, and when it exceeds 0.40 m3/kg, the fluidity tends to be low, and the moldability tends to be poor. When the density of the composition is less than 935 kg/m3, the stiffness tends to be low, and when it exceeds 968 kg/m3, ESCR tends to be low.
The resin composition comprising ethylene-based polymers of the present invention comprises components (A), (B) and (C), as mentioned above, but it may contain various additives, as the case requires. Such additives may be ones commonly used for polyolefin compositions. For example, an antioxidant, an antistatic agent, an ultraviolet light absorber, a lubricant, a flame retardant or a compatibilizer may be mentioned.
The method for producing a resin composition comprising ethylene-based polymers of the present invention comprises carrying out three steps (a), (b) and (c), and these steps can be carried out in an optional order. At first, step (a) is carried out at a polymerization temperature within a range of from 70 to 100xc2x0 C. The reason for selecting the polymerization temperature to be from 70 to 100xc2x0 C. is that if it is less than 70xc2x0 C., the productivity becomes too low and if it exceeds 100xc2x0 C., a part of the polymer melts and forms an aggregated state, whereby continuous operation becomes difficult. In this step (a), by carrying out homopolymerization of ethylene or copolymerization of ethylene with an xcex1-olefin, an ethylene homopolymer or an ethylene copolymer having an xcex1-olefin content of from 0 to 0.5 wt %, preferably from 0 to 0.3 wt %, and an intrinsic viscosity [xcex7] of from 0.035 to 0.17 m3/kg, preferably from 0.040 to 0.15 m3/kg, is produced as component (A). At this time, the polymerization is carried out so that the amount of the polymer polymerized in this step becomes from 10 to 90 wt %, preferably from 30 to 80 wt % of the total composition. Here, the reason for limiting the xcex1-olefin content, the intrinsic viscosity [xcex7] and the amount of polymer, is the same as the reason for the limitation in the above-mentioned component (A).
Then, step (b) is carried out at a polymerization temperature within a range of from 40 to 90xc2x0 C. The reason for selecting the polymerization temperature to be from 40 to 90xc2x0 C. is that if it is less than 40xc2x0 C., the productivity becomes too low, and if it exceeds 90xc2x0 C., the productivity lowers and the intrinsic viscosity [xcex7] becomes difficult to control. Further, in this step (b), by performing homopolymerization of ethylene or copolymerization of ethylene with an xcex1-olefin, an ethylene homopolymer or an ethylene copolymer having an xcex1-olefin content of from 0 to 0.5 wt %, preferably from 0 to 0.3 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, preferably from 0.25 to 0.8 m3/kg, is produced as component (B). Here, the reason for limiting the xcex1-olefin content and the intrinsic viscosity [xcex7] is the same as the reason for the limitation in the above-mentioned component (B).
Further, step (c) is carried out at a polymerization temperature within a range of from 30 to 80xc2x0 C. The reason for selecting the polymerization temperature to be from 30 to 80xc2x0 C. is that if it is less than 30xc2x0 C., the productivity becomes too low, and if it exceeds 80xc2x0 C., the productivity becomes too low and the intrinsic viscosity [xcex7] become difficult to control. Further, in this step (c), by performing copolymerization of ethylene with an xcex1-olefin, an ethylene copolymer having an xcex1-olefin content of from 0.7 to 15 wt %, preferably from 1.0 to 13 wt %, and an intrinsic viscosity [xcex7] of from 0.2 to 1.0 m3/kg, preferably from 0.25 to 0.8 m3/kg, is produced as component (C). Here, the reason for limiting the xcex1-olefin content and the intrinsic viscosity [xcex7] is the same as the reason for the limitation in the above-mentioned component (C).
In the present invention, the molecular weights of components (B) and (C) are higher than that of component (A), as evident from intrinsic viscosities of each components, but they are not ultrahigh molecular weight as mentioned above. Further, the present invention has a characteristic that the difference in the molecular weight between component (B) and component (C) is not made so large, and the difference in the molecular weight between both components is preferably such that the difference in the intrinsic viscosity is preferably not more than 0.1 m 3/kg, particularly preferably not more than 0.05 m3/kg, and it is preferred to carry out the production so that the difference in the intrinsic viscosity become as small as possible. The reason is that if the difference in the molecular weight is high, the compatibility of the composition deteriorates and consequently, the composition becomes ununiform and gel, imperfections or fish-eyes are likely to form.
As mentioned above, in the process of the present invention, steps (a), (b) and (c) can be carried out in any optional order. However, normally, it is preferred to carry out the process in the order of step (a), step (b), followed by step (c), or in the order of step (b), step (a), followed by step (c).
In order to produce the copolymer of ethylene constituting the resin composition of the present invention, it is necessary to copolymerize an xcex1-olefin as a comonomer particularly to the high molecular weight portion. For this purpose, it is necessary to use a catalyst capable of providing good incorporation as much as possible, or to select an advantageous condition for copolymerization. As a catalyst for this purpose, a Ziegler type catalyst or a metallocene type catalyst may preferably be used. Particularly a Ziegler type catalyst or a metallocene type catalyst supported on a solid carrier is preferably used.
A Ziegler type catalyst to be used in the process of the present invention preferably consists of a solid catalyst component (E) containing at least titanium, magnesium and a halogen, and an organic aluminum compound component, as its main components. Here, the solid catalyst component (E) containing at least titanium, magnesium and a halogen, is preferably a composite solid formed by contacting a magnesium compound and a titanium halide compound. The method for its production and the obtained catalyst are not particularly restricted, and conventional ones can be used. As a specific method for producing the solid catalyst component (E), a method described, for example, in JP-B-50-32270, JP-B-52-13232 or JP-B-62-54326, may be used.
As the magnesium compound useful for producing the solid catalyst compound (E), various compounds used as carriers for Ziegler type catalysts may usually be used. For example, a magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide or magnesium fluoride, magnesium hydroxide, magnesium oxide, magnesium sulfate, magnesium carbonate, a hydroxymagnesium halide such as hydroxymagnesium chloride or hydroxymagnesium iodide, an alkoxy magnesium such as methoxy magnesium, ethoxy magnesium, propoxy magnesium or butoxy magnesium, an alkoxymagnesium halide such as methoxymagnesium chloride, methoxymagnesium bromide, ethoxymagnesium chloride, ethoxymagnesium bromide, propoxymagnesium chloride, propoxymagnesium bromide, butoxymagnesium chloride or butoxymagnesium bromide, an alkylmagnesium halide such as methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, propylmagnesium chloride, propylmagnesium bromide, butylmagnesium chloride or butylmagnesium bromide, or a mixture of these, may be mentioned.
Further, as the magnesium compound useful for producing the solid catalyst component (E), a reaction product (D) of an organic silicon compound shown hereinafter, with an organic magnesium compound, or a product produced by having the reaction product (D) further reacted with an aluminum alkoxide compound or an aluminum alkoxyhalide compound, may also be used. An example of a process for producing such magnesium compounds is disclosed in JP-B-52-13232 and JP-B-62-54326.
The organic silicon compound to be used for producing the above-mentioned reaction product (D) of the present invention is preferably a hydropolysiloxane compound having an optional degree of polymerization, represented by the following formula:
R1aHbSiO(4xe2x88x92axe2x88x92b)/2xe2x80x83xe2x80x83(I)
wherein R1 is a monovalent organic group selected from a group consisting of an alkyl group, an aryl group, an aralkyl group, an alkoxy group and an aryloxy group, and a is 0, 1 or 2, and b is 1, 2 or 3, provided a+bxe2x89xa63, or a mixture of such hydropolysiloxane compounds. With regard to its nature, various ones from liquid ones having low degrees of polymerization and a low viscosity to greasy or waxy ones having various degrees of polymerizations and a viscosity of up to 100 Pascalxc2x7second at 25xc2x0 C., and solid ones, may be mentioned. Since the structure of the terminal group of this hydropolysiloxane gives no substantial influence on the activity, it may be blocked by an optional inert group such as a trialkylsilyl group. As a specific example, tetramethyldisiloxane, diphenyldisiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, ethoxyhydropolysiloxane, cyclooctylhydropolysiloxane or chlorophenylhydropolysiloxane may be mentioned.
Another group of organic silicon compounds useful for producing the above-mentioned reaction product (D) of the present invention may be ones in which organic groups and hydroxyl groups are bonded to a silicon atom, particularly silane type compounds represented by the following formula:
R2nSi(OH)4xe2x88x92nxe2x80x83xe2x80x83(II)
wherein R2 is a monovalent hydrocarbon residue having from 1 to 18 carbon atoms, and n is a number of 1, 2 or 3, and if multiple R2 exist in one molecule, they may be the same or different, and polysiloxane type compounds which correspond to condensates thereof. As an example of R2 in formula (II), an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkaryl group may be mentioned. Such a group may be any one of straight chain type, branched chain type, saturated type, unsaturated type and ring type. As an example of the silane type compound of the above-mentioned formula (II) wherein n is 3, trimethylhydroxysilane, triethylhydroxysilane, triphenylhydroxysilane, methyldiphenylhydroxysilane or benzyldiphenylhydroxysilane, may be mentioned. Further, as an example of the compound wherein n is 2, diethyldihydroxysilane, dipropyldihydroxysilane, diallyldihydroxysilane, dicyclohexyldihydroxysilane or diphenyldihydroxysilane, may be mentioned. Further, as the compound wherein n is 1, butyltrihydroxysilane or phenyltrihydroxysilane, may be mentioned.
As the polysiloxane type compounds which correspond to condensates of the compounds of the above formula (II), ones having a siloxane condensation of Sixe2x80x94Oxe2x80x94Si and having a straight chain, a branched chain or a three-dimensional network structure, may be used. Their degrees of polymerization are not particularly limited, and they may cover from ones having low degrees of polymerization and a viscosity of several m pascalxc2x7sec (mPaxc2x7sec) at 25xc2x0 C., to greasy or waxy ones having a viscosity of up to 1,000,000 mPaxc2x7sec, and complete solid ones. As shown in formula (II), the polysiloxane type compound may be any one so long as it contains at least one hydroxyl group per molecule. However, one wherein the number of hydroxyl groups is too small, is not practically useful, and the content of hydroxyl groups in the polysiloxane type compound is preferably at least 0.1 wt %. As an example of such a polysiloxane type compound, an xcex1, xcfx89-dihydroxydimethylpolysiloxane represented by HO[Si(CH3)2O]nH (wherein, n is an integer of at least 2), or an xcex1, xcfx89-dihydroxymethylphenylpolysiloxane represented by HO[Si(CH3) (C6H5)O]nH (wherein, n is an integer of at least 2), may be mentioned.
As the organic magnesium compound to be used for the reaction with an organic silicon compound represented by the above formula (I) or (II), various types of organic magnesium compounds may be used. A preferred example may be a compound of the formula
(MgR32)pxc2x7(R3MgX)qxe2x80x83xe2x80x83(III)
(wherein R3 is a hydrocarbon group, X is a halogen atom, and p and q are numbers of from 0 to 1, having a relation of p+q=1) obtained by a reaction of a halogen-containing organic compound with metallic magnesium, its ether complex or a mixture thereof. As such an example, a so-called Gringnard reagent in a narrow sense represented by R3MgX i.e. p is 0 and q is 1, a dihydrocarbirmagnesium represented by R32Mg i.e. p is 1 and q is 0, other various organic magnesium halides represented by (MgR32)pxc2x7(R3MgX)q, an ether complex thereof or a mixture thereof, may be mentioned. These organic magnesium compounds may easily be prepared by conventional methods, for example, in an ether type solvent such as diethyl ether, dibutyl ether or tetrahydrofuran, or a hydrocarbon solvent such as heptane, octane, benzene or toluene, in the presence of an appropriate amount of a complexing agent such as an ether or an amine.
The method for reacting the organic silicon compound with the organic magnesium compound, may, for example, be the following method. Namely, for example, a Gringnard reagent prepared in a suitable solvent is added little by little to the organic silicon compound while stirring under an inert gas atmosphere. After all the amount is added, the stirring is continued for an additional predetermined period of time, to complete the reaction. The organic silicon compound can be used as it is without dilution. However, in some cases, it is more advantageous to use it as diluted by a hydrocarbon solvent or the like. This reaction can be carried out usually at a temperature of from xe2x88x9250xc2x0 C. to 100xc2x0 C. However, it is more advantageous to carry out the reaction at a temperature higher than room temperature. The reaction time in this case may sufficiently be from 30 minutes to 5 hours.
As the solvent for reaction, an inert hydrocarbon type solvent, namely, an aliphatic or aromatic hydrocarbon compound can be used. Specifically, hexane, heptane, cyclohexane, benzene, toluene or xylene may, for example, be mentioned. Further, an ether type solvent which is usually used for preparation of the above-mentioned Gringnard reagent, may also be used. The charging ratio of the organic silicon compound and the organic magnesium compound as raw materials, is preferably, OH:MgR3=1:0.05 to 1, in the case of an organic silicon compound having a hydroxyl group, as expressed by a molar ratio of hydroxyl groups in the organic silicon compound to the magnesium-hydrocarbon group bond (MgR3), and in the same way in the case of a hydropolysiloxane, it is preferably, Si:MgR3=1:0.05 to 1, as expressed by the molar ratio of silicon atoms (Si) in the hydropolysiloxane to the magnesium-hydrocarbon group bond (MgR3). And, it can be optionally selected from these ranges.
In the present invention, as mentioned above, a product or a solid component obtained by reacting the reaction product (D) with an aluminum alkoxide compound or an aluminum alkoxyhalide compound, can be used. A preferred aluminum compound which may be used at that time, is a compound represented by the following formula (IV):
Al(OR4)nX3xe2x88x92nxe2x80x83xe2x80x83(IV)
(wherein R4 is an alkyl group having from 1 to 12 carbons, n is in the range of 0 less than nxe2x89xa63, and X is an halogen atom.)
As a specific example, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum mono-sec-butoxydiisopropoxide, aluminum tri-n-butoxide, aluminum tri-sec-butoxide, aluminum tri-t-butoxide, aluminum monoethoxydichloride, aluminum diethoxymonochloride, aluminum monoisopropoxydichloride or aluminum diisopropoxymonochloride may be mentioned.
The reaction of the reaction product (D) with the aluminum compound of the above formula (IV) is sufficiently achieved only by mixing or reacting them in an inert hydrocarbon solvent at a temperature within a range of from xe2x88x9210 to 150xc2x0 C. for from 5 minutes to 10 hours.
The halogen-containing titanium compound to be used for producing the Ziegler type solid catalyst component (E) of the present invention, is one represented by the formula TiXn(OR5)4xe2x88x92n (wherein X is a halogen atom, R5 is a hydrocarbon group having from 1 to 8 carbon atoms, and n is an integer from 1 to 4). A specific example may be titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichloro-n-butoxytitanium, dichlorodiethoxytitanium, dichlorodiisopropoxytitanium or dichlorodi-n-butoxytitanium. The Ziegler type solid catalyst component (E) of the present invention may contain vanadium besides titanium. A vanadium compound in this case may, for example, be vanadium tetrachloride, vanadyl trichloride, tetraethoxyvanadium, tetrabutoxyvanadium, triethoxyvanadium or tributoxyvanadium.
The reaction of the above-mentioned magnesium compound with the halogen-containing titanium compound, or with the halogen-containing titanium compound and the vanadium compound, is carried out usually preferably in an inert hydrocarbon solvent, at from 0 to 150xc2x0 C., preferably from 20 to 100xc2x0 C., for from 0.5 to 10 hours, preferably from 1 to 5 hours.
As the inert hydrocarbon solvent, an aromatic or halogenated aromatic hydrocarbon solvent such as benzene, toluene or chlorobenzene; or an aliphatic hydrocarbon solvent such as hexane, heptane or cyclohexane, may, for example, be used. After completion of the reaction, the solid phase is separated, and a free titanium or vanadium compound is removed by washing with an inert hydrocarbon solvent such as hexane, heptane or kerosine to recover the solid catalyst component (E).
The content of titanium, or titanium and vanadium, as transition metals in the solid catalyst component (E) thus obtained, can be appropriately adjusted by changing the condition for the reaction of the above-mentioned magnesium compound with the halogen-containing titanium compound, or with the halogen-containing titanium compound and the vanadium compound, such as the temperature, the time or the presence or absence of a solvent. Usually, the content is preferably from 1 to 120 mg as calculated as the transition metals per 1 g of the solid catalyst component (E). A catalyst using the solid catalyst component (E) having a content of the transition metals within this range, exhibits a high catalytic activity.
The metallocene catalyst as another catalyst preferably used in the present invention, is a catalyst which comprises a solid catalyst component (F) containing an aluminoxane and a metallocene compound, and an organic aluminum compound component, as the main components. Such a solid catalyst component (F) containing an aluminoxane and a metallocene compound, is a composite solid formed by contacting a solid carrier with an aluminoxane and a metallocene compound stepwise or all at once, and various known catalysts may be used without any particular restriction. For example, it can be obtained by reacting a solid carrier with an aluminoxane and a metallocene compound with stirring in a hydrocarbon solvent. A specific example of the method and the catalyst may be one disclosed in e.g. JP-A-8-208717, JP-A-10-255194 or JP-A-10-296535.
The solid carrier useful for the production of the solid catalyst compound (F) may, specifically, be an inorganic oxide such as silica, alumina, magnesia, zirconia or titania, a magnesium compound such as magnesium hydroxide, magnesium chloride or Mg(OH)Cl, a compound such as a chemically modified product of the above-mentioned reaction product (D), or an organic polymer such as polyethylene, polypropylene or polystyrene. Particularly, an inorganic oxide represented by silica or alumina, a magnesium compound represented by magnesium chloride or Mg(OH)Cl, or a chemically modified product of the above-mentioned reaction product (D), is preferably used.
As the solid carrier to be used in the present invention, a fine particulate solid having an average particle diameter within a range of from 1 to 500 xcexcm, preferably from 5 to 300 xcexcm, and having a specific surface area of from 5 to 1,000 m2/g, preferably from 50 to 800 m2/g, is preferred. One having a pore volume of from 0.3 to 3 cm3/g, preferably from 0.5 to 2.5 cm3/g, is preferred.
In the inorganic oxide or the magnesium compound as the solid carrier to be used in the present invention, the amount of water absorbed or the amount of hydroxyl groups on the surface varies depending on the treatment conditions. As their preferred ranges, the water content is at most 5 wt %, and the amount of hydroxyl groups on the surface is at least 1 pc/(nm)2 unit area. The water content and the amount of hydroxyl groups on the surface, can be controlled by selecting the calcination temperature or the calcination time. Usually, the calcination is carried out at a temperature of from 100 to 1,000xc2x0 C. for from 1 to 40 hours. Otherwise, instead of calcination, a chemical dehydration method using e.g. an organic aluminum compound, silicon tetrachloride or chlorosilane may be used.
As the chemically modified product of the reaction product (D), preferred is a fine particulate solid obtained by treating the reaction product (D) obtained by a reaction of the above-mentioned organic silicon compound with the organic magnesium compound, with an alcohol, followed by treating further with water, for example as disclosed in JP-A-10-255194.
As the aluminoxane to be used for producing the solid catalyst component (F), one commonly known, may be used. It may be prepared, for example, by a method of adding an aluminum compound little by little to a suspension in a hydrocarbon solvent containing a compound having absorbed water, such as silica, or a salt containing crystal water such as copper sulfate hydrate or copper aluminum sulfate hydrate, or a method of reacting an organic aluminum compound with water in a solid, liquid or gaseous phase in a hydrocarbon solvent.
As the metallocene compound to be used for the solid catalyst component (F), various known compounds may be used which have zirconium, titanium or hafnium as a metal centere, and which contain a ligand having e.g. a cyclopentadienyl skeleton or an indenyl skeleton, and contain a ligand X bonded to the transition metal. Here, the ligand X bonded to the transition metal may be optionally selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group and an aryloxy group wherein the hydrogen atom on the aromatic ring is substituted or not substituted.
As the above-mentioned metallocene compound, a group of compounds containing zirconium as the transition metal, and having a various aryloxy group such as a substituted or unsubstituted phenoxy group as the ligand X, may be mentioned.
Specifically, dicyclopentadienylbis(2-fluorophenoxy)zirconium, dicyclopentadienylbis(3-fluorophenoxy)zirconium, dicyclopentadienylbis(4-fluorophenoxy)zirconium, dicyclopentadienylbis(2-chlorophenoxy)zirconium, dicyclopentadienylbis(3-chlorophenoxy)zirconium, dicyclopentadienylbis(4-chlorophenoxy)zirconium, dicyclopentadienylbis(2-bromophenoxy)zirconium, dicyclopentadienylbis(3-bromophenoxy)zirconium, dicyclopentadienylbis(4-bromophenoxy)zirconium, dicyclopentadienylbis(2-iodophenoxy)zirconium, dicyclopentadienylbis(3-iodophenoxy)zirconium, dicyclopentadienylbis(4-iodophenoxy)zirconium, dicyclopentadienylbis(2,3-difluorophenoxy)zirconium, dicyclopentadienylbis(2,4-difluorophenoxy)zirconium, dicyclopentadienylbis(2,5-difluorophenoxy)zirconium, dicyclopentadienylbis(2,6-difluorophenoxy)zirconium, dicyclopentadienylbis(3,4-difluorophenoxy)zirconium, dicyclopentadienylbis(3,5-difluorophenoxy)zirconium, dicyclopentadienylbis(2,3-dichlorophenoxy)zirconium, dicyclopentadienylbis(2,4-dichlorophenoxy)zirconium, dicyclopentadienylbis(2,5-dichlorophenoxy)zirconium, dicyclopentadienylbis(2,6-dichlorophenoxy)zirconium, dicyclopentadienylbis(3,4-dichlorophenoxy)zirconium, dicyclopentadienylbis(3,5-dichlorophenoxy)zirconium, dicyclopentadienylbis(2,3,4-trifluorophenoxy)zirconium, dicyclopentadienylbis(2,3,5-trifluorophenoxy)zirconium, dicyclopentadienylbis(2,3,6-trifluorophenoxy)zirconium, dicyclopentadienylbis(2,4,5-trifluorophenoxy)zirconium, dicyclopentadienylbis(2,4,6-trifluorophenoxy)zirconium, dicyclopentadienylbis(3,4,5-trifluorophenoxy)zirconium, dicyclopentadienylbis(2,3,5,6-tetrafluorophenoxy)zirconium, dicyclopentadienylbis(pentafluorophenoxy)zirconium, dicyclopentadienylbis(2-fluoromethylphenoxy)zirconium, dicyclopentadienylbis(3-fluoromethylphenoxy)zirconium, dicyclopentadienylbis(4-fluoromethylphenoxy)zirconium, dicyclopentadienylbis(2-chloromethylphenoxy)zirconium, dicyclopentadienylbis(3-chloromethylphenoxy)zirconium, dicyclopentadienylbis(4-chloromethylphenoxy)zirconium, dicyclopentadienylbis(2-trifluoromethylphenoxy)zirconium, dicyclopentadienylbis(3-trifluoromethylphenoxy)zirconium, dicyclopentadienylbis(4-trifluoromethylphenoxy)zirconium, dicyclopentadienylbis(3,5-bistrifluoromethylphenoxy)zirconium, dicyclopentadienylbis(2-(2,2,2-trifluoroethyl)phenoxy)zirconium, dicyclopentadienylbis(3-(2,2,2-trifluoroethyl)phenoxy)zirconium, dicyclopentadienylbis(4-(2,2,2-trifluoroethyl)phenoxy)zirconium, dicyclopentadienylbis(2-trichloromethylphenoxy)zirconium, dicyclopentadienylbis(3-trichloromethylphenoxy)zirconium, dicyclopentadienylbis(4-trichloromethylphenoxy)zirconium, dicyclopentadienylbis(2-methylphenoxy)zirconium, dicyclopentadienylbis(3-methylphenoxy)zirconium, dicyclopentadienylbis(4-methylphenoxy)zirconium, dicyclopentadienylbis(2,3-dimethylphenoxy)zirconium, dicyclopentadienylbis(2,4-dimethylphenoxy)zirconium, dicyclopentadienylbis(2,5-dimethylphenoxy)zirconium, dicyclopentadienylbis(2,6-dimethylphenoxy)zirconium, dicyclopentadienylbis(3,4-dimethylphenoxy)zirconium, dicyclopentadienylbis(3,5-dimethylphenoxy)zirconium, dicyclopentadienylbis(2,3,4-trimethylphenoxy)zirconium, dicyclopentadienylbis(2,3,5-trimethylphenoxy)zirconium, dicyclopentadienylbis(2,3,6-trimethylphenoxy)zirconium, dicyclopentadienylbis(2,4,5-trimethylphenoxy)zirconium, dicyclopentadienylbis(2,4,6-trimethylphenoxy)zirconium, dicyclopentadienylbis(3,4,5-trimethylphenoxy)zirconium, dicyclopentadienylbis(pentamethylphenoxy)zirconium, dicyclopentadienylbis(2-methyl-4-fluorophenoxy)zirconium, dicyclopentadienylbis(2-chloro-4-fluorophenoxy)zirconium, dicyclopentadienylbis(2-chloro-4-trifluoromethylphenoxy)zirconium, dicyclopentadienylbis(2-fluoro-4-trifluoromethylphenoxy)zirconium, dicyclopentadienylbis(2-trifluoromethyl-4-fluorophenoxy)zirconium, dicyclopentadienylbis(2-ethylphenoxy)zirconium, dicyclopentadienylbis(3-ethylphenoxy)zirconium, dicyclopentadienylbis(4-ethylphenoxy)zirconium, dicyclopentadienylbis(2-isopropylphenoxy)zirconium, dicyclopentadienylbis(3-isopropylphenoxy)zirconium, dicyclopentadienylbis(4-isopropylphenoxy)zirconium, dicyclopentadienylbis(2-tertiarybutylphenoxy)zirconium, dicyclopentadienylbis(3-tertiarybutylphenoxy)zirconium, dicyclopentadienylbis(4-tertiarybutylphenoxy)zirconium, dicyclopentadienylbis(3,5-ditertiarybutylphenoxy)zirconium, dicyclopentadienylbis(2,8-dimethyl-1-naphtoxy)zirconium, dicyclopentadienylbis(1-tertiarybutyl-2-naphtoxy)zirconium, dicyclopentadienylbis(8-bromo-2-naphtoxy)zirconium, dicyclopentadienylbis(2-phenylphenoxy)zirconium, dicyclopentadienylbis(3-phenylphenoxy)zirconium, dicyclopentadienylbis(4-phenylphenoxy)zirconium, dicyclopentadienylbis(2-benzylphenoxy)zirconium, dicyclopentadienylbis(2-methoxycarbonylphenoxy)zirconium, dicyclopentadienylbis(2-acetoxyphenoxy)zirconium, dicyclopentadienylbis(2-cyanophenoxy)zirconium, dicyclopentadienylbis(2-nitrophenoxy)zirconium, dicyclopentadienylbis(2-dimethylaminophenoxy)zirconium, dicyclopentadienylbis(2-trifluoromethanesulfonylphenoxy)zirconium, dicyclopentadienylbis(4-fluorothiophenoxy)zirconium, dicyclopentadienylbis(2-trifluoromethylthiophenoxy)zirconium, dicyclopentadienylbis(3-trifluoromethylthiophenoxy)zirconium, bis(methylcyclopentadienyl)bis(2-chlorophenoxy)zirconium, bis(methylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, bis(1,2-dimethylcyclopentadienyl)bis(2-ethylphenoxy)zirconium, bis(1,3-dimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, bis(1,3-dimethylcyclopentadienyl)bis(3-tertiarybutylphenoxy)zirconium, bis(1,2,3-trimethylcyclopentadienyl)bis(2-fluorophenoxy)zirconium, bis(1,2,3-trimethylcyclopentadienyl)bis(3-fluorophenoxy)zirconium, bis(1,2,3-trimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, bis(1,2,3-trimethylcyclopentadienyl)bis(2-isopropylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(2-methylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(3-methylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(4-methylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(2,4-dimethylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(2,4-dichlorophenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(2-tertiarybutylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(3-tertiarybutylphenoxy)zirconium, bis(1,2,4-trimethylcyclopentadienyl)bis(4-tertiarybutylphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-methoxyphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-methoxyphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-methoxyphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-iodophenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-iodophenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-iodophenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-thiomethylphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-thiomethylphenoxy)zirconium, bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-thiomethylphenoxy)zirconium, bis(pentamethylcyclopentadienyl)bis(2-fluorophenoxy)zirconium, bis(pentamethylcyclopentadienyl)bis(3-fluorophenoxy)zirconium, bis(pentamethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, bis(ethylcyclopentadienyl)bis(2-ethylphenoxy)zirconium, bis(ethylcyclopentadienyl)bis(3-ethylphenoxy)zirconium, bis(ethylcyclopentadienyl)bis(4-ethylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(2-acetylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(3-acetylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(4-acetylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(2-methylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(3-methylphenoxy)zirconium, bis(isopropylcyclopentadienyl)bis(4-methylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(2-chlorophenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(3-chlorophenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(4-chlorophenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(2-tertiarybutylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(3-tertiarybutylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(4-tertiarybutylphenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(2-cyanophenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(3-cyanophenoxy)zirconium, bis(n-butylcyclopentadienyl)bis(4-cyanophenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(2-fluorophenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(3-fluorophenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(2-ethylphenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(3-ethylphenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(4-ethylphenoxy)zirconium, bis(tertiarybutylcyclopentadienyl)bis(2,4-dimethylphenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(2-chlorophenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(3-chlorophenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(4-chlorophenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium, bis(1,3-ditertiarybutylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, bis(phenylcyclopentadienyl)bis(2-phenylphenoxy)zirconium, bis(phenylcyclopentadienyl)bis(3-phenylphenoxy)zirconium, bis(phenylcyclopentadienyl)bis(4-phenylphenoxy)zirconium, bis(phenylcyclopentadienyl)bis(2,4-dichlorophenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(2-tertiarybutoxyphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(3-tertiarybutoxyphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(4-tertiarybutoxyphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(2-phenylphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(3-phenylphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(4-phenylphenoxy)zirconium, bis(trimethylsilylcyclopentadienyl)bis(2,4-difluorophenoxy)zirconium, bis(cyclohexylcyclopentadienyl)bis(2-iodophenoxy)zirconium, bis(cyclohexylcyclopentadienyl)bis(3-iodophenoxy)zirconium, bis(cyclohexylcyclopentadienyl)bis(4-iodophenoxy)zirconium, bis(indenyl)bis(2-methylphenoxy)zirconium, bis(indenyl)bis(3-methylphenoxy)zirconium, bis(indenyl)bis(4-methylphenoxy)zirconium, bis(1-methylindenyl)bis(2-fluorophenoxy)zirconium, bis(1-methylindenyl)bis(3-fluorophenoxy)zirconium, bis(1-methylindenyl)bis(4-fluorophenoxy)zirconium, bis(2-methylindenyl)bis(2-bromophenoxy)zirconium, bis(2-methylindenyl)bis(3-bromophenoxy)zirconium, bis(2-methylindenyl)bis(4-bromophenoxy)zirconium, bis(5,6-dimethylindenyl)bis(2-isopropylphenoxy)zirconium, bis(5,6-dimethylindenyl)bis(3-isopropylphenoxy)zirconium, bis(5,6-dimethylindenyl)bis(4-isopropylphenoxy)zirconium, bis(5,6-dimethoxyindenyl)bis(2-cyanophenoxy)zirconium, bis(5,6-dimethoxyindenyl)bis(3-cyanophenoxy)zirconium, bis(5,6-dimethoxyindenyl)bis(4-cyanophenoxy)zirconium, bis(fluorenyl)bis(2-chlorophenoxy)zirconium, bis(fluorenyl)bis(3-chlorophenoxy)zirconium, bis(fluorenyl)bis(4-chlorophenoxy)zirconium, bis(4,5,6,7-tetrahydroindenyl)bis(2-tertiarybutylphenoxy)zirconium, bis(4,5,6,7-tetrahydroindenyl)bis(3-tertiarybutylphenoxy)zirconium, bis(4,5,6,7-tetrahydroindenyl)bis(4-tertiarybutylphenoxy)zirconium, bis(2-methyltetrahydroindenyl)bis(2-nitrophenoxy)zirconium, bis(2-methyltetrahydroindenyl)bis(3-nitrophenoxy)zirconium, bis(2-methyltetrahydroindenyl)bis(4-nitrophenoxy)zirconium, bis(2,7-ditertiarybutylfluorenyl)bis(2-trifluoromethylphenoxy)zirconium, bis(2,7-ditertiarybutylfluorenyl)bis(3-trifluoromethylphenoxy)zirconium, bis(2,7-ditertiarybutylfluorenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(indenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(indenyl)bis(4-chlorophenoxy)zirconium, ethylenebis(indenyl)bis(2-fluorophenoxy)zirconium, ethylenebis(3-methylindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(3-methylindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(3-methylindenyl)bis(4-chlorophenoxy)zirconium, ethylenebis(3-methylindenyl)bis(2-fluorophenoxy)zirconium, ethylenebis(5,6-dimethylindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(5,6-dimethylindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(5,6-dimethylindenyl)bis(4-chlorophenoxy)zirconium, ethylenebis(5,6-dimethylindenyl)bis(2-fluorophenoxy)zirconium, ethylenebis(4,7-dimethylindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(4,7-dimethylindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(5,6-dimethoxyindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(5,6-dimethoxyindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(5,6-dihydroindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(5,6-dihydroindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(5,6-dihydroindenyl)bis(4-chlorophenoxy)zirconium, ethylenebis(5,6-dihydroindenyl)bis(2-fluorophenoxy)zirconium, ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium, ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-chlorophenoxy)zirconium, ethylenebis(4,5,6,7-tetrahydroindenyl)bis(2-fluorophenoxy)zirconium, methylenebis(cyclopentadienyl)bis(2-fluorophenoxy)zirconium, methylenebis(cyclopentadienyl)bis(2-ethylphenoxy)zirconium, methylenebis(methylcyclopentadienyl)bis(3-chlorophenoxy)zirconium, methylenebis(1,3-dimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium, methylenebis(n-butylcyclopentadienyl)bis(4-tertiarybutylphenoxy)zirconium, ethylenebis(3-methylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, ethylenebis(3-isopropylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(3-isopropylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, ethylenebis(3-tertiarybutylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, ethylenebis(3-tertiarybutylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, isopropylidene(cyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium, isopropylidene(cyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium, isopropylidene(methylcyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium, isopropylidene(methylcyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium, isopropylidenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium, isopropylidenebis(indenyl)bis(4-fluorophenoxy)zirconium, isopropylidene(cyclopentadienyl)(fluorenyl)bis(4-trifluoromethylphenoxy)zirconium, isopropylidene(cyclopentadienyl)(fluorenyl)bis(4-fluorophenoxy)zirconium, isopropylidene(3-methylcyclopentadienyl)(fluorenyl)bis(4-trifluoromethylphenoxy)zirconium, isopropylidene(3-methylcyclopentadienyl)(fluorenyl)bis(4-fluorophenoxy)zirconium, tetramethylethylidenebis(2-tertiarybutylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, tetramethylethylidenebis(2-tertiarybutylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-methylindenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(2-methylindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-ethylindenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(2-ethylindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-methyl-5-isopropylindenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(2-methyl-5-isopropylindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-tertiarybutylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(2-tertiarybutylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-tertiarybutyl-4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(2-isopropyl-4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(2,4,5-trimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,4-dimethylcyclopentadienyl)(3,5-dimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-tertiarybutylcyclopentadienyl)(4-tertiarybutylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-methylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,4-dimethylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,4-dimethylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3,4-dimethylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-tertiarybutylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-tertiarybutylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(2,4-dimethylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-tertiarybutylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(3-methylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylene(cyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylene(cyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium, diphenylsilylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium, diphenylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium, dibenzylsilylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium, dibenzylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium, methylphenylsilylenebis(2-methylindenyl)bis(4-trifluoromethylphenoxy)zirconium, methylphenylsilylenebis(2-methylindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(3,4-dimethylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium, dimethylsilylenebis(3,4-dimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium or dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium, may, for example, be mentioned.
Further, in the present invention, besides the above listed metallocene compounds, metallocene compounds having, for example, a chlorine atom, a bromine atom, a hydrogen atom, a methyl group, an ethyl group, a benzyl group or a phenyl group, as the ligand X, may also be used. Specifically, bis(cyclopentadienyl) zirconium monochloride monohydride, bis(cyclopentadienyl)zirconium monobromide monohydride, bis(cyclopentadienyl)methylzirconium hydride, bis(cyclopentadienyl)ethylzirconium hydride, bis(cyclopentadienyl)phenylzirconium hydride, bis(cyclopentadienyl)benzylzirconium hydride, bis(cyclopentadienyl)neopentylzirconium hydride, bis(methylcyclopentadienyl)zirconium monochloride monohydride, bis(indenyl)zirconium monochloride monohydride, bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dibromide, bis(cyclopentadienyl)methylzirconium monochloride, bis(cyclopentadienyl)ethylzirconium monochloride, bis(cyclopentadienyl)cyclohexylzirconium monochloride, bis(cyclopentadienyl)phenylzirconium monochloride, bis(cyclopentadienyl)benzylzirconium monochloride, bis(cyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadienyl)zirconium dichloride, bis(trimethylcyclopentadienyl)zirconium dichloride, bis(butylcyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)diphenylzirconium, bis(cyclopentadienyl)dibenzylzirconium, bis(indenyl) zirconium dichloride, bis(indenyl) zirconium dibromide, bis(fluorenyl)zirconium dichloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)methylzirconium monobromide, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium dichloride, dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(dimethylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(trimethylcyclopentadienyl)zirconium dichloride, isopropylidenebis(indenyl)zirconium dichloride or isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, may, for example, be mentioned.
Further, as the metallocene compound of the present invention, besides the above listed various compounds, metallocene compounds wherein the metal centere is changed from the zirconium atom to a titanium atom or a hafnium atom may also be used.
The method for preparing the solid catalyst component (F) of the present invention containing a metallocene compound and an aluminoxane, is not particularly restricted. For example, (1) a method of mixing the aluminoxane and a solid carrier, followed by supporting a catalytic reaction product of the metallocene compound with the aluminoxane, on the solid carrier, (2) a method of mixing the aluminoxane and the solid carrier, followed by contacting and supporting the metallocene compound thereon, (3) a method of supporting the metallocene compound on the solid carrier, followed by mixing with the aluminoxane, or (4) a method of contacting a reaction product of the metallocene compound with the aluminoxane, with the solid carrier, may be used.
The method of contacting and supporting the metallocene compound and/or the aluminoxane on the solid carrier, is usually carried out in an inert hydrocarbon solvent. As the inert hydrocarbon solvent in such a case, an aromatic hydrocarbon solvent such as benzene, toluene or xylene; an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane, decane or dodecane; or an alicyclic hydrocarbon solvent such as cyclopentane or cyclohexane, may, for example, be employed. Among them, an aromatic hydrocarbon solvent is particularly preferred.
The temperature for contacting the metallocene compound and/or the aluminoxane with the solid carrier, is usually from xe2x88x9250 to 200xc2x0 C., preferably from xe2x88x9220 to 100xc2x0 C., more preferably from 0 to 90xc2x0 C. Further, the contacting time is usually from 5 minutes to 100 hours, preferably from 10 minutes to 20 hours.
The ratio of the metallocene compound and the aluminoxane to be used in the present invention, is preferably such that the molar ratio of the metallocene compound/aluminum atoms in the aluminoxane, is from 1/1 to 1/1,000, preferably from 1/10 to 1/500.
The ratio of the solid carrier and the aluminoxane to be used in the present invention is preferably such that the ratio of mole of aluminum atoms in the aluminoxane/the solid carrier (g) is from 1/1 to 1/1,000, preferably from 1/10 to 1/500. Further, the ratio of the solid carrier and the metallocene compound is preferably such that the ratio of mole of the metallocene compound/the solid carrier (g) is from 1/5 to 1/10,000, preferably from 1/10 to 1/1,000.
The solid catalyst component (E) or the solid catalyst component (F) to be used in the present invention, may be pre-polymerized in the presence of an olefin. The method for such pre-polymerization is such that an xcex1-olefin is pre-polymerized in the presence of the solid catalyst component (E) or the solid catalyst component (F), if necessary in the presence of an organic aluminum compound.
The pre-polymerized solid catalyst component (E) or the pre-polymerized solid catalyst component (F) preferably contains the polymer in an amount of from 0.1 to 500 g, particularly from 0.3 to 300 g, per 1 g of the solid catalyst component (E) or the solid catalyst component (F).
In the present invention, ethylene is homo-polymerized, or ethylene and an xcex1-olefin having preferably at least 4 carbon atoms, particularly preferably from 4 to 20 carbon atoms, are copolymerized by a slurry polymerization method or a gas phase polymerization method in the presence of the solid catalyst component (E) or the solid catalyst component (F) subjected to or not subjected to the pre-polymerization as mentioned above. The xcex1-olefin may, for example, be 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene or 1-icocene. In the case of the slurry polymerization, the solvent for the polymerization may, for example, be an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane or kerosine; an alicyclic hydrocarbon such as cyclopentane, cyclohexane or methylcyclopentane; an aromatic hydrocarbon such as benzene, toluene or xylene; or a halogenated hydrocarbon such as ethylene chloride, chlorobenzene or dichloromethane. These media may be used alone or in combination as a mixture.
The amount of the solid catalyst component used for the polymerization, is usually from 10xe2x88x928 to 10xe2x88x923 g atom, preferably from 10xe2x88x927 to 10xe2x88x924 g atom per 1 l of the polymerization volume, as calculated based on the transition metal atoms in the solid catalyst component (E) or the solid catalyst component (F). Further, the amount of the organic aluminum compound for polymerization is usually from 1 to 1,000 mole, preferably from 10 to 500 mole, per 1 g atom of the transition metal atoms in the solid catalyst component (E) or the solid catalyst component (F).
The slurry concentration in the slurry polymerization is usually within a range of at least 100 g/l, preferably from 100 to 700 g/l, more preferably from 150 to 600 g/l, particularly preferably from 200 to 500 g/l.
The total pressure in polymerization is usually from atmospheric pressure to 10 MPa, preferably from atmospheric pressure to 5 MPa. The polymerization can be carried out in any one of a batch process, a semi-continuous process and a continuous process. The molecular weight of the olefin polymer can be controlled by addition of hydrogen to the polymerization system or by changing the polymerization temperature.
Now, the present invention will be further described in more detail by way of Examples. However, the present invention is by no means restricted to such specific Examples.
The physical properties of resin composition in the present invention were measured by the following methods.
(1) xcex1-olefin content (unit: wt %)
Calculated by 13C-NMR measurement
(2) Intrinsic viscosity [xcex7] (unit: m3/kg)
Measured in accordance with JIS K7367-3 in a decalin solution of 135xc2x0 C.
(3) Density (unit: kg/m3)
Measured in accordance with JIS K7112 by a density-gradient column method (23xc2x0 C.).
(4) Flexural modulus (unit: MPa)
Measured in accordance with JIS K7171.
(5) ESCR (unit: h)
Measured in accordance with the polyethylene test method in the attachment (regulations) in JIS K6922-2.

Resin composition comprising ethylene-based polymers and process for its production


The disclosure relates to a device and a method for the treatment of diseases of the skin, glands, mucousae, connective tissue, nerves and/or horny tissue. The device is adapted for the treatment of diseases of the skin, glands, mucousae, connective tissue, nerves and/or horny tissue and has at least one applicator, which applicator is arranged outside the device housing; at least one radio wave module, which radio wave module is adapted to generate an adjustable electromagnetic radiation with a variable frequency or with at least one constant frequency with an adjustable variable or at least one adjustable constant intensity.

Skin disorders can be referred for example to disorders of epidermis, dermis and/or hypodermis (ICD-10-Code L00 to L08). To simplify the attribution, the said diseases and the data in brackets refer to International Statistical Classification of Diseases and Related Health Problems, in short ICD-10. In particular, the said diseases can be triggered by external factors, pathogens, in particular microorganisms, as bacteria and/or fungi, and/or by viruses. Skin lesions, disturbance of the natural acid mantel of the skin und suppressed immune system can provoke pathogens, in particular microorganisms to penetrate the skin and evoke infection, in particular inflammatory or suppurative.

Device and/or method for treating diseases of the skin, glands, mucosae, connective tissue, nerves and/or horny tissue


An image forming apparatus for forming an image based on image data, includes: a power source for supplying power to various sections of the apparatus; a display section for displaying; and a control section for executing a controlling regarding operations of the apparatus, wherein the control section is provided with a normal power supply mode representing a state of normal power supply, and a power supply mode for operator part replacement representing the state of power supply different from said normal power supply mode, the power supply mode for operator part replacement to which an operator changes the state of power supply on changing a part or a unit of the apparatus.

In an image forming apparatus such as a photocopier, printer, facsimile and multi-functional peripheral wherein an image is formed based on image data, a document is exposed to an exposure lamp to read the reflected light, and an image data is generated. Based on this image data, an electrostatic latent image is formed on a photoconductor drum or the like by a writing unit using laser light. This electrostatic latent image is developed by the development unit containing toner and developer, and is transferred directly or through a transfer belt onto the sheet supplied by a sheet feed roller. After that, the toner is fixed onto the sheet by the pressure and heat applied by a fixer.
The approximate service life of the aforementioned parts such as photoreceptor drum, development unit, sheet feed roller, transfer belt, and fixing device are determined by the number of uses. These parts are designed to be replaceable, and are replaced at appropriate intervals, whereby high image quality can be maintained. In the conventional method, replacement, maintenance and inspection of these parts and units have been taken care of exclusively by a serviceman familiar with the structure of the apparatus. In the recent digital printing industry, replacement of the aforementioned parts can be performed quickly by an operator handling the apparatus, without having to wait for the dispatch of a serviceman.
Incidentally, to allow the maintenance, inspection and replacement of the parts to be performed, the image forming apparatus is provided with an open/close-type door. This open/close-type door is normally closed. Only when the aforementioned work is to be performed, the open/close-type door is opened to perform the work. The main body of such an apparatus incorporates a charging device that operates at a high voltage and a fixing device being heated to a high temperature. If these devices are kept operating with the open/close-type door open, working safety will not be ensured. Thus, the conventional image forming apparatus is provided with an interlock switch that operates in synchronism with the opening and closing of the door. When the door is opened, the power of the apparatus is automatically turned off by the interlock switch. When the open/close-type door has been closed, power supply is started to allow the operation to be performed (Unexamined Japanese Patent Application Publication No. Sho 62 (1987)-69277).
Generally, operators have a lower level of skill than servicemen. It is preferred that operators confirm the replacement work procedure during the replacement work. However, in the conventional image forming apparatus, at the time of parts replacement, the apparatus power is turned off by opening the open/close-type door. This makes it necessary to use a label or manual as instructions for the parts replacement procedure. When the parts replacement procedure is complicated particularly in the parts replacement work of a sophisticated large-sized apparatus, it is very difficult to instruct the operator on the details of the replacement procedure. Another problem is that, in the conventional image forming apparatus, the power of the apparatus is turned off in the replacement mode. Thus, the apparatus itself is incapable of determining if the parts have been replaced or not. This fails to notify the operator of the replacement on a real-time basis. Thus, in cases wherein the operator closes the door or turns on power without the parts and others having been completely replaced, the initial operation of the apparatus starts as the power is turned on, and the machine may be seriously damaged due to incomplete replacement. In the conventional art, there is an increase in the aforementioned risk because the replacement work having been done by the serviceman alone is released to the operator.
In view of the problems described above, it is an object of the present invention to provide an apparatus for ensuring safety and reliable replacement work to be performed in cases wherein the parts and units of the apparatus are replaced by an operator.

Image forming apparatus with an operator part replacement mode

Konica Minolta Business Technologies, Inc.


The present invention provides a method for preparing cell extract for high-performance cell-free protein synthesis reactions, comprising the elimination of low molecular weight substances that have protein synthesis inhibitory activity, from cell extracts that have cell-free protein synthesis activity, by such methods as dialysis, gel filtration and ultrafiltration. Also provided is a ready-made cell-extract for cell-free protein synthesis employing this method. Furthermore, the formation of insoluble matter can be reduced by performing the process for eliminating the low molecular weight substances that inhibit protein synthesis in the co-presence of ATP, GTP or amino acids, so as to stabilize the cell extract.

The development of technologies allowing proteins to be synthesized at will are expected to contribute greatly, not only to the fields of the life sciences and biotechnology, but also to the design of nano-machines and the development of molecular devices in such engineering fields as neural computing. Currently, genetic engineering techniques for introducing cloned DNA into living cells are widely used for protein synthesis, but exogenous proteins that can be produced by these methods are limited to molecules that are able to survive the life support mechanisms of their host. Meanwhile, advances in organic synthesis technology have made automatic synthesizers common, but while peptides comprising a few dozen amino acids are routinely synthesized, chemical synthesis of higher molecular weight proteins is currently extremely difficult, due to limitations in terms of the yield, side reactions, and the like. Furthermore, there has been strong ethical criticism in Europe and the United States of conventional using living organisms to produce proteins, or to search for novel molecules, and there is a concern that international regulations will become even stricter.
Cell-free protein synthesis is a novel protein synthesis method capable of overcoming these problems, which attempts to make maximal use of the outstanding characteristics of living organisms by applying chemical procedures to the same. These methods provide biological systems for the translation of genetic information within artificial containers and, using nucleic acids which have been designed and synthesized as templates, reconstruct systems capable of incorporating the desired amino acids, including those which do not exist in nature. As these systems are not subject to the limitations of living organisms, it can be expected that an almost limitless range of protein molecules can be synthesized.
With regard to cell-free protein synthesis systems, it was reported 40 years ago that pulped cell sap retained the ability to synthesize protein, and various methods of doing this have been developed in the past. Currently, cell extracts derived from E. coli, wheat embryo, and rabbit reticulocytes are widely employed in protein synthesis and the like. Cell-free systems allow for rapid translation speeds of 10 peptide bonds per second, which is roughly equal to in vivo translation speeds, and excellent reaction characteristics in terms of translation accuracy, but in all cell-free systems, the period of time for which synthesis can be continued is short and the yield is extremely low, at a few micrograms to a few dozen micrograms per milliliter of reaction volume, which is approximately 1/100 to 1/1000 of the yield of living cells, making this an impractical protein synthesis method.
A major disadvantage of conventional cell-free protein synthesis systems was that synthesis efficiency was extremely low, but no direct studies have been made of the cause. This is because it was common knowledge in the field of biochemistry that activity in cell extracts prepared with artificial buffer from physical ground cells was somewhat lower.
The inventors have already shown, based on the findings of past research into ribosome inactivating toxins, that the extreme drop in protein synthesis activity seen in cell-free protein synthesis systems using wheat embryo extract were the result of a switch for an auto ribosome inactivation mechanism (cell suicide mechanism), which is programmed into the original cell as a defense mechanism against pathogenic microorganisms, and which is triggered by grinding the embryo (Madin, K. et al., Proc. Natl. Acad. Sci. USA, 97, 559-564 [2000]). Then, it was demonstrated that protein synthesis reactions using wheat embryo extract that was prepared by a novel method, wherein tritin activity and the like were eliminated from embryo tissues, exhibit good protein synthesis characteristics over a long period of time (Madin, K. et al., Proc. Natl. Acad.Sci. USA, 97, 559-564 (2000), JP-2000-236896-A).
However, there are problems with wheat embryo extracts prepared according to such methods in that, depending on the target protein (for example, DNA binding proteins such as transcription factors) by the influence of other inhibition factors meant that it was not always possible to achieve a sufficient yield.
Furthermore, conventional cell extracts for cell-free protein synthesis presented problems in terms of storage stability when solutions that contained the amino acids, energy sources, ions and the like, which are necessary for protein synthesis were added. For this reason, it was necessary to supply the cell extract and the solution containing the energy source and the like separately, requiring that the researcher mix these together with the translation template each time that an experiment was performed. Because of such problems as the necessity of performing these operations at low temperatures, the overall experimental work became difficult, which often caused protein synthesis to fail. Furthermore, such methods for supplying reagents for cell-free protein synthesis reactions are not suited for comprehensive synthesis of proteins from a multiplicity of genes and a major problem facing future robotization is the solution of these problems of complicatedness.

Cell extract for cell-free protein synthesis and process for producing the same


A universal surface flush junction box which provides an improved way to transition from in-wall wiring to surface (out of wall) wiring in a building, which requires no additional mounting brackets or conduit bends, which thereby allows for a one trip complete rough-in installation and greatly reduces the amount of sealant required for smoke, fire and acoustical seal.

The disclosed invention relates to an electrical conduit junction box. In particular, the disclosed invention relates to an electrical conduit junction box that is useful in applications for connecting electrical conduit by facilitating a novel and improved method to transition from in-wall wiring to surface (out of wall) wiring in residential, commercial and industrial building applications. Wiring in such a building is typically installed in conduit located within the walls that exits the wall above the suspended ceiling for connection to other conduits in the electrical distribution system. Traditional electrical conduit junction boxes require the bending of an elbow or offset to the connecting conduit when there is a transition from in-wall wiring to surface wiring in a building. The elbow bend or offset is necessitated because, with a traditional electrical conduit junction box, one box is installed on one side of the wall and the other box is installed on the opposing side of the wall, necessitating the conduit to be bent to travel between the inner side of the wall and the outer side of the wall.
The use of a traditional electrical conduit junction box in applications for a transition from in-wall to surface wiring is labor intensive for both the electrician and the wallboard installer. In such applications, the electrician must bend conduit and then install the junction box and supporting hardware. The wallboard installer must cut a slotted opening for the conduit to exit through the wallboard and then fit the wallboard around the protruding conduit. The disclosed invention eliminates the need for bending of conduit and allows for simplified wallboard installation using a rotary cutter to cut the opening for the electrical conduit junction box.
When using a traditional electrical conduit junction box in transitioning from in-wall to surface wiring, traditional installations are usually performed in one of two ways. In the first traditional installation, conduit is installed from an in-wall device box with a 90 degree bend in the conduit required to exit the wall cavity to connect to a junction box independently supported from the structure (as seen in FIG. 8) per the National Electric Code section 314.23, which requires an enclosure mounted on a building or other surface to be rigidly and securely fastened in place. Performing such an installation with a traditional electrical conduit junction box requires a large opening to be cut into the wallboard that will likely require sealing for fire, smoke or acoustical reasons. Such an installation requires multiple return trips for various distinct contractors, such as electrical contractors, drywall contractors and carpenters, to complete the installation.
In the second traditional installation, conduit is installed from an in-wall device box with an offset bend in the conduit required to exit the wall cavity to connect to a junction box mounted to the wallboard (as seen in FIG. 9). Performing such an installation with a traditional electrical conduit junction box requires a large opening to be cut into the wallboard that will likely require sealing for fire, smoke or acoustical reasons. The surface box cannot be installed until after the wallboard installation. Such an installation requires multiple return trips for various contractors to complete the installation.
What is novel about the disclosed invention is that it's design enables an installation of the disclosed invention which requires no additional mounting brackets or conduit bends as required by the prior art. The disclosed invention is a novel design in which the junction box is installed within and passes thru a wall or wallboard, where said wall or wallboard might be constructed of drywall, dryvit or stucco, wood paneling, plaster and lath (or wire mesh), or any formed finished wall product in a building. Once the junction box is installed in the wallboard, said junction box extends to the interior and to the exterior of that wallboard allowing conduit to be connection both inside and outside of said wallboard. The disclosed invention allows a complete rough-in installation to be finished in a single trip by the electrical contractor and greatly reduces the amount of sealant required for any smoke, fire or acoustical seal resulting in a reduction in installation time that can be as much as 70 percent.
As seen in the prior art, U.S. Pat. No. 8,633,384 B1 demonstrates a telescoping adjustable junction box made to adjust the junction box to be flush with the wall finish after installation of wallboard and finishes, so that a wiring device (e.g., a switch) can be installed therein. The '384 Patent is made for cable or cord installation in the wall cavity only, has no knockouts for conduit entry and is not made to extend past the wall finish. Unlike the '384 Patent, the disclosed invention provides a transition method from in-wall wiring to surface wiring for conduit systems. The disclosed invention is designed to protrude from the wall cavity, permitting connection of conduits located on the surface of the wall to connect with those enclosed within the wall. While a wiring device could, under some circumstances, be installed within the disclosed invention, such as to provide an area to splice wires, the primary purpose is to permit a transition from in-wall wiring to surface wiring which allows for simpler and more cost effective installation.
As further shown by the prior art, U.S. Pat. No. 2,697,535 demonstrates an octagon shaped junction box primarily made for installations in plaster ceilings and designed to provide for conduit entry knockouts spaced in a way to prevent interference between lath channel and conduits entering the junction box. The '535 Patent is designed to mount flush with the finished surface and would primarily be used to support lighting fixtures in a ceiling constructed of lath and plaster.
U.S. Pat. No. 3,701,448 demonstrates a junction box that provides the ability to mount the junction box to corrugated roofing panels. The primary use of the '448 Patent would be for surface mounting only to permit wire splicing or fixture mounting, typically on a ceiling, in which circumstances the positioning of the knockouts reduces the need to bend conduit to enter the junction box.
U.S. Pat. No. 7,165,366 B2 demonstrates a junction box with a shape designed to fit within the corrugations of a roof panel, permitting conduit to be connected without necessitating offsets in the conduit to be bent for surface mounting applications only, typically on a ceiling for wire splicing or fixture mounting. Unlike the '535 Patent, '448 Patent and '366 B2 Patent, the disclosed invention is designed primarily to be used inside walls and provides the ability to transition from in-wall wiring to surface wiring for conduit systems. The knockout placement on the disclosed invention is specifically designed to reduce or eliminate an electrician's need to bend conduit to route it into the disclosed invention.
U.S. Pat. No. 3,724,795 demonstrates a junction box permitting it to be mounted quickly to structural framing members such that the junction box is square to the framing and at a specified depth and therefore flush with the finished wall. Its primary use is the installation of wiring devices to be accessible from a finished wall.
U.S. Pat. No. 6,800,806 B1 demonstrates a junction box designed to enable it to quickly be mounted to the side of a wall stud or floor or ceiling joist where the purpose would be to enable the installation of wiring devices flush with the wall surface. The '806 B1 Patent includes knockouts for conduit and clamps for non-metallic or armor-clad cable permitting a variety of cables and conduits to enter the junction box.
U.S. Pat. No. 7,022,912 B1 demonstrates a junction box that is made for installation in conduit rack systems without the necessity of bending conduit entering the rack system enclosure, the application of which is in the installation of surface mounted or suspended group conduit installation racks where a splice or junction is required.
U.S. Pat. No. 7,554,032 B2 demonstrates a molded electrical junction box with multiple mounting features, the primary purpose of which is to install wiring devices for mounting flush with the wall surface of a finished wall. Unlike the '795 Patent, '806 B1 Patent, '912 B1 Patent, and '032 B2 Patent, the disclosed invention permits an installation which is simpler and more cost effective than the prior art to transition from in-wall wiring to surface wiring for conduit systems and includes side mounting brackets to enable the disclosed invention to be mounted to structural framing members quickly, while maintaining proper alignment depth to other junction boxes in the wall cavity simultaneously with enabling conduit to enter the junction box on the wall surface.
U.S. Pat. No. 5,448,012 demonstrates a method for installing a series of junction boxes with variations of extended depth that permit installation of electrical conduit, in straight sections, between pairs of non-adjacent junction boxes. The primary use of the '012 Patent is installation of wiring devices flush with the wall surface of a finished wall. Unlike the '012 Patent, the disclosed invention is designed to protrude from the wall cavity to permit conduits on the wall surface to be connected with conduits enclosed within the wall, thus providing the ability to transition from in-wall wiring to surface wiring with an installation that is simpler and more cost effective when compared to the prior art.
US 2009/0183891 demonstrates a junction box is a telescoping adjustable box made to adjust the junction box to be flush with the wall finish after installation of wallboard and finishes. This box is made to finish flush with the wall finish, for installation of a wiring device, with no entry provisions outside the wall cavity. Unlike the '012 Patent and 2009.0183891 A1 Patent, the disclosed invention is designed to protrude from the wall cavity to permit conduits on the wall surface to be connected with conduits enclosed within the wall, thus providing the ability to transition from in-wall wiring to surface wiring with an installation that is simpler and more cost effective when compared to the prior art.
U.S. Pat. No. 8,193,444 B2 demonstrates a junction box with a stair stepped back that permits it to be mounted to a framing member or strut to permit conduit to enter the junction box without the need of bending the conduit. The application for the '444 B2 patent is for the installation of wiring devices or splices of wires in surface mounting applications or in applications where wallboard would not be installed over framing members. Unlike the '444 B2 Patent, the disclosed invention permits an installation which is simpler and more cost effective than the prior art to transition from in-wall wiring to surface wiring for conduit systems and includes side mounting brackets to enable the disclosed invention to be mounted to structural framing members quickly, while maintaining proper alignment depth to other junction boxes in the wall cavity simultaneously while enabling conduit to enter the junction box on the wall surface. Additionally, the disclosed invention's full depth provides greater wire capacity and working space.
The prior art in the field does not disclose a junction box which enables transition from an in-wall wiring to surface wiring for conduit systems without the necessity of bending conduit and creating a large wallboard opening at the transition point. The prior art references are either designed to mount flush with the wall surface or do not protrude far enough from the wall surface to accommodate conduit entry on the wall surface. The disclosed invention permits the transition from in-wall wiring to surface wiring in a singular box that is easy to mount, cost effective to use, and reduces or eliminates an electrician's need to bend conduit to enable it to enter the junction box.
Accordingly, a primary object of the disclosed invention is to provide an electrical conduit junction box with a design that extends beyond both sides of the wallboard such that it can be independently supported from the building structure in compliance with the National Electric Code, section 314.23, while facilitating the connection of conduit to the electrical conduit junction box without necessitating the bending or offsetting of such conduit and providing a quick, easy and more efficient means of completing its installation and connection to the building structure and connecting conduit, as well as minimizing the alteration to the wallboard made necessary to properly position the electrical conduit junction box, and thereby reducing the time and material required for sealing gaps in the wallboard surface for fire, smoke or acoustical reasons.


A bearing chamber housing for supporting a shaft of a turbomachine is provided, the bearing chamber housing including an additively built-up housing wall which bounds an oil chamber of the bearing chamber housing radially outwardly relative to an axis of rotation of the shaft, the housing wall being built up with an oil duct which has an inlet opening toward the oil chamber for admission of oil from the oil chamber into the oil duct, and which has an outlet opening for discharging the oil from the oil duct, the outlet opening being located at a different axial position and at a different circumferential position than the inlet opening, considered relative to the axis of rotation of the shaft, and the oil duct having an extent with both an axial component and a circumferential component, at least over a portion thereof.

The turbomachine may be, for example, a jet engine, such as a turbofan engine. The turbomachine is functionally divided into a compressor, a combustor and a turbine. In the case of the jet engine, for example, drawn-in air is compressed by the compressor and mixed with jet fuel and burned in the downstream combustor. The resulting hot gas, a mixture of combustion gas and air, flows through the downstream turbine and is expanded therein. The turbine is typically made up of a plurality of stages, each including a stator (stator vane ring) and a rotor (rotor blade ring), the rotors being driven by the hot gas. In each stage, a portion of the internal energy is removed from the hot gas and converted into motion of the respective rotor blade ring and thereby of the shaft.

Bearing chamber housing for a turbomachine


An image forming apparatus includes an arm member. The arm member includes a cartridge abutment surface configured to abut the cartridge when the cartridge moves from a state in which the cartridge is at the attached position to a state in which the cartridge is detached from the main body, an opening and closing member abutment surface configured to abut the opening and closing member when the cartridge moves from the state in which the cartridge is at the attached position to the state in which the cartridge is detached from the main body to press the cartridge abutment surface, the opening and closing member abutment surface being substantially parallel to the cartridge abutment surface, and a force transmission portion extending in a direction normal to the cartridge abutment surface to linearly connect between the cartridge abutment surface and the opening and closing member abutment surface.

1. Field of the Invention
The present invention relates to an image forming apparatus for forming an image on a recording medium and discharging the same. In particular, the present invention relates to an image forming apparatus in which components needing replacement as the apparatus is used are formed into a cartridge which is attachable to and detachable from a main body of the apparatus.
2. Description of the Related Art
An image forming apparatus of such a type has an opening and closing cover configured to rotate to open the interior of a main body of the apparatus for the attachment/detachment of the cartridge. Japanese Patent Application Laid-Open No. 2005-242213 discusses an image forming apparatus whose opening and closing cover is provided with a push-in member for pushing in the cartridge to a proper position as the opening and closing cover is closed.
The cartridge push-in member also serves to abut the cartridge to hold the same so that the cartridge may not get out of the image forming apparatus due to a shock, vibration or the like applied to the apparatus when the apparatus is being transported with the cartridge attached to the apparatus. The shock the cartridge push-in member receives from the cartridge when the cartridge push-in member abuts the cartridge to hold the same is absorbed by the cartridge push-in member (hereinafter referred to as the push-in member) itself and the opening and closing cover. However, in the construction discussed in Japanese Patent Application Laid-Open No. 2005-242213, a moment is generated around the portion of the push-in member connected with the opening and closing cover as a result of the cartridge abutting the push-in member. Thus, high strength is required of the push-in member so that it can withstand fracture due to this moment. To secure such high strength, it is necessary to increase the wall thickness of the push-in member or to provide it with a reinforcing structure such as a reinforcing rib, thus resulting in an increase in size and cost.

Image forming apparatus operable for installing attachable/detachable cartidge therein


A method for measuring microscopic object velocities in fluid flow in a capillary tube including scanning a microscope focal plane through a fluid filled space for objects, where the scanning follows an interrupted repeating pattern having sub-patterns where the sub-patterns position the microscope focus plane beginning at a selected focus position at a first time and ending at the selected focus position at a later second time. A sensor registers images in image frames during the scanning. A first object image is registered in a first image frame at the selected focus position and a second object image is registered in a second image frame at the selected focus position. The object in the first object image and the second object image are identified as the same object. A processor determines a velocity for the identified object.

Lung cancer is the second most prevalent cancer in the United States and is the most lethal. Over 31 million patients in the United States (US) are at high risk for the development of lung cancer, primarily due to age, smoking history, and pollution and other factors including radon exposure, family history of lung cancer, etc. Approximately 160,000 US patients die of lung cancer each year. At the time of this writing, lung cancer can only be cured with surgery when detected in early stages, mainly stage I and II. However, lung cancer is known to be preceded by pre-cancerous conditions presenting as dysplastic cells. The detection of such pre-cancerous conditions can trigger preventative treatment that can reduce the risk of contracting lung cancer.
Advances in 3D imaging of biological cells using optical tomography have been implemented by Nelson as disclosed, for example, in U.S. Pat. No. 6,522,775, issued Feb. 18, 2003, and entitled "Apparatus and Method for Imaging Small Objects in a Flow Stream Using Optical Tomography," the full disclosure of which is incorporated by reference. Further major developments in the field are taught in Fauver et al., U.S. Pat. No. 7,738,945, issued Jun. 15, 2010, entitled "Method and Apparatus for Pseudo-Projection Formation for Optical Tomography," (Fauver '945) and Fauver et al., U.S. Pat. No. 7,907,765, issued Mar. 15, 2011, entitled "Focal Plane Tracking for Optical Microtomography," (Fauver '765) the full disclosures of Fauver '945 and Fauver '765 are also incorporated by reference. Building on the teachings therein, an early lung cancer detection technology has been developed by VisionGate, Inc., Phoenix, Ariz. to provide measurement advantages that have demonstrated a great improvement in the operating characteristics of conventional morphologic cytology analyses.
Processing in such an optical tomography system begins with specimen collection and preparation. For diagnostic applications in lung disease, patient sputum can be collected non-invasively in a clinic or at home. At the clinical lab, the sputum is processed to remove non-diagnostic material, fixed and then stained. Stained specimens are then mixed with an optical gel, and the suspension is injected into a microcapillary tube. Images of objects, such as cells, in the specimen are collected while the cells are rotated around 360-degrees relative to the image collection optics in an optical tomography system. The resultant images comprise a set of extended depth of field images from differing perspectives called "pseudo-projection images." The set of pseudo-projection images can be mathematically reconstructed using backprojection and filtering techniques to yield a 3D reconstruction of a cell of interest. Having isometric or roughly equal resolution in all three dimensions is an advantage in 3D tomographic cell imaging, especially for quantitative feature measurements and image analysis.
The 3D reconstructed digital image then remains available for analysis in order to enable the quantification through the measurement of sub-cellular structures, molecules or molecular probes of interest. An object such as a biological cell may be stained or labeled with at least one absorbing contrast agent or tagged molecular probe, and the measured amount and structure of this biomarker may yield important information about the disease state of the cell, including, but not limited to, various cancers such as lung, breast, prostate, cervical, stomach and pancreatic cancers, and various stages of dysplasia.
In order to obtain quality images of objects, such as biological cells in flow, accurate measurement of object velocities must be made. Accuracy is required in order to identify and track target images from one image frame to others at different times. One challenge to this requisite tracking presented by flowing objects is that they can be oriented randomly and tumble when flowing through liquid medium in a capillary tube, for example. Until the present invention, methods and systems lacked the ability to track such target objects in flow accurately and at an acceptably fast throughput rate.

Apparatus and method for measuring microscopic object velocities in flow