A continuous process for mixing polymer melts with additives, in particular polycarbonate melts with additives in liquid form, in solution or in dispersion is described. The additives are added to a main stream of polymer melt and are then mixed, preferably directly, with the main stream in a static mixer.

Additives may as is known undergo undesirable reactions at high temperature, both with the polymer matrix or other additives as well as without further reactants. Due to such reactions the amount of metered additives is on the one hand reduced, which curtails their action. On the other hand secondary products of the reactions may have a deleterious effect on the quality of the polymer, for example by impairing the color. In this connection, a long residence time at high temperature is above all harmful.
For thermoplastic molding compositions there are as is known numerous specifications with which the person skilled in the art in this field is familiar. These may include for example the number average or weight average of the molecular weight, chemical composition, degree or order of branching, contents of volatile or extractable substances, degree of crosslinking of elastomeric phases, viscosities at various shear rates, melt flow index, contents of additives, contents of terminal groups of molecules, content of non-meltable and/or colored particles, odour, color, or the shape of the product after manufacture and processing. The reasons why these specifications may be difficult to meet are just as multifarious.
These may involve for example fluctuations in the quality of the starting products or a wide range of factors interfering in the process. A further reason for products that do not meet the specifications may lie in start-up procedures or in the need to depart from the specification if throughputs or types of products are changed. These products that do not comply with the relevant specifications are referred to here as secondary products. Secondary products (e.g. recycled products like recycled polycarbonate) can be marketed only at lower prices or have to be disposed of, which leads to high costs and environmental stress due to unnecessary consumption of resources. For this reason it is desirable to find a process by means of which these secondary products may be economically recovered.
The mixing of additives with various polymers by means of mixers without moving parts (static mixers) is in principle known. The use of static mixers for such purposes corresponding to the prior art is described in "Chemische Industrie", 37(7), pp. 474–476, where polystyrene, HIPS and LLDPE are mentioned. The SMX type mixers shown there in FIG. 2 correspond to the current state of the art and are commonly used on an industrial scale. FIG. 1 of said reference shows two process variants, which are characterized hereinafter as 2.1 and 2.2:    2.1. The additives are metered in liquid form in the main stream in front of a static mixer. The disadvantage of this process is that it requires a very long static mixer in the main stream in order reliably to prevent the penetration of droplets, which in turn produces a high pressure loss and requires a long residence time. The long residence time is unfavorable since during this time undesirable secondary reactions of the additive components, of the additive components with one another or with the main stream may occur.    2.2. Pigments and solid additives are conveyed through an extruder in front of the static mixer.
This literature reference also discloses that a low viscosity additive is mixed in a bypass mixer with a side stream comprising ca. 10% of the overall stream.
DE 40 39 857 A1 describes a further process for the mixing of additives in a polymer stream, polyamide and polyester melts being preferred. In this case a side stream is withdrawn from a main stream, the additives are mixed with the side stream with the aid of an extruder fed with melt, and are mixed again with the main stream using a static mixer. The disadvantage of this process is the unavoidable rise in temperature of part of the main stream in the extruder, which on the one hand can impair the quality of the polymer and, in turn, allow undesirable secondary reactions of the additive components, of the additive components with one another or with the polymer of the secondary stream or main stream. A recovery of secondary products is not described in this specification.
DE 198 41 376 A1 describes a further process for the mixing of additives in polymers, in which the examples involve polyesters and copolyesters. Here too a side stream is withdrawn from the main stream, and more specifically by means of a planetary gear pump. The additives are mixed via a static mixer with the side stream and the side stream is afterward in turn mixed via a static mixer with the main stream. In this process it is not possible to incorporate secondary products into the main stream. Also, the temperature is the same as that of the main stream, which means that harmful reactions of the additives may occur at this temperature.
In EP 0 905 184 A2 it is stated that extruders, Banbury mixers, roller mills or kneaders may be used for mixing additives into polycarbonate in the melt. All these devices have the disadvantage that they can damage the polymer and the additives due to input of energy and the associated rise in temperature. The handling of thermoplastic polycarbonate in a roller mill might well be suitable only for laboratory use.
The prior art furthermore includes the following applications and publications:
DE 199 47 630 A1 describes a process for the continuous production of a thermoplastic polymer blend and its use. In this process a stream is directly withdrawn from the primary production and is mixed in a mixer with a side stream of another polymer, which may contain additives.
DE 100 50 023 A1 describes a mixing device and a process for the production of thermoplastic molding compositions, in particular additive batches, using twin-screw machines.
In "Plastverarbeiter", 11(43), 1992, "Statisches Mischen in der Kunststoffverarbeitung und -herstellung" an overview is given of the mixing operations that are carried out with static mixers. This article specifically discusses the various possible uses of an SMX type static mixer, which includes inter alia the mixing of low viscosity additives in polymer melts. The only product example that is mentioned there is the mixing of mineral oil into polystyrene.
The object of the present invention was to provide a process for mixing a main stream of polycarbonate with additives that obviates the disadvantages of the prior art and that minimizes the temperature stress of the additives and permits the use of secondary products.
The invention provides a continuous process for the mixing of polycarbonate melts with additives in liquid form, in solution or in dispersion, in particular in a process for the production of polycarbonate molding compositions, characterized in that the additives are added to a main stream of polymer melt and are then mixed, in particular directly, in a static mixer with the main stream.
A process is preferred that is characterized in that the temperature of the main stream before the mixing is less than 320° C., preferably less than 310° C. and particularly preferably less than 300° C.
The residence time of the main stream in the static mixer is preferably 20 to 120 seconds, particularly preferably 30 to 60 seconds.
A process is also preferred that is characterized in that the additives are fed to the main stream in the form of a side stream consisting of a premixture of polycarbonate melt and additive.
The weight ratio of the side stream to main stream is preferably 1:4 to 1:30, particularly preferably 1:5 to 1:20.
Also preferred is a process that is characterized in that the side stream is formed from molten polycarbonate granules and/or fractured polycarbonate product, in particular from polycarbonate recycling material.
Likewise, a process is preferred that is characterized in that part of the additives or all additives are fed after the melting of the polycarbonate for the side stream and are mixed in using a further static mixer to form the side stream.
The residence time in the further static mixer for the side stream is preferably 10 to 300 seconds, particularly preferably 20 to 120 seconds and most particularly preferably 30 to 60 seconds.
The invention also provides a continuous process for the mixing of high viscosity polymer melts as main stream in a flow tube or flow pipe with additives from a liquid side stream, characterized in that the additives are premixed with a part (portion) of the polymer melt in the side stream, the additive-containing side stream is fed via a line (feed line), in particular arranged centrally in the flow tube, into the main stream, the combined streams are intensively mixed in a first static mixer (10, FIG. 1) directly connected downstream (i.e. the side stream enters the main static mixer just before the main static mixer), and this premixture is finely divided in a mixing tube of enlarged cross-section and in a second static mixer (16, FIG. 1) of finer structure (smaller mesh width). "Smaller mesh width" means that there are more product throughput openings per unit of surface area.
Suitable polymers include all thermoplastic polymers, preferably polystyrene, copolymers of styrene with acrylic acid, methacrylic acid, α-methylstyrene, acrylic acid esters such as methyl methacrylate, butyl acrylate, etc., and especially acrylonitrile (SAN). These polymers may be modified with a rubber phase, for example polybutadiene, polyisoprene, polychloroprene, EPDM, polybutyl acrylate, etc., i.e. rubber modified copolymers such as polybutadiene or polybutylacrylate grafted with the a.m. copolymers like ABS.
In a preferred process the cross-section of the mixing tube of the second static mixer (16, FIG. 1) is by a factor of at least 1.2, preferably by a factor of at least 2 and particularly preferably by a factor of at least 3 larger than the cross-section of the first static mixer (10, FIG. 1).
A process is also preferred in which the number of product throughput openings (per unit of surface area) in the second static mixer is at least 1.5 times the number of product throughput openings (per unit of surface area) in the first static mixer.
Product throughput openings include all bores and openings in the static mixer through which, seen in cross-section through the mixer and pipeline, flows product.
Also preferred is a process that is characterized in that the mixture is finely mixed in a third static mixer, with or without enlarged cross-section, arranged downstream of the second static mixer.
The process is particularly suitable for polymer mixtures in which the mixture has a viscosity in the range from 1 Pa×s to 107 Pa×s.
The invention furthermore provides thermoplastic molding compositions of polycarbonate produced according to one of the aforementioned processes. Additives may impart multifarious properties to the polymer. These additives may for example include antioxidants, UV absorbers and light stabilizers, metal deactivators, peroxide traps, basic co-stabilizers, nucleating agents, benzofurans and indolinones acting as stabilizers or antioxidants, mold release agents, flame-inhibiting additives, antistatics, colorants and melt stabilizers.
Particularly suitable additives for the implementation of the process are described for example in Additives for Plastics Handbook, John Murphy, 1999, or Plastics Additives Handbook, Hans Zweifel, 2001.    1.1. Preferred suitable antioxidants for the implementation of the process are for example:    1.1.1. Alkylated monophenols, for example 2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-dimethylphenol, 2,6-di-tert.-butyl-4-ethylphenol, 2,6-di-tert.-butyl-4-n-butylphenol, 2,6-di-tert.-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-diocta-decyl-4-methylphenol, 2,4,6-tricyclohexyl-phenol, 2,6-di-tert.-butyl-4-methoxymethylphenol, nonylphenols that are linear or branched in the side chain, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyl-heptadec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyl-tridec-1′-yl)phenol.    1.1.2. Alkylthiomethylphenols, for example 2,4-dioctyithiomethyl-6-tert.-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthio-methyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.    1.1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert.-butyl-4-methoxyphenol, 2,5-di-tert.-butylhydroquinone, 2,5-di-tert.-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert.-butylhydroquinone, 2,5-di-tert.-butyl-4-hydroxyanisole, 3,5-di-tert.-butyl-4-hydroxyanisole, 3,5-di-tert.-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert.-butyl-4-hydroxyphenyl)adipate.    1.1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (Vitamin E).    1.1.5. Hydroxylated thiodiphenyl ethers, for example 2,2′-thiobis(6-tert.-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert.-butyl-3-methylphenol), 4,4′-thiobis(6-tert.-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec.-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.    1.1.6. Alkylidene bisphenols, for example 2,2′-methylenebis(6-tert.-butyl-4-methylphenol), 2,2′-methylenebis(6-tert.-butyl-4-ethylphenol), 2,2′-methylenebis-[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2′-methylenebis-(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert.-butylphenol), 2,2′-ethylidenebis(4,6-di-tert.-butylphenol), 2,2′-ethylidenebis(6-tert.-butyl-4-isobutylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylenebis(2,6-di-tert.-butyl-phenol), 4,4′-methylenebis(6-tert.-butyl-2-methylphenol), 1,1-bis(5-tert.-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert.-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert.-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis (5-tert.-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylenegly-colbis[3,3-bis(3′-tert.-butyl-4′-hydroxyphenyl)butyrate], bis(3-tert.-butyl-4-hydroxy-5-methylphenyl)di-cyclopentadiene, bis[2-(3′-tert.-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert.-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-butane, 2,2-bis(3,5-di-tert.-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert.-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methylphenyl)pentane.    1.1.7. O-, N- and S-benzyl compounds, for example 3,5,3′,5′-tetra-tert.-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert.-butylbenzyl mercaptoacetate, tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)amine, bis(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert.-butyl-4-hydroxybenzyl)-sulfide, isooctyl-3,5-di-tert.-butyl-4-hydroxybenzyl mercaptoacetate.    1.1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert.-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-tert.-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-tert.-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)malonate.    1.1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert.-butyl-4-hydroxybenzyl)phenol.    1.1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert.-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert.-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert.-butyl-4-hydroxyphenoxy)-1,3,5 triazine, 2,4,6-tris(3,5-di-tert.-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxy-benzyl)isocyanurate, 1,3,5-tris(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate, 2,4,6-tris(3,5-di-tert.-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert.-butyl-4-hydroxyphenylpropioyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.    1.1.11. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N-(3,5-di-tert.-butyl-4-hydroxyphenyl)carbamate.    1.1.12. Esters of β-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    1.1.13. Esters of β-(5-tert.-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    1.1.14. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl-hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    1.1.15. Esters of 3,5-di-tert.-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl-hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    1.1.16. Amides of β-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionic acid, for example N,N′-bis(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)hexamethylene-diamide, N,N′-bis-(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)tri-methylenediamide, N,N′-bis(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hydrazide, N,N′-bis[2-(3-[3,5-di-tert.-butyl-4-hydroxyphenyl]-propionyl-oxy)ethyl]oxamide (Naugard® XL-1 from Uniroyal).    1.1.17. Ascorbic acid (Vitamin C).    1.1.18. Amine antioxidants, for example N,N′-diisopropyl-p-phenylenediamine, N,N′-di-sec.-butyl-p-phenylenediamine, N,N′-bis(1,4′-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylene-diamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylene-diamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N′-dimethyl-N,N′-di-sec.-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenyl-amine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert.-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p′-di-tert.-octyl-diphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, bis(4-methoxy-phenyl)amine, 2,6-di-tert.-butyl-4-dimethyl-aminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl-methane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenyl-methane, 1,2-bis [(2-methylphenyl)amino]-ethane 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert.-octylated N-phenyl-1-naphthylamine, a mixture of monoalkylated and dialkylated tert.-butyl/tert.-octyldiphenyl-amines, a mixture of monoalkylated and dialkylated nonyldiphenylamines, a mixture of monoalkylated and dialkylated dodecyldiphenylamines, a mixture of monoalkylated and dialkylated isopropyl/isohexyldiphenylamines, a mixture of monoalkylated and dialkylated tert.-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of monoalkylated and dialkylated tert.-butyl/tert.-octylphenothiazines, a mixture of monoalkylated and dialkylated tert.-octylphenothiazines, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperid-4-ylhexamethylene-diamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6,6-tetramethyl-piperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol. Individual examples of these compounds or mixtures thereof may be used.    1.1.19. Preferred suitable thiosynergists for the execution of the process include for example dilauryl thiodipropionate and/or distearyl thiodipropionate.    1.1.20. Secondary antioxidants, phosphites and phosphonites include for example tris-(nonylphenyl)phosphite, tris(2,4-di-tert.-butylphenyl)phosphite, 3,9-bis(2,4-di.-tert.-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]-undecane, 3,9-bis(2,6-di-tert.-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane, 2,2′-methylenebis(4,6-di-tert.-butylphenyl) octyl phosphite, tetrakis(2,4-di-tert.-butylphenyl)-[1,1-biphenyl]-4,4′-diylbis-phosphonite, 2,2′-ethylidenebis(4,6-di-tert.-butylphenyl) fluorophosphite, o,o′-dioctadecylpentaerythritol-bis(phosphite), tris[2-[[2,4,8,10-tetra-tert.-butyldibenzo[d,f][1,3,2]dioxa-phosphepin-6-yl]oxy]ethyl]amine, bis(2,4-di-tert.-butyl-6-methylphenyl) ethyl phosphite, 2-butyl-2-ethyl-1,3-propanediyl 2,4,6-tri-tert.-butylphenyl-phosphite, pentaerythritol-bis-((2,4-dicumyl-phenyl)-phosphite), 2-4-6-tri-tert.-butylphenyl-2-butyl-2-ethyl-1,3-propane-diol phosphite.    1.2. UV absorbers and light stabilisers may be used in the process according to the invention in an amount of 0.01 to 15 wt. %, preferably 0.03 to 8 wt. %, referred to the weight of the composition. Particularly suitable UV absorbers and light stabilizers for the implementation of the process include for example:    1.2.1. 2-(2′-hydroxyphenyl)benzotriazoles, for example 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di-tert.-butyl-2′-hydroxyphenyl)benzo-triazole, 2-(5′-tert.-butyl-2′-hydroxyphenyl)benzo-triazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert.-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert.-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole, 2-(3′-sec.-butyl-5′-tert.-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)-benzotriazole, 2-(3′,5′-di-tert.-amyl-2′-hydroxyphenyl)benzotriazole, 2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, 2-(3′-tert.-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzo-triazole, 2-(3′-tert.-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzo-triazole, 2-(3′-tert.-butyl-2′-hydroxy-5′-(2-methoxycarbonyl-ethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert.-butyl-2′-hydroxy-5′-(2-methoxycarbony-lethyl)phenyl)benzotriazole, 2-(3′-tert.-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert.-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-benzotriazole, 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′-tert.-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)-phenylbenzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol]; the transesterification product of 2-[3′-tert.-butyl-5′-(2-methoxycarbony-lethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R—CH2CH2—COO—CH2CH2]2, where R=3′-tert.-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole, 2-[2′-hydroxy-3′-(1,1,3,3-tetramethyl-butyl)-5′-(α,α-dimethylbenzyl)phenyl]-benzotriazole.    1.2.2. 2-hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy-, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.    1.2.3. Esters of substituted and unsubstituted benzoic acids, such as for example 4-tert.-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, bibenzoylresorcinol, bis(4-tert.-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert.-butylphenyl-3,5-di-tert.-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert.-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert.-butyl-4-hydroxy-benzoate, 2-methyl-4,6-di-tert.-butylphenyl-3,5-di-tert.-butyl-4-hydroxy-benzoate.    1.2.4. Acrylates, for example ethyl-α-cyan-β,β-diphenyl acrylate, isooctyl-α-cyan-β,β-diphenyl acrylate, methyl-α-carbomethoxy cinnamate, methyl-α-cyan-β-methyl-p-methoxy cinnamate, butyl-α-cyan-β-methyl-p-methoxy cinnamate, methyl-α-carbomethoxy-p-methoxy cinnamate and N-(β-carbomethoxy-β-cyanvinyl)-2-methylindoline.    1.2.5. Nickel compounds, for example nickel complexes of 2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithio carbamate, nickel salts of the monoalkyl esters, for example of the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert.-butylbenzylphosphonic acid, nickel complexes of ketoximes, for example of 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.    1.2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetra-methyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl), n-butyl-3,5-di-tert.-butyl-4-hydroxybenzyl malonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert.-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butantetracarboxylate, 1,1′-(1,2-ethanediyl) bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethyl-piperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert.-butylbenzyl)-malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethyl-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropyl-amino)ethane, the condensate of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropyl-amino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclo-hexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecyl succinimide, N-(1,2,2,6,6-penta-methyl-4-piperidyl)-n-dodecyl succinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane and epi-chlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N′-bis(formyl)-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diesters of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, the reaction product of maleic anhydride α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.    1.2.7. Oxamides, for example 4,4′-dioctyloxy oxanilide, 2,2′-diethoxy oxanilide, 2,2′-dioctyloxy-5,5′-di-tert.-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert.-butoxanilide, 2-ethoxy-2′-ethyl oxanilide, N,N′-bis(3-dimethylamino-propyl)oxanide, 2-ethoxy-5-tert.-butyl-2′-ethoxanilide and their mixtures with 2-ethoxy-2′-ethyl-5,4′-di-tert.-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.    1.2.8. 2-(2-hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxy-phenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropy-Ioxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-(2-hydroxy-4-[3-(2-ethyl-hexyl-1-oxy)-2-hydroxypropyloxy]phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Individual examples of these compounds or mixtures thereof may be used.    1.3. Particularly suitable metal deactivators for the implementation of the process are for example N,N′-diphenyloxamide, N-salicylal-N′-salicyloylhydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)-oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoylbisphenyl hydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide. Individual examples of these compounds or mixtures thereof may be used.    1.4. Particularly suitable peroxide traps for the implementation of the process are for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis-(dodecylmercapto)propionate. Individual examples of these compounds or mixtures thereof may be used.    1.5. Particularly suitable basic co-stabilisers for the implementation of the process are for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivates, hydrazine derivates, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. Individual examples of these compounds or mixtures thereof may be used.    1.6. Particularly suitable nucleating agents for the implementation of the process are for example inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably of alkaline earth metals; organic compounds such as monocarboxylic acids or polycarboxylic acids and their salts, for example 4-tert.-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers). Particularly preferred are 1,3:2,4-bis(3′4′-dimethyl-benzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol and 1,3:2,4-di(benzylidene)sorbitol. Individual examples of these compounds or mixtures thereof may be used.    1.7. Particularly suitable other additives for the implementation of the process are for example plasticisers, lubricants, emulsifiers, pigments, viscosity modifiers, catalysts, flow-improving agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.    1.8. Particularly suitable benzofuranones and indolinones for the implementation of the process are for example those described in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-43 16 611; DE-A-43 16 622; DE-A-43 16 876; EP-A-0 589 839 or EP-A-0 591 102, or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert.-butylbenzofuran-2-one, 5,7-di-tert.-butyl-3-[4-(2-stearoyloxy-ethoxy)phenyl]benzofuran-2-one, 3,3′-bis[5,7-di-tert.-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert.-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethyl-phenyl)-5,7-di-tert.-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxy-phenyl)-5,7-di-tert.-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert.-butyl-benzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert.-butyl-benzofuran-2-one, lactone antioxidants such as

These compounds act for example as antioxidants. Individual examples of these compounds or mixtures thereof may be used.    1.9. Particularly suitable fluorescing plasticisers for the implementation of the process are listed in "Plastics Handbook", Eds. R. Gächter and H. Müller, Hanser Verlag, 3rd Edition, 1990, pp. 775–789.    1.10. Particularly suitable mold release agents for the implementation of the process are esters of aliphatic acids and alcohols, for example pentaerythritol tetrastearate and glycerol monostearate; they are used alone or as a mixture, preferably in an amount of 0.02 to 1 wt. % referred to the mass of the composition.    1.11. Particularly suitable flame-inhibiting additives for the implementation of the process are phosphate esters, i.e. triphenyl phosphate, resorcinol diphosphoric acid ester, bromine-containing compounds such as brominated phosphoric acid esters, brominated oligocarbonates and polycarbonates, as well as salts such as C4F9SO3−Na+.    1.12. Particularly suitable antistatic agents for the implementation of the process are sulfonate salts, for example tetraethylammonium salts of C12H25SO3− or C8F17SO3−.    1.13. Particularly suitable colorants for the implementation of the process are pigments as well as organic and inorganic dyes.    1.14. Compounds that contain epoxy groups, such as 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl carboxylate, copolymers of glycidyl methacrylate and epoxysilanes.    1.15. Compounds that contain anhydride groups, such as maleic anhydride, succinic anhydride, benzoic anhydride and phthalic anhydride.
The compounds of the groups 1.14 and 1.15 act as melt stabilisers. They may be used individually or as mixtures.
Thermoplastic, aromatic polycarbonates within the meaning of the present invention include homopolycarbonates as well as copolycarbonates; the polycarbonates may, in a known manner, be linear or branched.
Up to 80 mole %, preferably from 20 mole % up to 50 mole %, of the carbonate groups in the suitable polycarbonates according to the invention may be replaced by aromatic dicarboxylic acid ester groups. Such polycarbonates, which contain acid radicals of carbonic acid as well as acid radicals of aromatic dicarboxylic acids incorporated in the molecular chain, are termed aromatic polyester carbonates. For the sake of simplicity, in the present application they are included under the heading of thermoplastic, aromatic polycarbonates.
The preparation of the polycarbonates to be used in the process according to the invention takes place in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, wherein for the preparation of the polyester carbonates a proportion of the carbonic acid derivatives may be replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, and more specifically according to the proportion of the carbonate structure units to be replaced in the aromatic polycarbonates by aromatic dicarboxylic acid ester structure units.
Details of the production of polycarbonates are available in hundreds of patent specifications published over the last 40 years or so. By way of example reference may be made here simply to Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964;                D. C. Prevorsek, B. T. Debona and Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Morristown, N.J. 07960: "Synthesis of Poly(ester Carbonate) Copolymers" in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 19, 75–90 (1980);        D. Freitag, U. Grigo, P. R. Müller, N. Nouvertne', BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pp. 648–718, and finally        Drs U. Grigo, K. Kircher and P. R. Müller "Polycarbonate" in Becker/Braun, Kunststoff-Handbuch, Vol. 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag, Munich, Vienna 1992, pp. 117–299.
The thermoplastic polycarbonates that are preferably used in the process, including the thermoplastic, aromatic polyester carbonates, have a weight average molecular weight Mw (determined by measurement of the relative viscosity at 25° C. in CH2Cl2 and at a concentration of 0.5 g per 100 ml CH2Cl2) of 12,000 to 120,000, preferably 15,000 to 80,000 and in particular 15,000 to 60,000.
Suitable diphenols for the production of the polycarbonates are for example hydroquinone, resorcinol, dihydroxydiphenyl, bis-(hydroxyphenyl)-alkanes, bis(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)-sulfides, bis(hydroxy-phenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfones, bis-(hydroxyphenyl)-sulfoxides, (α,α-bis-(hydroxyphenyl)-diisopropylbenzenes, as well as their nuclear-alkylated and nuclear-halogenated compounds.
Preferred diphenols are 4,4′-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-1-phenylpro-pane, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis-(4-hydroxyphenyl)propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-m/p diisopropylbenzene, 2,2-bis-(3-methylthydroxyphenyl)-propane, bis-(3,5dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5dimethyl-4-hydroxyphenyl)-sulfone, 2,4-bis-(3,5-dimethyl-4hydroxyphenyl)2-methylbutane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-m/p-diisopropylbenzene,2,2- and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
Particularly preferred diphenols are 4,4′-dihydroxydiphenyl, 1,1-bis-(4-hydroxyphenyl)-phenylethane, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-propane), 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-m/p diisopropylbenzene and 1,1-bis-(4-hydroxy-phenyl)-3,3,5-trimethylcyclohexane.
These and further suitable diphenols are described for example in the patent specifications: U.S. Pat. No. 3,028,635, U.S. Pat. No. 2,999,835, U.S. Pat. No. 3,148,172, U.S. Pat. No. 2,991,273, U.S. Pat. No. 3,271,367, U.S. Pat. No. 4,982,014 and U.S. Pat. No. 2,999,846, in German laid-open specifications DE-A-1 570 703, DE-A-2 063 050, DE-A-2 036 052, DE-A-2 211 956 and DE-A-3 832 396, in French patent specification FR 1 561 518, in the monograph by H. Schnell "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York 1964, as well as in the Japanese laid-open specifications 62039/1986, 62040/1986 and 105550/1986.
In the case of homopolycarbonates only one diphenol is used, while in the case of copolycarbonates several diphenols are used, in which connection obviously the bisphenols that are used, like all other chemicals and auxiliary substances added to the synthesis, may be contaminated with impurities derived from their own synthesis, although it is desirable to work with raw materials that are as pure as possible.
Suitable chain terminators include monophenols as well as monocarboxylic acids. Suitable monophenols include phenol, alkylphenols such as cresols, p-tert.-butylphenol, p-n-octylphenol, p-iso-octylphenol, p-n-nonylphenol and p-iso-nonylphenol, halogenated phenols such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol, and their mixtures.
Suitable monocarboxylic acids include benzoic acid, alkylbenzoic acids and halogenated benzoic acids.
Preferred chain terminators are phenols of the formula (I)R6-Ph-OH  (I)wherein R6 denotes H or a branched or unbranched C1–C18-alkyl radical.
The amount of chain terminators used is 0.5 mole % to 10 mole % relative to moles of diphenols used in each case. The addition of the chain terminators may take place before, during or after the phosgenation.
Suitable branching agents are the trifunctional or higher than trifunctional compounds known in polycarbonate chemistry, particularly those with three or more phenolic OH groups.
Suitable branching agents are for example phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene-2,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxy-phenyl)-phenylmethane, 2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis-(4-hydroxyphenylisopropyl)-phenol, 2,6-bis-(2-hydroxy-5′-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, hexa-(4-(4-hydroxyphenylisopropyl)phenyl)-ortho-terephthalic acid ester, tetra-(4-hydroxy-phenyl)-methane, tetra-(4-(4-hydroxyphenyl-isopropyl)-phenoxy)-methane and 1,4-bis(4′,4″-dihydroxy-triphenyl)-methyl)-benzene, as well as 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.
The amount of branching agents optionally used is 0.05 mole % to 2.5 mole % relative to moles of diphenols used in each case.
The branching agents may be added either together with the diphenols and the chain terminators in the aqueous alkaline phase, or may be dissolved in an organic solvent and added before the phosgenation.
All these procedures for the production of the polycarbonates are known to the person skilled in the art.
Suitable aromatic dicarboxylic acids for the production of the polyester carbonates are for example phthalic acid, terephthalic acid, isophthalic acid, tert.-butylisophthalic acid, 3,3′-diphenyldicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4-benzophenonedicarboxylic acid, 3,4′-benzophenonedicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 2,2-bis-(4-carboxyphenyl)-propane, trimethyl-3-phenylindane-4,5′-dicarboxylic acid.
Among the aromatic dicarboxylic acids, terephthalic acid and/or isophthalic acid are particularly preferably used.
Derivatives of the dicarboxylic acids include the dicarboxylic acid dihalides and the dicarboxylic acid dialkyl esters, in particular the dicarboxylic acid dichlorides and the dicarboxylic acid dimethyl esters.
The replacement of the carbonate groups by the aromatic dicarboxylic acid ester groups takes place substantially stoichiometrically and also quantitatively, so that the molar ratio of the reactants is also reproduced in the finished polyester carbonate. The incorporation of the aromatic dicarboxylic acid ester groups may take place randomly as well as in a blockwise manner.
Preferred processes for producing the polycarbonates, including the polyester carbonates, to be used according to the invention are the known phase interface process and the known melt transesterification process.
In the first case phosgene is preferably used as carbonic acid derivative, while in the latter case diphenyl carbonate is preferably used. Catalysts, solvents, working-up, reaction conditions, etc., for the production of the polycarbonates are sufficiently described and known in both cases.
The polycarbonate molding compositions according to the invention may be processed into molded articles in conventional processing equipment according to known methods under the processing parameters conventionally used for polycarbonates.
A molten main stream may occur in the primary production of polycarbonate from various processes. The following cases 3.1 and 3.2 should be understood as examples that illustrate the scope of the invention without however restricting it.    3.1. DE 100 05 151 A1 (corresponding to U.S. Pat. No. 6,620,906 that is incorporated herein by reference) describes a multistage process for the production of very pure polycarbonate by the phase interface process. In this process the washed and filtered solution with a polymer fraction of 5 to 20 wt. % is adjusted to a concentration of 60 to 75 wt. % in one or more steps in which in each case there may be used tubular heat exchangers with downstream-connected separators, thin-layer evaporators or spiral coil evaporators with downstream-connected separators or a combination of tubular heat exchangers and spiral coil evaporators with downstream-connected separators, and in which the pressure in the last stage is between 0.1 MPa and 0.4 MPa. In a further stage the solution is fed to a tubular heat exchanger with downstream-connected separator, which at a temperature of 250° to 350° C. concentrates the solution to at least 95 wt. %, in particular to 98 to 99.5 wt. %. In a further stage the solution containing residues of solvent and/or other volatile components is concentrated in a further tubular heat exchanger or an extrusion vapourizer at a temperature of 250° to 350° C. to a solvent content of 5 to 500 ppm. The main stream according to the invention is in this case added to the discharge of the last stage.    3.2 DE 101 198 51 (corresponding to U.S. Pat. No. 6,630,563 that is incorporated herein by reference) describes a process for the continuous production of polycarbonates from oligocarbonates according to the transesterification process with vapourization of monophenols in a reactor, which permits the constant formation of free films at film formation rates greater than 10. The reactor is in this connection designed as an horizontal cylinder in which perforated discs rotate on a hollow shaft. The film formation rate is defined as the ratio of the amount of the material that when pulled off from the rotating disc flows downwardly again in the form of a free film, to the total amount of the throughput of the reactor. The main stream according to the invention is in this case added to the discharge from this reactor.
It was surprisingly found that molten polycarbonate may be mixed with additives at the high temperatures prevailing in the static mixer and at the residence time required in the static mixer, a product thereby being formed that has excellent color and very good properties. The temperatures of the main stream are in this connection below 320° C., preferably below 310° C. and particularly preferably below 300° C. The residence times in this static mixer (hereinafter termed main static mixer) are between 10 and 600 seconds, preferably between 20 and 120 seconds and particularly preferably between 30 and 60 seconds. Additives in solid form or in the form of a premixutre with polymer (so-called master batches) may also be mixed with the granules. In addition it is possible to mix liquid additives in the melting device. In both cases a premixing of the additives with the polymer stream may be carried out in the melting device. The polymer stream that is thereby obtained is mixed in a static mixer (hereinafter termed side static mixer) with further, liquid additives with a residence time between 10 and 300 seconds, preferably between 20 and 180 seconds and particularly preferably between 30 and 120 seconds, and is added to the main stream, with which it is mixed in turn by means of a static mixer. It is particularly convenient as regards the product quality if the temperature of the side stream is below that of the main stream, since in this way the overall residence time of the additives at the high temperature of the main stream is less than in the case of direct metering in front of the main static mixer. It was surprisingly found that under these conditions the quality of the main stream remains within the specifications even when using secondary products. A ratio of side stream to main stream of between 1:4 and 1:30 is preferred, the ratio particularly preferably being between 1:5 and 1:20.
The melting device may be designed according to the prior art by a person skilled in the art and may for example be a single-screw extruder, a co- or counter rotating twin screw extruder, an intermeshing co-rotating twin screw extruder, multi screw extruder rotating in the same direction, or a co-kneader. An intermeshing co-rotating twin screw extruder is preferably used. A unit to increase the pressure, preferably a gear pump, may be employed after the melting device.
The static mixers that are used may likewise be designed according to the prior art by a person skilled in the art. SMX type static mixers may preferably be employed (see U.S. Pat. No. 4,062,524) as well as mixers according to DE 100 31 766 A1 or U.S. Pat. No. 6,394,644 B1.
The invention is described in more detail hereinafter by way of example and with reference to FIG. 1, which shows diagrammatically the process procedure.

Process for mixing polymer melts with additives


A construction machine is provided with a control device having an operating panel with operating elements, which can assume numerous switching states/positions, a control and monitoring unit for controlling machine components via control signals signalling the switching state/position of associated operating elements, and a display/signal unit interacting with the control and monitoring unit. The control device provides first and second signal transmission paths for transmitting a first control signal signalling the switching state/position of a first operating element and a second control signal signalling the switching state/position of a second operating element, respectively. The control signals are checked for the existence of a plausibility criterion. If the plausibility criterion is not met, signal transmission over one or the other signal transmission path is deactivated, wherein the functionality of the relevant component is checked. Switching to emergency operation is only possible after confirmation of the functionality of the relevant component.

The known self-propelled construction machines generally have a machine frame which is supported by a chassis having at least two running gears and at least one piece of work equipment arranged on the machine frame. The running gears can have chains or wheels or bandages. Self-propelled construction machines are known which have equipment for working the ground, for example for removing damaged road layers (road milling machine), for preparing the ground for road construction or reprocessing existing road surfaces (stabilisers, recyclers) or for mining mineral resources (surface miner). Lifting devices can generally be assigned to the individual running gears of the construction machine in order to be able to lower and raise the machine frame together with the work equipment relative to the ground surface. A height-adjustable edge protector can be provided on both sides of the milling or cutting roller. The roller housing can be closed on the front side in the working direction by a height-adjustable hold-down element and on the rear side by a height-adjustable scraper.
Examples of construction machines also include the known slipform pavers, road pavers, rollers, crushers, graders, loaders, cranes, etc.
The known construction machines have a variety of components that can perform certain functions. These components include, for example, the lifting devices for height adjustment of the machine frame, the height-adjustable edge protection and the height-adjustable hold-down element or scraper. "Components of a construction machine" are also understood to mean, for example, pumps or headlights that can be switched on or off.
The individual components of the construction machine are controlled by a control and monitoring unit. Operating elements are provided for operating the construction machine, with which the machine operator can influence the individual components. The operating elements can assume a plurality of switching states or positions. For example, by actuating the operating elements, the machine operator can extend and retract the lifting devices and adjust the height of the edge protection, hold-down element or scraper, or switch a pump or a headlight on and off. Piston arrangements/cylinder arrangements, which are controlled by the control and monitoring unit, are generally provided for extending and retracting the lifting devices and for adjusting the height of the edge protection, hold-down element or scraper.
In addition, the known construction machines have a display and/or signal unit which interacts with the control and monitoring unit and on which the individual operating states can be indicated or signalled optically and/or acoustically and/or in a tactile manner.
With increasing automation, the demands on the safety of the construction machine increase. Safe operation of the construction machine requires correct functioning of the different components of the construction machine. If the machine operator actuates an operating element on the operating panel, it must be ensured that the component(s) assigned to the operating element function(s) correctly. In the event of a safety-relevant malfunction, the operation of the construction machine should be interrupted.
WO 2005/003869 A1 describes a device and a method for the automated control of an operating sequence of a technical system. The device comprises two control units. One control unit generates control commands that are designed to control the system, and the other control unit generates control commands that are designed to perform safety functions.
A controller for a construction machine is known from EP 2 844 804 B1, which has an operating panel having operating elements and a control and monitoring unit for controlling actuators of the construction machine. The device comprises a display unit which can take over the function of the operating panel in the event of a malfunction.

Construction machine having a device for controlling the construction machine and method for controlling a construction machine


A improved liquid dispenser is provided which consists of a container for holding liquid therein. A mechanism extending into and upwardly from the container is for dispensing the liquid out of the container, so that the liquid can be used in convenient amounts. A cover engages with the liquid dispensing mechanism extending upwardly from the container to allow the liquid to exit from the cover.

1. Field of the Invention
The instant invention relates generally to receptacles and more specifically it relates to an improved liquid dispenser.
2. Description of the Prior Art
Numerous receptacles have been provided in prior art that are adapted to hold and carry various types of materials, so that the materials can be utilized therefrom. While these units may be suitable for the particular purpose to which they address, they would not be as suitable for the purposes of the present invention as heretofore described.

Liquid dispenser having movable head as pump actuator


The present invention relates to a pharmaceutical composition useful for preventing/treating pain, which comprises combination of gabapentin or pregabalin, or pharmaceutically acceptable salts thereof and N-type calcium channel antagonists or pharmaceutically acceptable salts thereof such as a compound having the following structure.

The present invention relates to a pharmaceutical composition comprising as active substances (a) gabapentin or pregabalin or pharmaceutically acceptable salts thereof and (b) N-type calcium channel antagonist or pharmaceutically acceptable salts thereof, those pharmaceutical composition is primarily effective for prevention, reduction and treatment of pain.
The present invention also relates to a method for preventing, reducing and treating pain using the above-mentioned active substances, and the use of these active substances.
Gabapentin is known to have a pain relief effect, although its mechanism of action remains elusive. Gabapentin is a derivative of γ-amino butyric acid (GABA), but it is shown not to bind to GABA receptors. Nonetheless, gabapentin can work to increase the concentration of GABA in human brain and the ratio of GABA synthesis. The GABA is an inhibitory neurotransmitter and GABA agonist has been identified as providing outstanding antiallodynia action in animal models, which suggests that gabapentin can exert its analgesic effects through the above-mentioned mode of action associated with GABA (Acta Neurol. Scand. 101:359-371, 2000). In addition, it is suggested that gabapentin can inhibit calcium current because gabapentin is shown to bind to the α2δ subunit of calcium channels. However, it is reported on one hand that gabapentin does not act on voltage-dependent calcium channels including N-type calcium channel (Epilepsy Res. 16:89-98, 1993); and it is reported on the other hand that gabapentin does not act on N-type calcium channel, but acts on P/Q type calcium channel (Br. J. Pharmacol. 130:900-906, 2000). Further, there is also a report concluding that gabapentin acts on all of N-, L- and P/Q type calcium channels (Br. J. Pharmacol. 135:257-265, 2002). As mentioned above, there are still a variety of different suggestions and a reliable theory has not yet been established.
Pregabalin is also a derivative of GABA and is known to share the pain control effectiveness. Although the mechanism of action associated with pregabalin has not yet been clarified, pregabalin is thought to increase the GABA concentration in nervous tissues in a similar manner of gabapentin. In addition, it is known that pregabalin works to liberate gabapentin from its binding site (Epilepsy Res. 34:1-41, 1999).
As is known, the N-type calcium channel antagonist has a pain control effect, too. The N-type calcium channel antagonist acts on the N-type calcium channels specifically positioned in the nerve system to inhibit calcium influx into the nerves. The N-type calcium channels, which are present at high density in presynaptic terminals of the afferent nociceptive nerve serving to transmit pain signals are concerned in transmission of the pain signals to central nervous system (Exp. Opin. Ther. Patents 8:1237-1250, 1998). The N-type calcium channel antagonist can inhibit the influx of calcium into the nerves via the N-type calcium channels to modulate release of the neurotransmitter and inhibit transmission of pain signals to central nervous system. In this way the N-type calcium channel antagonist can exhibit its analgesic action.
There are conventionally known some embodiments where gabapentin or pregabalin is used in combination with different kinds of pharmaceutical drugs, as cited in the following references and patent specifications:
(1) Combination of (a) gabapentin with (b) lamotrigine or carbamazepine (Eur. Neurol., vol. 44, 45-48, 2000)
(2) Combination of (a) gabapentin with (b) a non-NMDA antagonist, 6-cyano-7-nitroquinoxaline-2,3-dione (Anesthesiology, vol. 92, 500-506, 2000)
(3) Combination of (a) gabapentin with (b) a nonsteroidal anti-inflammatory drug, ibuprofen (Anesthesiology, vol. 91, 1006-1013, 1999)
(4) Combination of (a) gabapentin with (b) morphine (Pain, vol. 72, 375-382, 1997)
(5) Combination of (a) gabapentin or pregabalin with (b) any of an analgesic, N-methyl-D-aspartate receptor antagonist or nonsteroidal anti-inflammatory drug (WO 99/12537)
(6) Combination of (a) gabapentin or pregabalin with (b) a sodium channel inhibitor (WO 00/61188)
Nonetheless, there is not known any pharmaceutical composition comprising as active substances (a) gabapentin or pregabalin or pharmaceutically acceptable salts thereof and (b) N-type calcium channel antagonist or pharmaceutically acceptable salts thereof, and there is not recognized any effect as obtained by the use of gabapentin or pregabalin together with N-type calcium channel antagonist.
Further, WO2001/76576 discloses a pharmaceutical composition for treatment of pain and migraine, comprising (a) nicotine receptor partial agonist, (b) analgesic, and (c) pharmaceutically acceptable carrier. According to the disclosure, the component (b) of the above-mentioned pharmaceutical composition, that is, an analgesic drug, includes anticonvulsants, N-type calcium channel inhibitors or the like, wherein as the anticonvulsant gabapentin, pregabalin or the like is used. However, WO2001/76576 discloses a pharmaceutical composition for treatment of pain and migraine, characterized by comprising the three components (a), (b) and (c), and the composition can achieve its efficacy resulting from the combined use of the three components (a), (b) and (c). There is no description about a pharmaceutical composition of the present invention which comprises as active substances (a) gabapentin or pregabalin or pharmaceutically acceptable salts thereof and (b) N-type calcium channel antagonist or pharmaceutically acceptable salts thereof. No description is found that suggests the effects as obtained by the combined use of (a) gabapentin or pregabalin or pharmaceutically acceptable salts thereof with (b) N-type calcium channel antagonist or pharmaceutically acceptable salts thereof.
In the area of prevention and treatment of pain, there is an increasing demand for a significantly improved pharmaceutical drug with potentiated efficacy as compared with the conventional ones, with producing no side effects. For example, evaluation by the patients with post-herpetic neuralgia reported that the treatment effectiveness for gabapentin reached approximately 60% (Acta Neurol. Scand. 101:359-371, 2000). To further potentiate the efficacy is therefore considered to be of great significance in the treatment of pain.
Gabapentin at high doses is needed when gabapentin is used for the treatment of pain. However, it has been proved that gabapentin at high doses produce side effects such as somnolence, dizziness and ataxia (Pharmacol. Ther. 88:163-185, 2000)
Also, a significant depression of motor system has been observed in rats at high doses of pregabalin (Br. J. Pharmacol. 121: 1513-1522, 1997), and in addition, development of side effects associated with pregabalin including somnolence and dizziness has been recognized in clinical tests (Neurology. 54(S3): A421, 2000).
Accordingly, there is an increasing demand for a pain control therapy capable of lowering an incidence of side effects which are recognized in many of the currently available treatments of pain.

Pharmaceutical composition containing gabapentin or pregabalin and N-type calcium channel antagonist


An embodiment of the invention includes a memory and apparatus for packet processing in a switching network. The memory includes a plurality of words where each word includes a plurality of bits. Each word in the plurality of words is addressed by separate and distinct read address. A logic circuit performs a logical “OR” function on all the bit in all the words addressed by the separate and distinct read addresses and outputs a result.

OpenFlow packet processing centers around flow tables containing flow entries, each having ternary values for a selected set of packet header fields. For each packet, flow entries are searched in order, with the first matching entry returned. OpenFlow defines a set of recognized packet header fields including the commonly used Medium Access Control (MAC) source and destination addresses, ether type, Internet Protocol (IP) source and destination addresses, IP protocol, Transmission Control Protocol (TCP) port numbers, Virtual Local Area Network (VLAN) and Multiprotocol Label Switching (MPLS) tags, etc., in addition to user defined extensible fields, and a metadata field to hold non-packet information. The input port Identification (ID) is also provided as a match input.
Associated with each flow entry is a set of actions to be executed upon a match. The defined actions include setting values into any of the packet header's recognized fields, pushing and popping VLAN and MPLS tags, performing Provider Backbone Bridge (PBB) encapsulations and decapsulations, as well as miscellaneous operations such as Time to Live (TTL) manipulations. Actions can also include assigning the packet to an output port and queue, sending the packet to the controller, or dropping it. With OpenFlow still a new and evolving standard, it is anticipated that implementors will create user defined extensions for any required capabilities not yet in the standard, such as other encapsulation types (Generic Routing Encapsulation (GRE), Network Virtualization using Generic Routing Encapsulation (NVGRE), Virtual Extensible Local Area Network (VXLAN) etc.).
Openflow 1.0 defined a single flow table. Later versions allow multiple tables, numbered and processed sequentially, with actions taken as a result of any stage modifying the packet before it is sent to the next stage. A different action option allows selected modifications to be postponed until after all match stages are executed. A flow entry match also specifies the address of the next table to be executed as a forward-only branch.
Openflow groups provide for implementation of capabilities including multicasting and Equal Cost Multipath (ECMP). An OpenFlow group is a type of action, defined as a collection of buckets, where each bucket contains actions of the types defined above, in addition to optionally recursively containing other groups. OpenFlow ALL groups implement multicast by executing all buckets, each on a different copy of the packet. OpenFlow SELECT groups execute one randomly selected bucket, implementing ECMP, equal cost multipath, and with optional weights attached to each bucket, unequal cost multipath (uECMP). The random selection is typically done by hashing on a selected set of packet headers, so that different flows are routed to different buckets, but all packets from the same flow receive identical treatment. Fast failover groups execute the first bucket associated with a live output port, allowing quick reaction to link failures. OpenFlow indirect groups contain a single bucket, and are useful simply as a layer of indirection.
OpenFlow defines an implementation of meters, which are used to measure data flow rates. Meters are a type of action executable on a flow table match. A meter includes a number of bands, typically two or three, each of which has a defined maximum data rate and optional burst size. Using a leaky bucket analogy, a meter band is a bucket filled by the packet data rate and drained at a constant allowed data rate. Overflow occurs if the integration of data rate exceeding quota is larger than the burst size. Overflowing one band triggers activity into the next band which presumably allows a higher data rate. Meter bands are often informally named with colors, such as green, yellow and red for a three color meter. Openflow provides for remarking the packet Differentiated Services Code Point (DSCP) field as a result of overflowing the base band. This information might be used later to direct the packet to a different queue where it may be more subject to delay or dropping in case of congestion.
OpenFlow defines statistics collecting counters, mostly packet and byte counters, for flow tables, flow table entries, groups and group buckets, meters and meter bands, input/output ports and queues. While most of them are optional, the statistics information they provide are useful to implementers.
As will be explained later, memory requirements for flow tables, action entries and statistics counters contribute a great deal to cost considerations for a large portion of a switch chip.
OpenFlow switches communicate with a network controller through a set of messages defined by the standard. Messages are provided for initial configuration, and for set up, modification, or deletion of flow table, group and meter entries. Statistics information can be requested by the controller and communicated back by the switch. Flow entries can as an action direct a packet to be sent to the controller, and the controller can send packets back to the switch for OpenFlow processing. A common mode of operation is that if a packet is unexpectedly unmatched in a flow table, the packet is sent to the controller, which responds by installing flows into one or more switches. This implements Software Defined Networking (SDN) canonical separation of data plane and control plane processing; switch functionality is confined to matching flows and taking the indicated actions; any unrecognized pattern is sent up to the controller which shoulders the responsibility for all high level decisions.
A description will be provided of the high level design of a match stage, a unit which can be cascaded to implement the core of OpenFlow functionality: providing the flow tables, matching of packet fields against flow table entries, taking the actions indicated by the match, and collecting statistics. U.S. patent application Ser. No. 14/072,989 "An Openflow Match and Action Pipeline" herein incorporated by reference, provides additional background material in this area by describing additional aspects of a match stage implementation. The implementation to be described targets a 64 port by 10 Gbit/s switch, which produces a maximum packet rate of 960M packets/s. If a match stage pipeline is run at 1 GHz or slightly less, each packet has a single clock cycle to flow through the pipe.
The parser accepts the incoming packet data and produces a 4 k bit packet header vector as its output, with each defined header field in a fixed, though configurable, position. This 4 k bit vector provides the input data to the match pipeline of match units. The 4 k bit vector is composed of a number of 8, 16, and 32 bit fields, each of which has an associated valid bit.
OpenFlow defines all tables with ternary matching capability; that is, each table bit can have the ternary values of 0, 1 or don't-care. Wildcarding bits allow single table entries to match a wide variety of packets. At the performance levels targeted, 1 packet per clock cycle, ternary match tables are implemented with TCAM (ternary content addressable memory) modules. Another useful type of table is an exact match table, where no wildcarding is allowed, and packets must exactly match table entries. These can be implemented as hash tables in SRAM, with the advantage that an SRAM is significantly less area, than a TCAM table of equivalent bit count.
Exact match tables are implemented by using SRAMs as hash tables. Generally a hash table takes some or all of the input bits of a search word, and generates a pseudorandom, but predictable, number from those bits. One method of hashing generates an N bit address from an M bit input, where for each of the N hash output bits, a separate M bit mask is and'ed with the input data, and then the parity of the result is taken. The input bit mask for each hash output bit is different, and there are methods known in the art to select masks with desirable properties. This method is equivalent to the mathematical operation of a Galois Field multiplication. There are multiple methods of generating hash addresses known in the art, but all of them attempt to generate an address, where for all data inputs, the addresses end up uniformly distributed across the N bit address space, so that hash table entries are evenly spread out over all words of the SRAMs used for hash table data storage.
Hash tables operate by accessing an array of data at that hashed location and checking to determine whether the accessed data is the desired data. This check is performed by doing a comparison between the desired data and accessed data to determine their equality. Hash tables also have to contend with the possibility of address collisions, where multiple distinct inputs hash to the same address. There are many techniques known in the art for accomplishing this. Multiway hashing addresses this by making K hash addresses instead of one and looking up the data in those K separate locations in K individual arrays. When an entry is to be added, these multi-way hash tables provide several possible locations, all equally good, increasing the probability that one of the locations will be empty.
A further refinement is to implement exact match tables using Cuckoo hash tables, multi-way hash tables distinguished by a fill algorithm providing high hash table occupancy. When adding an entry, if all possible locations for that entry are full, since all current occupants also have other choices for their locations, one of them can be evicted to an alternative location, possibly resulting in a chain of evictions and continuing until an entry is placed in an empty location. Cuckoo hash tables routinely achieve high efficiencies, for example, above 95% occupancy for 4-way hash tables. Reads are deterministically performed in one cycle, with all ways accessed in parallel. While all of this is known art, the essential element is that to implement OpenFlow exact match tables, multi-way hash tables are used where a number (preferably at least 4) separate SRAM modules each compute individual hash keys and determine whether the search data exists at the computed hash location. As a result, a number of SRAM modules are used.
Tables can be made deeper by incorporating additional memory modules, with each memory either adding another way to the hash table or incrementing the number of items contained in an individual way. If multiple items are contained in an individual way, an address lookup yields multiple entries, any of which when compared may turn out to be the desired data. Alternatively, this can be viewed as a multi-bank hash table where some of the banks use the same hashed address, so the number of hash keys is less than the number of banks.
Match data input to tables may vary significantly in width, from single fields to hundreds of bits. For example, a max match width may be 640 bits. Narrower widths can be accommodated by breaking the 640 b match memory into units, for example 8 units of 80 bits each. Then these 8 units may be combined to make an 8× deeper table (with 8×the number of entries) or may instead create 8 separate tables. Memory units may be combined in groups, for example 2 units wide for 160 bits, etc. If 4 ways are required in the exact match table of a match stage, this results in an array of 8×4 memory units, each of which can match 80 bit wide data. The 80 bits of match per unit memory is an approximation which will be explained in more detail further below. Each memory is 1000 words deep in this example.
Ternary matches using TCAM are also configured to match wide or narrow entries, with a 640 b wide memory split into 8 80 bit units, which like the SRAM exact match memory may be used to create narrow deeper memories or separate memories or combined in groups as desired. Given the larger area of TCAM, less of it is typically provided than exact match memory, for example, ½ or ¼. The TCAM could also be divided into a different number of units, for example into 16 40 bit units.
When either a ternary or exact match is found, it provides several pointers which together contain the required information to perform the desired actions. These include an instruction memory address, an action memory address and size, and a next table address. Actions are performed by modifying fields of the 4000 bit packet header vector. There are 64, 96 and 64 words of 8, 16 and 32 b respectively in the packet header vector, with an associated valid bit for each. Note that the number of words of each size described above is illustrative and could easily be changed to larger or smaller numbers in a specific design. As will be described later in more detail, the action engine inventively uses a Very Long Instruction Word (VLIW) architecture, where each of these words has its own functional unit to compute updated values. The units of smaller words can be combined to execute a larger field instruction, for example, 2 8 bit units can merge to operate on their data as a single 16 bit field. There is a VLIW instruction memory with individual instruction fields for each of these words.
OpenFlow specifies simple actions such as setting a field to a value as well as complex operations, such as PBB encapsulate or inner-to-outer or outer-to-inner TTL copies where the outer and inner fields may be one of a number of choices. Complex operations can be easily decomposed into multiple actions on separate fields but complex modifications to each individual field become more difficult as the data line rate increases. These complex modifications can be subroutines at low speeds but must be flattened into single-cycle operations at the packet per clock cycle rate of this device. It is important to provide action capabilities powerful enough to handle the expected types of operations. A general set of conditionalized arithmetic, logical, multiplexing, and bit field manipulation capabilities is provided. Since the chip area of the action engine is dominated by selecting source operands (action data and packet header words) rather than by computation, flexible action capabilities come at relatively low cost.
Action operations may get their sources from packet header fields, or from an action memory. An action indicated by a match may be simple and require only a small amount of data from action memory or complex and require a large amount of data. Action memory is 640 bits wide, and may be output in units of 1, ½, ¼, ⅛, or 1/16 of that full width. Action memory is accessed by providing a size and an aligned pointer. Action memory is separate from instruction memory in the same way that instructions and data are separate entities in a processor. For example, a common action of an IP router is to decrement the IP TTL field, set the MAC source and destination addresses, and set the switch output port and queue. These individual modifications to the various affected fields are all grouped together into a single VLIW instruction where the various needed constants, like subroutine arguments, are in specific places in the delivered action word. While each match entry may require an individual action word for the data constants, they may all reference the same VLIW instruction word. The number of required instruction words is considerably less than the number of required action words.
In addition to the action size and address and the instruction address, a next table address is provided as a result of a match.
The 4 bit action size (to specify from 1× to 1/16× size) and 13 to 17 bit action address (to allow a range of from 8K 640 bit entries to 128 k 40 bit entries) can be combined into a single 18 bit entry as follows:
TABLE 1Action memory address and size codingwwww00000 ;1x13 bit addresswwwwf1000 ;1/2x14 bit addresswwwwff100 ;1/4x15 bit addresswwwwfff10 ;1/8x16 bit addresswwwwffff1 ;1/16x17 bit addresswhere w specifies a bit of the word (640 bits) address and f specifies an address of a fractional portion of that 640 bits. As will be seen later, with a maximum of 16 individual tables in a stage and 32 stages, 9 bits are required for a next table address. With an instruction memory of 32 VLIW words per stage, 5 bits are required for instruction address. If all of these fields are contained in extra bits of the match memory, this equals 32 bits of overhead. There are 4 valid bits which together provide both valid and rule version information. There are also 4 field-valid bits. The match data is composed of 8, 16, and 32 bit words from the packet header vector. The 4 field-valid bits allows the rule to check field presence or absence of each individual field. 8 Error Correction Code (ECC) bits are also provided. This totals 48 bits of overhead including ECC. With a 112 b memory, 64 bits are provided for match data in a single unit memory, with this detailed explanation showing that less than the 80 bits described above as a general explanation are actually available for matching. When two memories are combined for a wider word, the overhead bits are paid once over a larger width, yielding 168 bits of match data width (with 11 field valid bits). In all cases of appending two or more units, the match width is greater than N×80 bits for N units.

This patent is subject to a terminal disclaimer.

Packet processing VLIW action unit with OR-multi-ported instruction memory


A beamforming system includes a plurality of channelizers and a channel switching module in signal communication with the channelizers. Each channelizer is configured to receive a respective input radio frequency signal and to generate a plurality of respective channels in response to downsampling the respective input radio frequency signal. The channel switching module includes a channel combining circuit configured to selectively combine a common channel generated by each channelizer to form at least one steered analog beam.

The present disclosure relates to electronic signal processing, and more specifically, to directional signal transmission and/or reception.
Hardware implementations of wideband systems are inhibited with respect to the increased demand for bandwidth requirements. One technique used to address the increase in bandwidth requirements is to reduce a signal band into a plurality of sub-bands using a channelizer. Each of the sub-bands can then be processed on parallel channels. Conventional beamforming systems require digital channelizers to mix down the incoming radio frequency (RF) signal at the channelizer array level, which results in very low spurious content. Further, a digital channelizer typically requires a field-programmable gate array (FPGA), which inherently limits the system from sampling high frequency signals such as frequencies operating in the Ku band.

Programmable beamforming system including element-level analog channelizer


A plasma processing apparatus includes at least three gas supply lines connected to a process chamber in parallel to allow a gas to flow therethrough, and at least three flow-rate controllers provided on the gas supply lines to detect the flow rate of the gas flowing through each of the flow-rate controllers to control the flow rate to a set value and a diagnosis method. The apparatus has a function of splitting and supplying a gas controlled to a predetermined flow rate by the third flow-rate controller, to a first flow-rate controller for the smallest detectable range of the three flow-rate controllers and to a second flow-rate controller, in order to test the operation of the control of the flow rate of the first flow-rate controller, based on the value obtained from the flow rate of the gas flowing through the second flow-rate controller and the predetermined flow rate.

1. Field of the Invention
The present invention relates to a plasma processing apparatus for processing a substrate sample such as a semiconductor wafer placed in a process chamber within a vacuum vessel by a plasma formed in the process chamber. The present invention also relates to a diagnosis method of a plasma processing apparatus for diagnosing the operation of a flow-rate controller that controls the flow rate of a process gas supplied to the process chamber of the plasma processing apparatus.
2. Description of the Related Art
A plasma processing apparatus has been widely used for forming the structure of a device circuit by applying a desired process to a substrate sample such as a silicon semiconductor wafer or an LCD substrate in the process of manufacturing semiconductor devices. The plasma processing apparatus forms a plasma by exciting a process gas of one or a plurality of types of gases introduced into a process chamber placed in a vacuum vessel by the electric field or magnetic field supplied to the process chamber. Then, the plasma processing apparatus performs etching or other processes by using charged particles such as ions and highly reactive particles in the plasma.
In the process of the plasma processing apparatus described above, it is necessary to stabilize the flow rate of a plurality of process gases to be introduced, and to reproducibly supply the process gases. In recent years, the types of process gases used for manufacturing semiconductor devices as well as the conditions used for processing the flow rate and the like have been diversified. In these circumstances, it is required to achieve the conditions of a wide range of flow rates from large to small flow rates in one process chamber to process the sample. For this reason, the process gases of a wide range of flow rates (speeds) are supplied by using a flow-rate controller of one type and configuration.
In such apparatus, it is necessary to detect a very small value of the flow rate of the process gas, in order to stably and reproducibly achieve the small value of the flow rate of the process gas. Thus, there has been developed a process gas flow-rate controller for plasma processing apparatus including a manometer that can detect the range of low gas pressure with high accuracy, or including a flow-rate detector that can detect small flow rate with high accuracy.
An example of the related art is a semiconductor manufacturing apparatus including a mass-flow-rate controller and an opening/closing valve in a fluid feed passage with an exhaust device provided in an end thereof, which is for example described in Japanese Unexamined Patent Application Publication No. 2007-214406. The semiconductor manufacturing apparatus has a controller for controlling the operation of the mass-flow-rate controller, the opening/closing valve, the exhaust device, and the like. Then, the mass-flow-rate controller has a testing function and/or a flow-rate correction function for flow rate control.

Plasma processing apparatus and diagnosis method thereof


A method of sequentially performing a LSB program operation and an MSB program operation of a nonvolatile memory device, wherein the nonvolatile memory device comprises multi-level memory cells each configured to store two pieces of bit information and page buffers each coupled to a bit line coupled with the memory cells and configured to comprise a first latch coupled to first and second nodes and a second latch coupled to third and fourth nodes, the method including inputting data of MSBs to the second and fourth nodes and setting data of the second and fourth nodes according to a state of data of LSBs stored in the memory cells, and precharging the bit line according to a combination of data stored in the first and second latches and performing the MSB program operation according to a state of a LSB program operation stored in the memory cells.

One or more embodiments relate to a nonvolatile memory device and, more particularly, to a method of programming a nonvolatile memory device which is capable of performing operations using a reduced number of latches in a page buffer.
A nonvolatile memory device includes a memory cell array, a row decoder, a page buffer unit, etc. The memory cell array includes a plurality of word lines extending in rows, a plurality of bit lines extending in columns, and a plurality of cell strings corresponding to the respective bit lines.
The row decoder is coupled to a string selection line, word lines, and a common source line and is placed on one side of the memory cell array. The page buffer unit coupled to the plurality of bit lines is placed on the other side of the memory cell array.
Recently, to further increase the degree of integration of flash memory cells, active research is being done on a multi-bit cell capable of storing data of plural bits in a single memory cell. This type of a memory cell is called a multi-level cell (MLC). A memory cell capable of storing a single bit is called a single level cell (SLC).
In a nonvolatile memory device, the number of latches for sensing data or storing program data is gradually increasing.
In a nonvolatile memory device using MLCs, it is important to narrow a distribution of the threshold voltages of the cells. To control the distribution, a program operation is performed in various manners, such as double verification and reprogram.
In a nonvolatile memory device including MLCs, to meet the number of increased programs, the number of latches of a page buffer for storing data is also increased. Furthermore, since the page buffer occupies a large area in the nonvolatile memory device, the area occupied by the page buffer is increased with an increase in the number of latches.

Method of programming nonvolatile memory device


Valve apparatus for converting a direct water drain valve into an indirect water drain valve, the direct water drain valve having at least one drain conduit, the apparatus including: a part having an inner volume and a fluid transfer aperture for fluid to enter the inner volume, the part being arranged to be connected, directly or indirectly, to the direct water drain valve so as to convert at least some of the inner volume into a substantially fluid-tight passageway between the fluid transfer aperture and the at least one drain conduit of the direct water drain valve.

Vehicles such as aeroplanes require fuel tanks to store fuel for use in the vehicle's propulsion system. A known problem that can occur in an aircraft's fuel tank is that water builds up in the tank. For example, water vapour may enter a vent of a fuel tank and as the altitude of the aircraft increases and the temperature decreases the water vapour condenses within the tank and, due to water being denser than aviation fuel, settles at the bottom of the tank.
A known way of removing water from a fuel tank is to provide one or more valves to enable water to be drained from the tank upon activation of a valve. Different types of valve are used for this purpose. A direct drain valve drains water from an area adjacent the valve. An indirect drain valve includes a tube or duct, one end of which is connected to the valve conduit and the other is positioned at a remote location, such that water from the remote location can be drawn through the indirect drain valve. These two types of valve are structurally different to one another.
It is desirable to place a water drain valve at the lowest area or areas of the fuel tank. Where it is possible to do so, a direct water drain valve will generally be provided. However, where it is not possible to do so, for example because there is insufficient room to place a valve or from a structural perspective it is not desirable to cut a hole in the tank for a valve at that position, as may be the case with aircraft wings, an indirect water drain valve will be provided in the near vicinity and a tube will connect the indirect water drain valve to the drainage area. Thus, it will be appreciated that in some cases it is necessary to use two different types of valve within a single aircraft, or even within a single fuel tank.
Furthermore, it will be appreciated that a fuel tank can be made from a number of different materials. In order to provide a valve in the body of a fuel tank, the outer surface of the fuel tank generally has a recess formed in it. The recess corresponds in shape to a flange around the base of a valve. In some cases, to prevent rotation of the valve relative to the body, a hole will be drilled in a face of the recess for receiving a corresponding projection on the valve. For some materials, such as metal, it is relatively simple to form the hole within the recessed part for receiving the projection. However, when a fuel tank is made of a material such as carbon composite it can be difficult to machine the hole due to the size thereof.


A connection apparatus for transmitting power and signals for a notebook PC is described. The power and signal connection apparatus includes a hinge and an arc-shaped connector. The hinge interconnects a battery module, a display panel and a base unit of the notebook PC. When the display panel is opened, the base unit is lifted at the hinge side by the battery module. The arc-shaped connector maintains an electrical connection between the battery and a motherboard of the notebook PC.

1. Field of Invention
The present invention relates to a power and signal connection apparatus. More particularly, the present invention relates to a power and signal connection apparatus for a notebook PC.
2. Description of Related Art
In order to replace desktop PCs and satisfy customer demands, the computing performance of notebook PCs has been continuously enhanced. Now, a user may use a notebook PC to process all his work for a whole day, rather than just for one or two hours.
Notebook PC designers tend to create notebooks with good heat dissipation and long-time comfortable use. After a long time, the notebook PC system may operate inefficiently because of bad heat dissipation, or users may feel uncomfortable or tired because the notebook PC may not be suitable for long-time use. Generally speaking, lifting a base unit of the notebook PC such that a space is left between the base unit and the surface on which the base unit is put can improve bad heat dissipation.
However, common users are not aware of bad heat dissipation until the notebook PC malfunctions. Therefore, common users may not recognize when to lift the base unit of the notebook PC.
For the foregoing reasons, there is a need for notebook PC designers to overcome this problem.


A system and method for the production of liquefied light hydrocarbon gases by a system and a process that produces a liquefied gas product more efficiently and with reduced emissions of carbon dioxide (CO2) to the atmosphere.

In recent years, there has been continuing interest in liquefying natural gas and other light hydrocarbon gases at remote sites where there is little or no nearby market for the natural gas. Natural gas located at such remote sites is of market value only if it can be pipelined or otherwise transported to a marketplace. In many instances, it is not feasible to construct pipelines to transport such natural gas. Therefore, in many instances it has been found desirable to liquefy the natural gas on site so that it can be transported by tanker to markets.
A variety of processes for liquefying natural gas are known. In most of these processes, the natural gas is treated to remove acid gases and otherwise treated to remove water and hydrocarbons heavier than about C3 as necessary prior to liquefaction. Known natural gas refrigeration processes comprise processes that may use multiple pure component refrigerants, multi-component refrigerants or combinations thereof Refrigeration processes using one or more refrigerant sections and the like may be used. A variety of such processes are known and could be used with the present invention. All such processes generally require that a compressed refrigerant be made available at a pressure such that upon cooling it can be liquefied and thereafter vaporized to produce the refrigeration required to liquefy the natural gas.
Most such processes are quite energy intensive and require substantial energy input to compress the refrigerant for repeated cycling through a refrigeration zone to produce the refrigeration necessary to at least partially liquefy the natural gas and the like. Further, substantial energy may be required in many instances to recompress the natural gas after treatment to remove acid gases or water from the natural gas or to remove heavier hydrocarbons from the natural gas. All these processes typically require large quantities of electrical power and mechanical energy with the resultant emission of large quantities of carbon dioxide (CO2) into the atmosphere.
Recently it has been considered that release of CO2 into the atmosphere is detrimental to the atmosphere. Accordingly, it has been deemed desirable that the amount of CO2 emitted in such processes should be reduced. Typically such processes have been operated in areas where there was an abundance of cheap fuel. Therefore, little concern has been directed to limiting the emission of CO2 into the atmosphere since it was more convenient and economical to simply discharge combustion exhaust streams into the atmosphere than to limit the amount of fuel consumed since such fuel is readily available at little or no cost at the liquefaction site. As well known to those skilled in the art, hydrocarbon fuels, especially light hydrocarbon gases, have been used widely for generation of electrical power and for production of mechanical energy via light hydrocarbon gas fired turbines and the like.
Recently, it has become apparent that it would be desirable to provide a system and a process for providing compressed refrigerant and electrical power for a light hydrocarbon gas liquefaction process wherein reduced emissions of CO2 were produced and wherein the mechanical energy and electrical power for the process could be produced on site.
In many instances, especially with aeroderivative turbines such as General Electric Company turbine models PGT16/LM1600, PGT25/LM2500, LM6000 and PGT225+/LM2500+HSPT, power losses as high as 15 percent can occur as a result of ambient air variations in temperature, humidity and the like. This large power loss dramatically reduces the quantity of light hydrocarbon gas that can be produced in a light hydrocarbon gas liquefaction process. Continued efforts have been directed to the development of systems and methods to avoid this power loss.

Reduced carbon dioxide emission system and method for providing power for refrigerant compression and electrical power for a light hydrocarbon gas liquefaction process using cooled air injection to the turbines