Folding apparatus and systems are described for providing multi-folded products utilizing a folding board having at least one pressurized nip positioned proximate the folding operation. A folded product is directed through a first pressurized nip, comprising a roller and a first surface of a second folding board, positioned upstream of the folding operation and a second pressurized nip, comprising a roller and a second surface of the folding board, positioned downstream of the folding operation. Positioning pressurized nips proximate the folding operation improves the integrity of the folds created within the product and also creates distinct, uniformly oriented fold lines.

Folding devices, such as boards or plates, have long been used to longitudinally fold webs and other sheet-like materials in order to form a stack of folded sheets. The sheets are, generally speaking, drawn over the folding device wherein the shape and configuration of the device causes the sheet to twist and bend thereby producing the desired fold. Folding devices have heretofore been provided in a variety of shapes and configurations in order to achieve the desired fold lines and folding patterns. Folding devices have been used to form a number of different folds including, for example, half-folds, quarter folds, c-folds, v-folds, j-folds, w-folds, z-folds, and so forth.
In addition, for more complex folds requiring multiple fold lines, it is known to form the necessary fold lines using two or more folding devices in series. In this regard, folding boards have also been used in series to achieve inter-folded or inter-leafed sheets, that is to say sheets folded such that they partially envelope portions of another sheet. Inter-leafed sheets are commonly employed in stacks as a mechanism to facilitate removal of the individual sheets from a dispenser. Withdrawal of a first sheet through a dispenser opening pulls the enveloped potion of a second sheet through the dispenser opening such that it extends out of the dispenser opening and is exposed. Having a portion of the subsequent sheet extending out of the dispenser opening greatly facilitates removal of the same from the dispenser by the user. By way of example only, various folding devices, folding patterns and inter-folding schemes are described in the following U.S. Pat. Nos. 3,401,928; 3,679,094; 3,817,514; 3,841,620; 4,131,271; 4,502,675; 5,868,276; 6,045,002; and 6,168,848.
These folding devices are often advantageous since they allow folding of rolls of sheet material and, typically, allow for increased converting speed relative to many mechanized or rotary folding machines. However, due to the manner in which the sheets are folded, stress and friction associated with drawing the continuous sheet material across and/or through the folding devices can cause various aesthetic and physical defects within the sheet material. As an example, the twisting and pulling forces can alter the dimensions of the sheet material. In addition, these and other physical forces can also create undesirable wrinkles or creases in the sheet material. In this regard it is believed that the stress resulting from the twisting forces and friction cause the sheet material to xe2x80x9cbucklexe2x80x9d or wrinkle in order to decrease the physical forces upon the sheet. Further, when using multiple folding devices in a series, these same forces can act to degrade previously formed fold lines and/or to cause prior folds to xe2x80x9crollxe2x80x9d thereby changing the location of the fold within the sheet material. This can, undesirably, cause the formation of a fold line with an irregular orientation, i.e. a fold line that does not have uniform direction and/or placement. Still further, these forces can also cause the formation of a double fold line, i.e. a xe2x80x9cshadowxe2x80x9d fold. These and like irregularities are defects that are aesthetically displeasing to the end user. Further, defects such as irregular fold lines and other fold defects can also create problems with packaging and/or dispensing of the product. For example, stacks of folded sheets are commonly packaged in a clip and variation in stack height, such as due to variations in sheet folds, can make packaging difficult or ultimately destroy the packaging clip, such as where a paper sleeve is used.
Thus, there exists a need for folding devices capable of longitudinally folding webs and sheet materials that avoid the formation of defects such as wrinkles and unwanted creases. Further, there exists a need for such a device that produces uniform fold lines and prevents the formation of irregularly oriented fold lines. Still further, there exists a need for a folding device that avoids the formation of double folds along an intended fold line. Still further, there exists a need for a folding device that generates accurate and stable dimensions within the resulting folded product and stack.

Device and method for longitudinally folding a stack of webs


A roofing or siding system having an improved average resulting reflectivity. The roofing and/or siding system is at least partially coated with a plurality of granules. At least one layer of paint is applied to the roofing and/or siding system to increase the resulting reflectivity of the roofing and/or siding system.

Weather resistant granules of various hues, embedded on the surface of various types of roofing and/or siding, have been used extensively to provide an aesthetically pleasing color to such surfaces. In North America, asphalt-based roofing materials are a popular medium for covering roofs of homes and other structures. Asphalt-based roofing materials typically come in shingle or roll form, the shingle being the more widely used material. A typical asphalt shingle has an asphalt substrate and a multitude of granules placed thereon. The granules are generally embedded in the asphalt coating on the surface of an asphalt-impregnated base material such as roofing felt. The granules, which are embedded in one surface of the asphalt-impregnated and/or asphalt-coated fiber sheet material, form a coating to provide an inherently weather-resistant, fire-resistant, and/or decorative exterior surface. Because the granule coating provides the aesthetic effect observable with respect to the roofing material, the appearance of the granules is of major marketing importance. For this reason, a pigmented color coating is ordinarily applied to the granules to enhance their visual decorative effect.
The granules employed for roofing and siding are generally derived from a hard mineral base rock such as slate, basalt or nephelite. The granules are typically ground to a particle size of about 10 to about 35 US mesh. These granules, which comprise a base substrate, are then coated with a pigment composition having a thickness of about 4 to about 18 microns. Colored roofing granules are typically prepared by heating mineral rock granules of about 12-40 US mesh up to approximately 1000° F. A paint slurry containing a pigment is then applied to the heated granules in a mixer. Kaolin clay is used extensively in silicate paint formulations for coloring roofing granules. It serves as a filler, extender, moisture release agent, and reactant to aid film insolubilization during high temperature firing. Although kaolin clay is a major component of such coating formulations, it alone lacks the brightness and opacity needed to hide the dark underlying base rock of the granule. Light colored roofing granule coatings using natural kaolin clay frequently require appreciable amounts of TiO2 to achieve desired color specifications. Light colored roofs are particularly favored in many areas. The TiO2 is commonly used in conventional insolubilized alkali silicate coatings, such as those described in U.S. Pat. Nos. 2,379,358; 3,255,031; and 3,479,201, which are incorporated herein by reference. Other types of coating compositions have been used. For example, U.S. Pat. No. 3,528,842, which is incorporated herein by reference, discloses artificially colored roofing granules. These granules consist primarily of crushed and screened minerals, in which the granules are coated with a suitable pigment contained in an inorganic matrix or bond. Some common pigments include red iron oxide, yellow iron oxide, titanium dioxide, chrome hydrate, chrome oxide, chrome green, ultramarine blue, phthalocyanine blue and green, carbon black, metal ferrites, and mixtures thereof. The bond is usually applied in the form of a soluble silicate solution and is insolubilized either by heat treatment or by a combination of heat treatment and chemical action. Minnesota Mining and Manufacturing Company ("3M") has offered pigmented roofing granules known under the trade designations "LR-7000", "LR-7070", 3M Brand "4100", and 3M Brand "9300". These granules include multiple silicate-clay coatings which may include cuprous oxide or zinc oxide. Other types of pigment compositions include an aqueous slurry of an iron oxide pigment and a mixture of a silicate and clay.
Although the color of a particular roofing system plays an important role in determining which roofing system will be purchased by consumers, other factors are also of importance in determining the color of a particular roofing system. One such factor is the energy efficiency of the roofing system. Several cities and states are beginning to consider legislation or currently require some roofing structures to have a certain resulting reflectivity. This is of particular importance in temperate regions, such as in the Southern and Southwest regions of the United States. For instance, California is planning to require in 2005 "cool roof" systems to have a resulting reflectively of at least 70% and a emmissivity of at least 0.9. Lighter colored roofs are known to reduce the roof temperature, thereby reducing the cooling costs of the roofed structure. For instance, on a 90° F. sunny day, the roof temperature of a light colored granular coated roof can be about 20-30° F. cooler than an aluminum roof system and about 70-80° F. cooler than a black asphalt roof. As a result, the lighter colored roof system can amount to an energy savings of about 5-10%. The cooler temperature of the light colored roof system not only reduces the cooling costs associated with the building, but the heat generated by the light colored roof contributes less heat to the surrounding environment, thus improving air quality, especially in urban areas.
Typical light colored roofing systems have light colored granules having a reflectivity of up to 30% and a resulting roofing reflectivity of up to 27%. Darker colored granules typically have a lower reflectivity and a resulting roofing reflectivity that is less than roofing systems having lighter colored granules. The Garland Company has recently developed a highly reflective granular roof system that has a resulting reflectivity of at least 45%. This granular roofing system is disclosed in United States Patent Publication No. 20040071938 published on Apr. 15, 2004. Although this granular roof system constituted a significant advance in the roofing, the achievable resulting reflectively on granular roofing systems form on a bitumen layer was limited to less than 70%. The bitumen layer on the roofing system is a generally black color, thus has a low reflectivity. When coating the bitumen layer with reflective particles, some of the bitumen surface remains exposed, thus reducing the resulting reflectivity of the roofing system.
One practice for obtaining a highly reflective surface on a roofing system is in apply a thick coating of highly reflective white paint to the surface of the installed roofing system. Typically a wet paint coating thickness of about 32 mils or more was applied after the roofing system is installed on a structure. Although the application of a highly reflective paint layer on the existing roof system achieved a resulting reflectivity of 70% or greater, the application of the paint on the roof system was expensive due to the large volume of paint needed to obtain the needed paint coating thickness to achieve the desired resulting reflectivity, and from the labor and materials required to apply the paint to the surface of the roofing system. Furthermore, the application of a paint coating on an existing roof system can be problematic due to the problems associated with paint spray during application of the paint and/or the added weight to the roof system due to the application of the thick paint layer.
In view of the continued demand for greater energy savings, there is a demand for a prefabricated roofing system having increased reflectivity.

Method of forming a prefabricated roofing or siding material


An adaptive cruise system for a vehicle maintains a desired selected operator-set speed in the absence of a detected preceding target vehicle and adjusts the vehicle speed when a target vehicle is detected to maintain a following distance that is set by the vehicle operator. An alert distance is computed that is a predetermined function of a distance based on driver reaction time. To provide for the driver selectable trailing distance, the driver reaction term of the alert distance is adjusted by the vehicle operator to achieve a desired distance to the target vehicle.

This invention relates to an adaptive cruise control system for a vehicle.
It is well known to provide automatic vehicle cruise control systems for maintaining the speed of a vehicle at an operator-set speed. It is further known to provide, in conjunction with these known cruise systems, a system for detecting the presence and the distance to a preceding vehicle and for adjusting the vehicle speed to maintain a trailing distance to the preceding vehicle. In essence, the vehicle speed is controlled to the speed of the preceding vehicle with a predetermined separation from the preceding vehicle with the vehicle speed being limited at the operator-set cruise speed.
Typically, the trailing distance provided by these known systems is a predetermined calibrated value or schedule of values as a function of parameters such as vehicle speed. These calibration values generally do not take into account varying traffic conditions, weather conditions, road surface conditions or personal driving habits of the vehicle operator. The calibrated values are accordingly a compromise that may be optimum for one operator and for a specific set of weather/road/traffic conditions but may not be optimum for different operators and varying conditions.


Methods, systems, and media for synchronizing audio and video content on multiple media devices are provided. In some embodiments, the method comprises: receiving, at a media device, an indication of a media content item to be presented using the media device, wherein the media device includes an audio component for presenting audio content associated with the media content item and a video component for presenting video content associated with the media content item; determining that the media device is associated with a group of media devices for presenting the media content item, wherein the group of media devices includes the media device and at least one audio device that presents the audio content associated with the media content item; generating an audio timestamp that controls the presentation of the audio content on the group of media devices; generating a video timestamp that control the presentation of the video content on the group of media devices; and causing, at the media device, the video content associated with the media content item to be presented using the generated video timestamp and causing the audio content associated with the media content item to be simultaneously presented by the at least one audio device in the group of media devices by transmitting the audio timestamp to the at least one audio device in the group of media devices.

With the increase in networked media devices, users are interested in combining multiple devices to view media content to create a richer media experience. For example, a user may be interested in viewing a video on a television device while routing the audio associated with the video to speakers associated with the television device as well as to other speakers in the same room as the television device to create a surround-sound experience. It can, however, be difficult to synchronize audio playback on the multiple speakers and it can also be difficult to synchronize the audio playback on the speakers with the video playback on the television device. Synchronization may be particularly difficult in cases where media content is streamed, for example, from a video sharing service, due to variations in network speed and quality during streaming.
Accordingly, it is desirable to provide new methods, systems, and media for synchronizing audio and video content on multiple devices.

Methods, systems, and media synchronizing audio and video content on multiple media devices


An image processing apparatus includes an image compression device which performs a discrete wavelet transform of pixel values for each rectangular portion to produce wavelet coefficients, and performs a hierarchical compression coding of the wavelet coefficients for each rectangular portion so that a codestream is produced. A codestream transform device is provided to reduce an amount of code data in the codestream. The codestream transform device comprises a syntax analysis unit which analyzes header information of each rectangular portion in the codestream. A comparison unit determines a similarity of pixel values between a current frame and a preceding frame in the codestream based on a result of the analysis. A codestream generating unit deletes code data of a corresponding rectangular portion of the current frame when the similarity is larger than a given threshold value.

1. Field of The Invention
The present invention relates to an image processing apparatus, an image recording apparatus, an image reproducing apparatus, a camera system, a computer program, and a storage medium. More specifically, the present invention relates to image processing that is provided to cancel the redundancy of compressed image data in case there is no motion of the image between the frames, for use in a standard system with the Motion-JPEG2000 method being adopted.
2. Description of The Related Art
Conventionally, the image compression/expansion algorithms include the MPEG1/MPEG2/MPEG4 for motion pictures and the Motion JPEG which handles the still pictures as continuous frames.
Recently, the Motion-JPEG2000 standard is under development as a new intra-frame coding method for motion pictures utilizing the still image coding standard JPEG2000.
One of the differences between the MPEG method and the JPEG method is that the latter performs only the intra-frame coding. Not only this, another difference is that the former method has the ability to take correlations of the images in the same frame as well as the images between different frames and to increase the compressibility of images more.
The JPEG method, which handles the respective frames independently, has the ability to edit each frame, as compared with the former, and the error of one frame at the time of transmission does not affect other frames.
Thus, the MPEG method and the JPEG have the features respectively, and one of them is selectively used for different applications properly.
The Motion-JPEG2000 method utilizes the discrete wavelet transform (DWT) as the compression coding method. Japanese Laid-Open Patent Application No. 2001-309381 discloses a technique which carries out the compression coding of image data using the discrete wavelet transform.
In the technique of Japanese Laid-Open Patent Application No. 2001-309381, the discrete wavelet transform of the pixel values is performed and the correlation of the images between different frames is taken, and the redundancy of image data in case there is no motion of the image between the frames is canceled. Hence, the compressibility of image data can be increased.
However, after carrying out the discrete wavelet transform of the pixel values of image data, the above-mentioned technique takes the correlation of the images between different frames using the wavelet transform coefficients before quantizing and coding, and it is made to cancel the redundancy of image data in case there is no motion of the image between the frames.
Therefore, it is difficult for a standard system, which is provided to treat the data format of the Motion-JPEG2000 method, to make use of a codestream obtained through the above technique after the data compression. Moreover, it is impossible to leave a codestream which is obtained through the compression coding by the Motion-JPEG2000 method but the redundancy of the image data in case there is no motion of the image between the frames is not yet canceled.
Therefore, the codestream generated by the above technique has too small flexibility, and it cannot be easily used by the standard system in which the Motion-JPEG2000 method is adopted. In order to use such codestream, it is necessary to prepare a special system of exclusive use.

Image processing apparatus, image recording apparatus, image reproducing apparatus, camera system, computer program, and storage medium


A hood and wheel brace comprising of a horizontal bar, encased in a plastic sleeve, being hollow and having two ends, with extendable bars slideably mounted and extending from each end of the horizontal bar operationally adjustable for sizing of a vehicle's hood and wherein each extendable bar is received in an insertion hole defined in one end of a retractable tower to align with the insertion hole and locked within the retractable tower; said retractable towers each having two ends, with a hook extending downward at one end inclined to allow the hook to embrace an inner side of the vehicle's front wheel; and a vertical shaft which includes a plurality of ratchet teeth longitudinally extending over a portion thereof, configured to allow the vertical shaft to slideably extend the sizing of the retractable tower.

Many high performance engines include specialized parts that are expensive to produce and to maintain. Persons with knowledge of cars can readily identify engines that have been enhanced with after market engine components to increase their performance. Although all car enthusiasts would enjoy having their engines running at peak or at a minimum high performance, some simply cannot afford the engine components to accomplish this dream and do not mind paying a reduced rate for "hot" or stolen parts. As such, the theft rate for high performance engine components is quite high and to date the prior art has yet to find a way to successfully deter or eliminate this problem.
Audible alarms are quite popular as a theft deterrent but over the years thieves have been able to quickly silence alarms, open the hood, remove and/or strip the engine in record time. Thus there needs to be a practical solution to protect engine components beneath the vehicle hood in a new and novel manner that does not damage the vehicle's exterior yet effective as a deterrent.
Accordingly, the various embodiments and disclosures described herein satisfies these long felt needs and solves the limitations of the prior art in a new and novel manner.


An improved gas appliance having a burner, a gas valve through which the flow of combustion gas to the burner is controlled, and a motor driven blower that supplies combustion air to the burner. The improvement includes means for increasing gas flow through the gas valve as blower speed increases, and decreasing gas flow through the gas valve as blower speed decreases, based on a pressure signal generated independently of combustion air pressure. This improvement allows a constant ratio of gas to air to be maintained in the burner while a combustion flow rate varies dependent on the blower motor revolutions per minute. Thus input pressures of combustion can be controlled at low cost.

The present invention relates generally to gas appliances and, more particularly, to controls for gas input to gas appliances.
Gas appliances typically include valves for controlling gas input to the appliance""s burners. Gas control valves are used in induced draft systems and in forced draft systems with pressure-assist modulation (PAM) to deliver gas to be combined with air for combustion. It is desirable to control gas and air input pressures in order to achieve desired combustion rates in appliance burners. One method of controlling gas input pressure is to electronically modulate gas control valve output relative to the air input pressure, by using a pressure transducer. Such an approach, however, is expensive.
The present invention in one embodiment is an improved gas appliance having a burner, a gas valve through which the flow of combustion gas to the burner is controlled, and a motor driven blower that supplies combustion air to the burner. The improvement includes means for increasing the flow of gas through the gas valve as the blower speed increases, and decreasing the flow of gas through the gas valve as the blower speed decreases, based on a pressure signal generated independently of the combustion air pressure. In a preferred embodiment, a pump provided on the shaft of the blower motor is driven by the blower motor to generate the pressure signal for controlling the gas valve.
The above-described system allows a constant ratio of gas to air to be maintained to the burner while a combustion flow rate varies dependent on the blower motor revolutions per minute. Thus input pressures to the burner can be simply and reliably controlled at low cost.

System and methods for modulating gas input to a gas burner


The class of k Nearest Neighbor (k NN) queries in spatial networks has been studied in the literature. Existing approaches for k NN search in spatial networks assume that the weight of each edge in the spatial network is constant. However, real-world edge-weights are time-dependent and vary significantly in short durations, hence invalidating the existing solutions. The problem of k NN search in time-dependent spatial networks, where the weight of each edge is a function of time, is addressed herein. Two indexing schemes (Tight Network Index and Loose Network Index) are proposed to minimize the number of candidate nearest neighbor objects and reduce the invocation of the expensive fastest-path computation in time-dependent spatial networks. We demonstrate the efficiency of our proposed solution via experimental evaluations with real-world data-sets, including a variety of large spatial networks with real traffic-data.

This specification relates to k Nearest Neighbor (k NN) queries in spatial networks.
Recent advances in online map services and their wide deployment in hand-held devices and car-navigation systems have led to extensive use of location-based services. The most popular class of such services is k-nearest neighbor (k NN) queries where users search for geographical points of interests (e.g., restaurants, hospitals) and the corresponding directions and travel-times to these locations. Accordingly, numerous algorithms have been developed (e.g., Hanan Samet and Jagan Sankaranarayanan and Houman Alborzi. Scalable Network Distance Browsing in Spatial Databases. Proceedings of SIGMOD, pages 33-40, Toronto, Canada, 2008; Mohammad Kolandouzan and Cyrus Shahabi. Voronoi-based K NN search in spatial networks. Proceedings of VLDB, pages 840-851, Toronto, Canada, 2004; Dimitris Papadias and Jun Zhang and Nikos Mamoulis and Yufei Tao. Query processing in spatial networks. Proceedings of VLDB, pages 802-813, Berlin, Germany, 2003; Cho, Hyung-Ju and Chung, Chin-Wan. An efficient and scalable approach to CNN queries in a road network. Proceedings of VLDB, pages 865-876, Trondheim, Norway, 2005; Huang, Xuegang and Jensen, Christian S. and Saltenis, Simonas. The Island Approach to Nearest Neighbor Querying in Spatial Networks. Proceedings of SSTD, pages 33-40, Toronto, Canada, 2005; Ulrith Lauther. An Extremely Fast, Exact Algorithm for Finding Shortest Paths in Static Networks with Geographical Background. Geoinformation and Mobilitat, pages 33-40, Toronto, Canada, 2004; and Wagner, Dorothea and Willhalm, Thomas. Geometric Speed-Up Techniques for Finding Shortest Paths in Large Sparse Graphs. Proceedings of Algorithms-ESA, 2003) to efficiently compute the distance and route between objects in large road networks.

Efficient K-nearest neighbor search in time-dependent spatial networks


Provided is a herbicidal composition comprising a compound of Formula (I) as a herbicidally active ingredient, and an agronomically acceptable additive,

Allelochemicals or secondary metabolites in many plants can affect seed germination, growth and development, density, and distribution of plants, and are an important source for the development of herbicides (Cespedes et al., 2014). A large number of natural products having herbicidal activities are being screened and tested throughout the world by researchers. For example, Conyza canadensis, Cephalotaxus sinensis, Flaveria bidentis, Partheniumhy sterophorus, corn protein powder and other plant extracts have been confirmed to contain herbicidally active ingredients (Gao Xingxiang, et al., 2010; Ma Shujie et al., 2016; Li Jianqiang, et al., 2012; Chen Yebing et al., 2010; Yang Jian and Lu Changyi, 2010).
Only a few plant derived herbicides, however, are registered or approved for use. These include cinmethylin, a highly effective broad-spectrum herbicide successfully developed as a derivative of cineole extracted from plants. After entering into plants such as rice, soybean, cotton, and peanuts, this compound can be metabolized into a hydroxyl derivative, which then binds to glycosides in the plants to form a conjugate, thus losing its toxicity (Grayson et al., 1987). Another successful example of herbicides developed from the plant allelochemicals is the triketone herbicides, specifically sulcotrione and mesotrione, with leptospermone developed as a lead compound. Leptospermone is a highly effective inhibitor of Phydroxyphenyl-pyruvate dioxygenase (HPPD). When used for pre- and post-emergence treatment, certain grass (Poacea) and broad-leaved weeds develop symptoms of albinism; however, maize is resistant to leptospermone (Mitchell et al., 2001).
The development of commercially viable, highly effective, broad-spectrum and safe plant-derived herbicides remains an arduous and lengthy process, and it is necessary to expand the plant species to be screened, and make structural derivatives of natural compounds having herbicidal activities.
Fatty acid herbicides are well known in the art and are generally considered to be environmentally friendly. Fatty acid herbicides are typically supplied as concentrates that are diluted with water and applied as an oil-in-water emulsion. These concentrates usually contain the fatty acid active ingredient and emulsifying agents including surfactants and oils such as sodium dodecyl benzene sulfonate (ABS).
Caprylic acid, also referred to as n-octanoic acid, and widely found in Myristica fragrans, lemongrass, apples, coconut oil, wine, and hops etc., has a molecular formula of C8H16O2 and is a colorless transparent oily liquid having a sweat smell. It is mainly used in the production of dyes, drugs, spices, plasticizers, lubricants, or as preservatives and fungicides, etc. (Parag et al., 2014; Salimon et al., 2012; and Liu et al., 2008).
U.S. Pat. Nos. 4,975,110; 5,106,410 and 5,098,467 disclose fatty acid herbicidal compositions that contain C8-12 fatty acids, a surfactant and water with pelargonic acid being a preferred fatty acid herbicide. U.S. Pat. Nos. 5,098,468 and 5,035,741 also disclose fatty acid herbicidal compositions that contain C8-12 carbon fatty acids, an oil component, an emulsifier and water. Single phase concentrates are disclosed in U.S. Pat. Nos. 5,098,468 and 5,035,741 that contain the fatty acid(s), oil and emulsifier.
U.S. Pat. No. 5,919,734 discloses herbicides comprising fatty acids and a compatible oil component.
Fatty acid herbicides include fatty acid esters of C6-C20 monocarboxylic acids such as those disclosed in U.S. Pat. No. 5,284,819.
Additionally, fatty acid salts such as those disclosed in U.S. Pat. Nos. 2,626,862; 4,975,110; 5,035,741, and 6,930,075 can be employed as fatty acid herbicides.
However, no water soluble fatty acid salt has been found to be an effective herbicide alone without another petrochemical-based herbicide (e.g. glyphosate), or without an emulsifier, or without an oil component.
Caprylic acid was mentioned as a component in prior art herbicidal compositions (e.g. U.S. Pat. Nos. 4,031,140; 4,663,364, disclosing a herbicidal powder; U.S. Pat. No. 5,919,734, disclosing an oil-based fatty acid herbicidal composition; U.S. Pat. No. 6,930,075, disclosing a fatty acid-based herbicidal composition; and U.S. Pat. No. 9,578,877, disclosing cocoalkylpolyamine alkoxylates as agents for high strength herbicide compositions, where caprylic acid is mentioned as a supplement.
Caprylic acid, however, has never been used as a primary agrochemical active ingredient or herbicidal ingredient prior to the instant invention. Further, no disclosure of the isopropyl amine salt of caprylic acid as an effective herbicidal agent was found in the prior art.

Herbicide composition containing isopropylamine caprylate

Abstract: Also provided is a method of controlling undesirable vegetation using the herbicide composition.

HUNAN AGRICULTURAL BIOTECHNOLOGY RESEARCH INSTITUTE


The present invention relates to improved lubricant compositions highly resistant to oxidative degradation comprising selected 5-tert.-butyl-4hydroxy-3-methylphenyl substituted fatty acid esters, diphenylamines and zinc dithiophosphates. The compositions as defined above are characterized by superior antioxidative properties. This can be demonstrated in various standard tests such as Deposit and Oxidation Panel Test (DOPT) and Pressurized Differential Scanning Calorimetry (PDSC).

The present invention relates to improved lubricant compositions, which are highly resistant to oxidative degradation, and which comprise selected phenolic and amine antioxidants. The invention also relates to the use of these lubricant compositions for improving the performance properties of lubricants, such as greases, metalworking fluids, gear fluids and hydraulic fluids.
It is known that additives improve the performance properties of lubricants, such as mineral oils or synthetic or semi-synthetic oils. Particularly additives are highly desirable which reduce the formation of oxidative degradation products and promote a long shelf life and high performance stability of lubricants.
The technical requirements for modern motor oils under the conditions of high temperature oxidation, as expressed by recent technical specifications, have become more severe. According to recent developments in the construction of combustion engines, particularly spark ignition internal combustion engines, higher amounts of nitrogen oxides (NOx) are produced which reenter the crankcase as blow-by gases.
The lubricating oil also functions in the combustion chamber as a tight seal between the up-stroke of the piston and the cylinder head resulting in a contamination with high-boiling fuel components. These functions deteriorate in the presence of NOx-gases.
Blow-by gases with increasing NOx-content enhance the susceptibility of the lubricating oil to oxidation and the formation of undesirable oxidation products. Nuclei for deposits are formed which ultimately generate undesirable deposits, popularly known as black sludge. It is assumed that this degradation process is caused by NOx-initiated autooxidation of the lubricating oil. Many attempts have been made to improve the performance of lubricating oils by the addition of different antioxidants.
EP-A-0 346 283 discloses phosphite-free lubricating oil compositions which comprise, among others, phenolic antioxidants in combination with different aromatic amines and mixtures of these amines. So-called sterically hindered phenolic antioxidants are specifically disclosed wherein the phenolic group is substituted in 3- and 5-position with tert.-butyl groups.
EP-A-0 781 834 discloses lubricating oil compositions which comprise 5-tert.-butyl-4-hydroxy-3-methylphenyl substituted fatty acid ester in combination with conventional oil additives other than diphenylamines.
The Japanese Published Patent Application Hei 11-209777 discloses lubricating oil compositions which comprise 3-(5-tert.-butyl-4-hydroxy-3-methylphenyl)propionic acid C5- and -C13alkyl esters in combination with alkylated diphenylamines. No additional additives are specifically disclosed. The composition is used for preventing the discoloration of lubricating oils. No other technical uses and applications or improved antioxidative properties are disclosed.
EP-A-0 896 050 discloses lubricating oil compositions which comprise a large group of different phenolic antioxidants of divergent structures in combination with different aromatic amines and sulfur containing oil additives. Among them zinc dithiophosphates are disclosed.
Novel lubricant compositions have now been found which possess improved antioxidative properties as compared with the prior art compositions. The novel lubricant compositions comprise a selected group of 5-tert.-butyl-4-hydroxy-3-methylphenyl substituted fatty acid esters in combination with specific diphenylamines and zinc dithiophosphates. The novel lubricant compositions are highly resistant to oxidative degradation and are capable of reducing the negative effects of deposits, such as black sludge, in motor combustion engines, particularly spark ignition internal combustion engines.
The present invention relates to a composition, which comprises:
a) a base oil of lubricating viscosity;
b) at least one phenol of the formula:
xe2x80x83wherein
R1 represents branched C8-C22alkyl;
c) at least one aromatic amine of the formula:
xe2x80x83wherein R1 and R2 represent hydrogen or together represent the group:
xe2x80x83and one of R3 and R3xe2x80x2 represents hydrogen and the other one C2-C30alkyl or both R3 and R3xe2x80x2 represent C2-C30alkyl; and
d) at least one zinc dithiophosphate of the formula
xe2x80x83wherein R1 and R2represent straight chained or branched C3-C20alkyl.
The compositions defined above containing 5-tert.-butyl-4-hydroxy-3-methylphenyl substituted fatty acid esters are characterized by their superior antioxidative properties as compared with the corresponding compositions containing 3,5-di-tert.-butyl-4-hydroxyphenyl substituted fatty acid esters. This can be demonstrated in various commonly accepted tests such as Deposit and Oxidation Panel Test (DOPT) and Pressurized Differential Scanning Calorimetry (PDSC).
The compositions according to the instant invention are particularly suitable for use as lubricants having excellent antioxidative properties in internal combustion engines, such as spark-ignition internal combustion engines (popularly known as Otto motor engines) or self-ignition internal combustion engines (popularly known as Diesel motor engines).
The compositions are particularly suitable as motor oils which correspond in the API (American Petroleum Institute) classification to the categories SF, SG and CD, in the CRC (Coordinating Research Council) classification to the standardized Caterpillar Tests 1-G 1 or 1-G 2 and in the CCMC (Committee of Common Market Automobile Constructors) classification to the specifications G 1, G 2, G 3, D 1, D 2, D 3 and/or PD 1.
The definitions and general terms used in the description of the present invention preferably have the following meanings:
Component a)
A base oil of lubricating viscosity can be used for the preparation of engine oils, gear fluids, or hydraulic fluids, but also for fuel additives, greases or metal working fluids.
Suitable engine oils, gear fluids and hydraulic fluids are based, for example, on mineral oils or synthetic oils or mixtures thereof. The lubricants are known and familiar to the person skilled in the art and are described in standard reference books, such as in Chemistry and Technology of Lubricants; Mortier, R. M. and Orszulik, S. T. (Editors); 1992 Blackie and Son Ltd. for GB, VCH-Publishers N.Y. for U.S., ISBN 0-216-92921-0, pages 208 et seq. and 269 et seq.; in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition 1969, 1. Wiley and Sons, New York, Vol. 13, page 533 et seq. (Hydraulic Fluids); Performance Testing of Hydraulic Fluids; R. Tourret and E. P. Wright, Hyden and Son Ltd. GB, on behalf of The Institute of Petroleum London, ISBN 0 85501 317 6; Ullmann""s Encydopedia of Ind. Chem., Fifth Completely Revised Edition, Verlag Chemie, DE-Weinheim, VCH-Publishers for U.S., Vol. A 15, page 423 et seq. (lubricants), Vol. A 13, page 165 et seq. (hydraulic fluids).
The base oil of lubricating viscosity is preferably a mineral oil derived lubricating base oil containing 80% by mass or more of a saturated hydrocarbon component. Various methods for producing the mineral oil derived lubricating base oil are available. For example, the lubricating base oil may be a paraffin oil or a naphthenic oil obtainable by subjecting a lubricating oil fraction derived from an atmospheric or vacuum distillation of crude oil to refining processes such as deasphalting, solvent refining such as solvent extraction with furfural, hydrocracking, solvent or catalytic dewaxing, such as solvent or catalytic dewaxing, hydrotreating, such as hydrocracking or hydrofinishing, clay treatment, such as washing with acid treated or activated clay, or chemical refining such as washing with caustic soda or sulfuric acid and the like. Combinations of these methods are also available for producing the mineral oil derived lubricating base oil.
Preferred methods for producing the mineral oil derived lubricating base oil consists of the following technical procedures, wherein one of the following oils is used as feedstock oil:
1) a distillate derived from the atmospheric distillation of a paraffin crude oil and/or a mixed crude oil;
2) a whole vacuum gas oil (WVGO) of a paraffin crude oil and/or a mixed crude oil;
3) an oil obtained by subjecting the product obtained according to 1) and/or 2) to mild hydrocracking (MHC);
4) a mixture of two or more selected from products obtained according to 1) to 3);
5) a deasphalted oil (DAO) from products obtained according to 1), 2), 3) or 4);
6) an oil obtained by subjecting the product obtained according to 5) to mild hydrocracking; and
7) a mixture of two or more oils selected from the group of oils obtained according to 1) through 6).
Either the feedstock oil itself or a lubricating oil fraction recovered therefrom is refined by conventional refining processes, such as the ones mentioned above, to obtain a lubricating oil fraction which is useful as the component a) of the claimed composition. The base oil may be present in the composition as an individual component or in a combination of two or more of the above-mentioned base oils.
Other base oils of lubricating viscosity are oils and greases, for example based on vegetable and animal oils, fats, tallow, wax and mixtures thereof. Vegetable and animal oils, fats, tallow and wax are, for example, palm-kernel oil, palm oil, olive oil, rapeseed oil, rape oil, linseed oil, soybean oil, cottonseed oil, sunflower oil, coconut oil, maize oil, castor oil, low-grade olive oil and mixtures thereof, fish oils, and also the chemically modified, for example epoxidized and sulfoxidized, forms thereof, or forms thereof produced by genetic engineering, for example genetically engineered soybean oil.
Examples of synthetic oils include lubricants based on aliphatic or aromatic carboxy esters, polymeric esters, polyalkylene oxides, phosphoric acid esters, poly-xcex1-olefins or silicones, the diester of a divalent acid with a monohydric alcohol, such as, for example, dioctyl sebacate or dinonyl adipate, a triester of trimethylolpropane with a monovalent acid or with a mixture of such acids, such as, for example, trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, a tetraester of pentaerythritol with a monovalent acid or with a mixture of such acids, such as pentaerythritol tetracaprylate, or a complex ester of monovalent and divalent acids with polyhydric alcohols, for example a complex ester of trimethylolpropane with caprylic and sebacic acid, or a mixture thereof. Apart from mineral oils, poly-xcex1-olefins, ester-based lubricants, phosphates, glycols, polyglycols and polyalkylefne glycols, and also mixtures thereof with water are especially suitable.
An organic or inorganic thickener (base fat) may also be added to the above-mentioned lubricants or mixtures thereof. Metal-working fluids and hydraulic fluids may be prepared on the basis of the same substances as those described above for the lubricants, such fluids frequently being emulsions of such substances in water or other liquids.
Component b)
In the compound of the formula I, R1 is defined as branched C8-C22alkyl, e.g. isooctyl types, e.g. 3,4-, 3,5- or 4,5-dimethyl-1-hexyl or 3- or 5-methyl-1-heptyl, other branched octyl types such as 1,1,3,3-tetramethylbutyl or 2-ethylhexyl, or branched alkyl groups with more than 8 carbon atoms, e.g. 1,1,3-trimethylhexyl, 1-methylundecyl, 2-n-butyl-n-octyl, isotridecyl, 2-n-hexyl-n-decyl or 2-n-octyl-n-dodecyl.
In a particularly preferred embodiment of the invention R1 consists of isooctyl types selected from the group consisting of 3,4-, 3,5- or 4,5-dimethyl-1-hexyl and 3- or 5-methyl-1-heptyl, or branched alkyl groups with more than 8 carbon atoms wherein a side chain is attached in 2-position of the carbon chain, e.g. 2-n-butyl-n-octyl, 2-n-hexyl-n-decyl or 2-n-octyl-n-do-decyl.
Compounds of the formula I are known and may be prepared by any known process, for instance a 6-tert.-butyl-2-methylphenol reacts with a methylacrylate in the presence of a strong basic catalyst, such as metallic sodium thus producing methyl 3-(5-tert.-butyl-4-hydroxy-3-methylphenyl)propionate. This ester is then subjected to a transesterification reaction with the corresponding C8-C22alkanols.
Some compounds of the formula I are commercially available, e.g. under the names Exxal(copyright) (Exxon Corporation) 8, 9, 10, 11, 12, 13, Acropol(copyright) 35 or Isofol(copyright) (Condea) 12, 14, 16, 18, 20.
Component b) may consist of one individual compound (I) as defined above or may be present in the composition as mixture of two or more compounds defined by the formula I. The total content of component b) in the composition is in the range between 0.1 and 10.0, preferably 0.2 and 5.0, and even more preferably 0.2 and 3.0 percent by mass based on the total weight of the composition.
Component c)
In a compound of the formula II R1 and R2 represent hydrogen or together represent the group A. In the event that R1 and R2 together represent the group
the compound of the formula II has the following structural formula
In this embodiment R3 preferably is hydrogen and R3xe2x80x2 represents C2-C30alkyl. R3xe2x80x2 preferably is in the 4-position of the phenyl ring.
R3 and R3xe2x80x2 defined as C2-C30alkyl is ethyl or straight chained or branched C3-C30alkyl, e.g. n-propyl, isopropyl, n-, iso- or tert.-Butyl, n-pentyl, isoamyl, neopentyl, 2-ethylbutyl, n-hexyl, 1-methylpentyl, 1,3-dimethylbutyl, n-heptyl, isoheptyl, n-octyl, 1,4,4-trimethyl-2-pentyl, 3,4-, 3,5- or 4,5-dimethyl-1-hexyl, 3- or 5-methyl-1-heptyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, branched octyl as obtained from a dimer of isobutylene, n-nonyl, 1,1,3-trimethylhexyl, branched nonyl as obtained from a trimer of tripropylene, 1-methylundecyl, 2-n-butyl-n-octyl, branched dodecyl obtained from a trimer of isobutylene or a tetramer of propylene, branched pentadecyl obtained from a pentamer of propylene, 2-n-hexyl-n-decyl or 2-n-octyl-n-dodecyl.
In a preferred embodiment of the invention the aromatic amine has the formula
wherein R1 and R2 represent hydrogen or together represent the group (A) and one of R3 and R3xe2x80x2 represents hydrogen and the other one C8-C16alkyl or both R3 and R3xe2x80x2 represent C8-C1alkyl, preferably branched C8-C18alkyl as defined above. R3 and R3xe2x80x2 is preferably branched octyl as obtained from a dimer of isobutylene, branched nonyl as obtained from a trimer of tripropylene, branched dodecyl obtained from a trimer of isobutylene or a tetramer of propylene, or branched pentadecyl obtained from a pentamer of propylene.
In a particularly preferred embodiment of the invention the aromatic amine has the formula IIxe2x80x2, wherein R1 and R2 represent hydrogen or together represent the group (A) and one of R3 and R3xe2x80x2 represents hydrogen and the other one 1,4,4trimethyl-2-pentyl or straight chained or branched nonyl or both R3 and R3xe2x80x2 represent 1,4,4-trimethyl-2-pentyl or straight chained or branched nonyl.
Aromatic amines of the formulae II and IIxe2x80x2 are known and can be obtained by methods such as the ones described in EP-A-0 149 422. Some compounds of the formula II are commercially available, e.g. under the trade marks Irganox(copyright) (Ciba Specialty Chemicals) L 57 or L 06.
Component c) may consist of one individual compound (II) as defined above or may be present in the composition as a mixture of two or more compounds defined by the formula II, wherein the alkyl groups on the phenyl ring differ by their chain length.
Although the total content of the component c) in the composition is not critical, the preferred total content of component c) in the composition is in the range between 0.1 and 5.0, preferably 0.1 and 1.5 percent by mass based on the total weight of the composition.
Component d)
In the zinc dithiophosphate of the formula III R1 and R2 represent straight chained or branched C3-C20alkyl, e.g. isopropyl or C4-C20alkyl as defined above under component b). Particularly preferred groups R1 and R2 are isopropyl, sec.-butyl and tert.-butyl.
Zinc dithiophosphates of the formula III are known and commercially available, e.g. under the trademark Hitec(copyright) (Hitec Corp.) 769.
Although the total content of the component d) in the composition is not critical, the preferred total content of component c) in the composition is in the range between 0.1 and 5.0, preferably 0.3 and 1.5 percent by mass based on the total weight of the composition, or, in the alternative, between 0.01 and 0.1%, or, preferably, between 0.01 and 0.05%, as expressed as phosphorus content in the composition.
Optional Components: Component e)
The addition of at least one additional customary oil additive to the composition is optional but preferred. The mentioned lubricant compositions, e.g. greases, gear fluids, metal-working fluids and hydraulic fluids, may additionally comprise further additives that are added in order to improve their basic properties still further. Such additives include: further antioxidants, metal passivators, rust inhibitors, viscosity index enhancers, pour-point depressants, dispersants, detergents, further extreme-pressure additives and anti-wear additives. Such additives are added in the amounts customary for each of them, which range in each case approximately from 0.01 to 10.0%, preferably 0.1 to 1.0%, by weight. Examples of further additives are given below:
1. Examples of Phenolic Antioxidants:
1.1. Alkylated monophenols: 2,6-di-tert-butyl-4-methylphenol, 2-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-(xcex1-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear nonylphenols or nonylphenols branched in the side chain, such as, for example, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1xe2x80x2-methyl-undec-1xe2x80x2-yl)-phenol, 2,4-dimethyl-6-(1xe2x80x2-methylheptadec-1xe2x80x2-yl)-phenol, 2,4-dimethyl-6-(1xe2x80x2-methyltridec-1xe2x80x2-yl)-phenol and mixtures thereof;
1.2. Alkylthiomethylphenols: 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
1.3. Hydroquinones and alkylated hydroquinones: 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;
1.4. Tocopherols: xcex1-, xcex2-, xcex3 or xcex4-tocopherol and mixtures thereof (vitamin E);
1.5. Hydroxylated thiodiphenyl ethers: 2,2xe2x80x2-thio-bis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-thio-bis (4-octylphenol), 4,4xe2x80x2-thio-bis(6-tert-butyl-3-methylphenol), 4,4xe2x80x2-thio-bis(6-tert-butyl-2-methylphenol), 4,4xe2x80x2-thio-bis(3,6-di-sec-amylphenol), 4,4xe2x80x2-bis(2,6-dimethyl-4-hydroxy-phenyl)disulfide;
1.6. Alkylidene bisphenols: 2,2xe2x80x2-methylene-bis (6-tert-butyl4-methylphenol), 2,2xe2x80x2-methylene-bis (6-tert-butyl-4-ethylphenol), 2,2xe2x80x2-methylene-bis [4-methyl-6-(xcex1-methylcyclohexyl) phenol], 2,2xe2x80x2-methylene-bis (4-methyl-6-cyclohexylphenol), 2,2xe2x80x2-methylene-bis (6-nonyl-4-methylphenol), 2,2xe2x80x2-methylene-bis (4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidene-bis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidene-bis(6-tert-butyl-4-isobutylphenol), 2,2xe2x80x2-methylene-bis[6-(xcex1-methylbenzyl)-4-nonylphenol], 2,2xe2x80x2-methylene-bis[6-(xcex1,xcex1-dimethyl-benzyl)-4-nonylphenol], 4,4xe2x80x2-methylene-bis(2,6-di-tert-butylphenol), 4,4xe2x80x2-methylene-bis(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, ethylene glycol bis[3,3-bis(3xe2x80x2-tert-butyl-4xe2x80x2-hydroxyphenyl)-butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-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;
1.7. O-. N- and S-benzyl compounds: 3,5,3xe2x80x2,5xe2x80x2-tetra-tert-butyl-4,4xe2x80x2-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;
1.8. Hydroxybenzylated malonates: dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecyl-mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di[4-(1,1,3,3-tetramethylbutyl)-phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate;
1.9. Hydroxybenzyl aromatic compounds: 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;
1.10. Triazine compounds: 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-hydroxybenzyl)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-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate;
1.11. Acylaminophenols: 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamic acid octyl ester;
1.12. Esters of xcex2-(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid: with polyhydric alcohols, e.g. with 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
1.1 3. Esters of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, xcex3-(3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid, 3,5-di-tert-butyl-4-hydroxyphenylacetic acid: with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, isooctanol, 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,Nxe2x80x2-bis-hydroxyethyl oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
1.14. Amides of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid: N,Nxe2x80x2-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine;
1.15. Ascorbic acid (vitamin C);
1.1 6. Aminic antioxidants: N,Nxe2x80x2-diisopropyl-p-phenylenediamine, N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, N,Nxe2x80x2-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-methylheptyl)-p-phenylenediamine, N,Nxe2x80x2dicyclohexyl-p-phenylenediamine, N,Nxe2x80x2-diphenyl-p-phenylenediamine, N,Nxe2x80x2-di(naphth-2-yl)-p-phenylenediamine, N-isopropyl-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1-methylheptyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-cyclohexyl-Nxe2x80x2-phenyl-p-phenylenediamine, 4-(p-toluenesulfonamido)-diphenylamine, N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethyl phenol, 2,4xe2x80x2-diaminodiphenylmethane, 4,4xe2x80x2-diaminodiphenylmethane, N,N,Nxe2x80x2,Nxe2x80x2-tetramethyl-4,4xe2x80x2-diaminodiphenylmethane, 1,2-di[(2-methylphenyl)amino]-ethane, 1,2-di(phenylamino)propane, (o-tolyl)biguanide, di[4-(1xe2x80x2,3xe2x80x2-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and di-alkylated tert-butyl/tert-octyl-diphenylamines, mixture of mono- and di-alkylated nonyldiphenylamines, mixture of mono- and di-alkylated dodecyldiphenylamines, mixture of mono- and di-alkylated isopropyl/isohexyl-diphenylamines, mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and di-alkylated tert-butyl/tert-octyl-phenothiazines, mixtures of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,Nxe2x80x2,Nxe2x80x2-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. Examples of further antioxidants: aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid or salts of dithiocarbamic acid, 2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,11-trithiatridecane and 2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane.
3. Examples of Metal Deactivators. e.g. for Copper:
3.1. Benzotriazoles and derivatives thereof: 2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 4- or 5-alkylbenzotriazoles (e.g. tolutriazole) and derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole, 5,5xe2x80x2-methylene-bis-benzotriazole; Mannich bases of benzotriazole or tolutriazole, such as 1-[di(2-ethylhexyl) aminomethyl]tolutriazole and 1-[di(2-ethylhexyl)aminomethyl]benzotriazole; alkoxyalkylbenzotriazoles, such as 1-(nonyloxy-methyl)benzotriazole, 1-(1-butoxyethyl)-benzotriazole and 1-(1-cyclohexyloxybutyl)-tolutriazole;
3.2. 1,2,4-Triazoles and derivatives thereof: 3-alkyl-(or -aryl-) 1,2,4-triazoles, Mannich bases of 1,2,4-triazoles, such as 1-[di(2-ethylhexyl)aminomethyl]-1,2,4-triazole; alkoxyalkyl-1,2,4-triazoles, such as 1-(1-butoxyethyl)-1,2,4-triazole; acylated 3-amino-1,2,4-triazoles;
3.3. Imidazole derivatives: 4,4xe2x80x2-methylene-bis(2-undecyl-5-methyl) imidazole and bis [(N-methyl)imidazol-2-yl]carbinol-octyl ether;
3.4. Sulfur-containing heterocyclic compounds: 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercaptobenzothiadiazole and derivatives thereof; 3,5-bis [di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-one;
3.5. Amino compounds: salicylidene-propylenediamine, salicylaminoguanidine and salts thereof.
4. Examples of Rust Inhibitors:
4.1. Organic acids, their esters, metal salts, amine salts and anhydrides: alkyl- and alkenylsuccinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl- and alkenyl-succinic acids, 4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxy-carboxylic acids, such as dodecyloxyacetic acid, dodecyloxy (ethoxy) acetic acid and amine salts thereof, and also N-oleoyl-sarcosine, sorbitan monooleate, lead naphthenate, alkenylsuccinic acid anhydrides, e.g. dodecenylsuccinic acid anhydride, 2-(2-carboxyethyl)-1-dodecyl-3-methylglycerol and salts thereof, especially sodium and triethanolamine salts thereof.
4.2. Nitrogen-containing Compounds:
4.2.1. Tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, e.g. oil-soluble alkylammonium carboxylates, and 1-[N,N-bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol;
4.2.2. Heterocyclic compounds: substituted imidazolines and oxazolines, e.g. 2-heptadecenyl-1-(2-hydroxyethyl)-imidazoline;
4.2.3. Sulfur-containing compounds: barium dinonyinaphthalene sulfonates, calcium petroleum sulfonates, alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic 2-sulfocarboxylic acids and salts thereof.
5. Examples of viscosity index enhancers: polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene/acrylate copolymers, polyethers.
6. Examples of pour-point depressants: poly(meth)acrylates, ethylene/vinyl acetate copolymers, alkyl polystyrenes, fumarate copolymers, alkylated naphthalene derivatives.
7. Examples of dispersants/surfactants: polybutenylsuccinic acid amides or imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.
8. Examples of extreme-pressure and anti-wear additives: sulfur- and halogen-containing compounds, e.g. chlorinated paraffins, sulfurized olefins or vegetable oils (soybean oil, rape oil), alkyl- or aryl-di- or -tri-sulfides, benzotriazoles or derivatives thereof, such as bis (2-ethylhexyl) aminomethyl tolutriazoles, dithiocarbamates, such as methylene-bis-dibutyidithiocarbamate, derivatives of 2-mercaptobenzothiazole, such as 1-[N,N-bis(2-ethylhexyl)aminomethyl]-2-mercapto-1H-1,3-benzothiazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole, such as 2,5-bis(tert-nonyidithio)-1,3,4-thiadiazole.
9 Examples of coefficient of friction reducers: lard oil, oleic acid, tallow, rape oil, sulfurized fats, amides, amines. Further examples are given in EP-A-0 565 487.
10. Examples of special additives for use in water/oil metal-working fluids and hydraulic fluids:
Emulsifiers: petroleum sulfonates, amines, such as polyoxyethylated fatty amines, non-ionic surface-active substances; buffers: such as alkanolamines; biocides: triazines, thiazolinones, tris-nitromethane, morpholine, sodium pyridenethiol; processing speed improvers: calcium and barium sulfonates.
The above-mentioned components may be admixed with the above-mentioned, components a)-d) in a manner known per se. It is also possible to prepare a concentrate or a so-called xe2x80x9cadditive packxe2x80x9d, which can be diluted to give the working concentrations for the intended lubricant.
A preferred embodiment of the invention relates to a composition which comprises:
a) a base oil of lubricating viscosity used for engine oils, gear fluids or hydraulic fluids;
b) at least one phenol of the formula (I), wherein R1 represents branched C8-C18alkyl;
c) at least one aromatic amine of the formula:
xe2x80x83wherein R1 and R2 represent hydrogen or together represent the group:
xe2x80x83and one of R3 and R3xe2x80x2 represents hydrogen and the other one C8-C18alkyl or both R3 and R3xe2x80x2 represent C8-C18alkyl;
d) at least one zinc dithiophosphate of the formula (III) wherein R1 and R2 represent branched C3-C18alkyl selected from the group consisting of isopropyl, sec.-butyl and tert.-butyl; and
e) at least one customary oil additive.
A particularly preferred embodiment of the invention relates to a composition, which comprises:
a) a base oil of lubricating viscosity used for engine oils, gear fluids or hydraulic fluids;
b) at least one phenol of the formula (I), wherein R1 consists of isooctyl types selected from the group consisting of 3,4-, 3,5- or 4,5-dimethyl-1-hexyl and 3- or 5-methyl-1-heptyl, or branched alkyl groups with more than 8 carbon atoms, wherein a side chain is attached in 2-position of the carbon chain selected from the group consisting of 2-n-butyl-n-octyl, 2-n-hexyl-n-decyl and 2-n-octyl-n-dodecyl;
c) at least one aromatic amine of the formula IIxe2x80x2, wherein R1 and R2 represent hydrogen or together represent the group (A), one of R3 and R3xe2x80x2 represents hydrogen and the other one branched octyl as obtained from a dimer of isobutylene, branched nonyl as obtained from a trimer of tripropylene, branched dodecyl obtained from a trimer of isobutylene or a tetramer of propylene, or branched pentadecyl obtained from a pentamer of propylene, or both R3 and R3xe2x80x2 represent branched octyl as obtained from a dimer of isobutylene, branched nonyl as obtained from a trimer of tripropylene, branched dodecyl obtained from a trimer of isobutylene or a tetramer of propylene, or branched pentadecyl obtained from a pentamer of propylene;
d) at least one zinc dithiophosphate of the formula (III) wherein R1 and R2 represent branched C3-C18alkyl selected from the group consisting of isopropyl, sec.-butyl and tert.-butyl; and
e) at least one customary oil additive.
High preference is given to a preferred embodiment of the invention that relates to a composition, which comprises:
a) a base oil of lubricating viscosity used for engine oils, gear fluids or hydraulic fluids;
b) at least one phenol of the formula (I), wherein R1 represents isooctyl types selected from the group consisting of 3,4-, 3,5- or 4,5-dimethyl-1-hexyl and 3- or 5-methyl-1-heptyl;
c) at least one aromatic amine of the formula IIxe2x80x2, wherein R1 and R2 represent hydrogen or together represent the group (A) and one of R3 and R3xe2x80x2 represents hydrogen and the other one 1,4,4-trimethyl-2-pentyl or straight chained or branched nonyl or both R3 and R31xe2x80x2 represent 1,4,4-trimethyl-2-pentyl or straight chainedor branched nonyl;
d) at least one zinc dithiophosphate of the formula (III) wherein R1 and R2represent branched C3-C18alkyl selected from the group consisting of isopropyl, sec.-butyl and tert.-butyl; and
e) at least one customary oil additive.
Highest preference is given to a preferred embodiment of the invention that relates to a composition, which comprises:
a) a base oil of lubricating viscosity used for engine oils, gear fluids or hydraulic fluids;
b) 0.2-3.0 weight-% of at least one phenol of the formula (I), wherein R1 represent isooctyl types selected from the group consisting of 3,4-, 3,5- or 4,5-dimethyl-1-hexyl and 3- or 5-methyl-1-heptyl;
c) 0.1-1.5 weight-% of at least one aromatic amine of the formula IIxe2x80x2, wherein R1 and R2 represent hydrogen or together represent the group (A) and one of R3 and R3xe2x80x2 represents hydrogen and the other one 1,4,4-trimethyl-2-pentyl or straight chained or branched nonyl or both R3 and R3xe2x80x2 represent 1,4,4-trimethyl-2-pentyl or straight chained or branched nonyl;
d) 0.01-0.05% (weight-% P) of at least one zinc dithiophosphate of the formula (III) wherein R1 and R2represent branched C3-C18alkyl selected from the group consisting of isopropyl, sec.-butyl and tert.-butyl; and
e) 0.1-1.0 weight-% of at least one customary oil additive.
The present invention also relates to a concentrate that can be used in the preparation for a composition which comprises:
b) at least one phenol of the formula I, wherein R1 represents branched C8-C22alkyl;
c) at least one aromatic amine of the formula II, wherein
R1 and R2 represent hydrogen or together represent the group A and one of R3 and R3xe2x80x2 represents hydrogen and the other one C2-C30alkyl or both R3 and R3xe2x80x2 represent C2-C30alkyl;
d) at least one zinc dithiophosphate of the formula II, wherein R1 and R2represent straight chained or branched C3-C20alkyl.
The oil additives mentioned above under component e) are optionally present in the concentrate. The components are combined in the concentrate that the concentrate is fluid at room temperature without the addition of the base oil a) or a solvent.
The invention also relates to a process for preventing or reducing black sludge formation in lubricating oils for combustion engines; for keeping black sludge particles in suspension in the lubricating oil; and for reducing black sludge deposits in the lubricating system of spark-ignition internal combustion engines, which comprises applying to the lubrication system the composition defined above.
The invention relates also to a method of improving the performance properties of lubricants, which comprises adding to the lubricant at least one composition as defined above.
The invention relates also to the use of compounds of components b), c) and d), and optionally e), preferably in the mentioned concentration, as additives in motor oils, turbine oils, gear oils, hydraulic fluids, metal-working fluids or lubricating greases.

Lubricants with 5-tert.-butyl-4-hydroxy-3-methylphenyl substituted fatty acid esters


The invention relates to a process for conditioning material for pyrometallurgical conversion to magnesium, the process comprising carrying out de-sulfation of the material in a slurry to reduce sulfur content of the material; and carrying out de-ferration of the de-sulfated material in a slurry to reduce iron content of the material to produce a conditioned material suitable for pyrometallurgical conversion to magnesium.

Magnesium is a useful and valuable metal and is commonly used in aluminium alloys, in die-casting (alloyed with zinc), to remove sulfur in the production of iron and steel, and in the production of titanium. Magnesium is used in several high volume part manufacturing applications, including automotive and machine components. Because of its low weight, good mechanical and electrical properties, magnesium is widely used for manufacturing of mobile phones, laptop computers, cameras, and other electronic components.
Most of the world supply of magnesium comes from processing naturally occurring materials such as dolomite and magnesite. Another potential source of magnesium is waste ash material from coal fired power stations burning brown coals.
There are several brown coal deposits around the world. Some of the larger deposits of brown coal, also referred to as lignite, are found in Russia, the United States Germany, Poland and Australia.
The brown coal is typically prepared as a pulverized fine powder (PF) in which form it is delivered to vertical water wall boilers where it is combusted to release heat for steam generation by turbines. The majority of the combustion products are fine particles which are carried by the flue gases out of the boiler and are known as fly ash. The coarser ash particles, principally sand, settle to the bottom of the boiler from where they are collected. This fraction is known as bottom ash and generally constitutes about 20% of the total ash content of the combusted coal. The flue gases from the boiler are often treated with an electrostatic precipitator to remove the fine particles (>99%) and this fraction is known as electrostatic precipitator (EP) fly ash and comprises about 80% of the total ash content of the combusted coal. The fly ash typically contains about 5-20% char (unburnt or partially carbonised coal).
The two ash types are typically mixed with recycled ash pond water and temporarily held in a large ash pit within the power station where some chemical reactions and hydrochemical alterations to the ash begin to occur. The mixed ash slurry, with a liquid to solid ratio typically ranging from about 100:1 down to 10:1, depending on the particular power station, is then pumped to an ash pond for disposal.
Emplaced ash typically continues to 'age', i.e. undergoes further chemical alterations, including most notably hydration and decomposition of brownmillerite (calcium alumino-ferrite) Ca2(Al,Fe)2O5 to a variety of products such as hydrated calcium alumino-ferrites, hematite, iron hydrotalcites, hematite and magnetite and absorption of carbon dioxide (CO2) from the atmosphere which may markedly increase the chemically fixed CO2 content of the emplaced mixed ash. The CO2 content of raw dry EP fly ash is relatively low, typically <1.0% but with ageing in a wet or dry ash emplacement the emplaced mixed ash CO2 content slowly increases, with the CO2 being largely fixed as calcite (calcium carbonate; CaCO3) and magnesite (magnesium carbonate; MgCO3).
The ash from brown coals has a wide variety of applications including soil conditioning/fertilization, as an extender in cement and concrete production and as fillers in non-metallic minerals and building materials. The relatively high magnesium and calcium contents in brown coals results in the brown coal fly ash being classified as 'Class C' fly ash in the American classification system and this also raises the possibility of recovering magnesium (Mg) from the fly ash.
One of the principal methods of manufacture of magnesium metal from suitable feedstock is the pyrometallurgical method known as the Pidgeon Process.
Most raw materials collected from brown coal power generation ash pits or ponds do not have suitable compositional qualities for direct conversion to magnesium using the Pidgeon Process, Failure to treat such raw material, as well as other raw material having similar composition, to achieve compositional qualities suited to the Pidgeon Process or other suitable reductive pyrometallurgical process may inhibit or prevent magnesium formation. Furthermore, magnesium generated from the raw starting material may have multiple impurities rendering it unfit for commercial use or sale.
Furthermore, the calcining stage typically used in the Pidgeon Process to convert dolomite-type feedstock into dame-type form for generation of magnesium requires significant temperatures, which can be energy and cost inefficient.
The present inventor has developed a process particularly suitable for processing fly ash and other materials for reductive pyrometallurgical magnesium production by the Pidgeon Process or other suitable reductive pyrometallurgical processes.


Two connected valve units each formed by serially connecting plural electromagnetic valves in a direct abutment state are disposed in parallel between two end blocks. The two end blocks are tightened with plural connecting bolts disposed therebetween so as to directly clamp and fix the two connected valve units from both sides in the serial connection direction of the electromagnetic valves. One of the end blocks is provided with a power supply connector, and the other is provided with an air inlet port and a discharge port.

1. Field of the Invention
The present invention relates to a parallel type valve assembly having plural electromagnetic valves serially connected in two rows.
2. Description of the Related Art
Generally, the process for installing plural electromagnetic valves on the manifold base and the rail to form a valve assembly has been employed for controlling the fluid pressure equipment such as the air cylinder using those electromagnetic valves. In the aforementioned case, the plural electromagnetic valves are generally arranged in a single row. Preferably, the electromagnetic valves are arranged in two rows for the purpose of efficiently forming the valve assembly using more electromagnetic valves as disclosed in Japanese Unexamined Patent Application Publication Nos. 2004-11858 and 2004-156719.
The valve assembly disclosed in the above documents has plural electromagnetic valves arranged and installed on the single manifold base. The use of the manifold base may unavoidably cause the valve assembly to be large as a whole. The operation for installing the plural electromagnetic valves is complicated as they are individually attached to the manifold base using screws. The number of the electromagnetic valves to be installed on the manifold base is determined in the stage for designing the manifold base. In order to change the number of the electromagnetic valves for the valve assembly, the use of the manifold base with the different structure designed to be adapted to the number of the electromagnetic valves is required.