Transmission fluid compositions comprising a zinc detergent and at least one phosphorus-containing additive have enhanced performance capabilities. The use of the zinc detergent and the phosphorus-containing additive provide transmission fluids that exhibit high steel-on-steel coefficients of friction, particularly useful in continuously variable transmissions (CVT).

This invention relates to transmission fluid compositions comprising a zinc detergent and at least one phosphorus-containing additive having enhanced performance capabilities, including high steel-on-steel coefficients of friction, under conditions similar to those experienced by transmission systems.
There is worldwide activity by automobile manufacturers to develop continuously variable transmissions (CVT). These developments are being driven by benefits from CVTs towards Corporate Average Fuel Economy (CAFE) requirements in the U.S.A.
The advent of ECCC and continuously variable transmissions (CVT) and the manufacturing of passenger cars with smaller transmissions which tend to operate with higher energy densities and higher operating temperatures have challenged lubricant suppliers to formulate transmission fluids with new and unique performance characteristics including higher torque.
CVTs can provide improved fuel efficiency, reduced exhaust emissions and improved driving performance compared to conventional automatic transmissions. The CVT is significantly different from a conventional automatic transmission in several ways. A major feature of the CVT is the transmission of high torque between a steel belt and pulleys providing a continuously variable gear ratio between the input and output shafts. In order to realize high torque transmission between a steel belt and pulleys, high friction between metal/metal contacts is required with normal wear. Loss of transmitting torque between the belt and the pulleys leads to inefficiency and could result in damage to the CVT. A CVT fluid that can transmit high torque generates a high friction force, and, as a result, the belt and the pulleys transmit high torque efficiently. Some CVTs employ a torque converter with an electronically controlled lock-up clutch engaging at low vehicle speeds for further gains in fuel economy and drivability. Acceptable metal/clutch material frictional properties are also required of the CVT fluid when torque converters with a lock-up clutch are used with the CVT.
U.S. Pat. No. 4,897,209 discloses lubricating compositions comprising metal dihydrocarbylaromatic sulfonates and a dialkyl or trialkyl phosphite, wherein the metals are taught to be calcium, barium, sodium, magnesium and lithium. This reference fails to teach transmission fluids containing mixtures of zinc detergents and at least one phosphorus-containing compound or the increased steel-on-steel coefficients of friction obtained by using the fluids of the present invention.
In accordance with this invention there is provided, in one of its embodiments, a transmission fluid comprising a zinc detergent and at least one phosphorus-containing additive.
In another embodiment of the present invention, a method of increasing steel-on-steel friction in continuously variable transmissions is set forth. Said method comprises adding to, and operating in, a continuously variable transmission a fluid comprising (1) a major amount of a base oil and (2) a minor amount of an additive composition which comprises (A) a zinc detergent and (B) at least one phosphorus-containing additive, wherein the transmission fluid contains from about 10 to about 500 parts by weight of zinc per million parts by weight of transmission fluid (ppm w/w), preferably about 20 to 300 ppm w/w of zinc and more preferably from about 30 to about 100 ppm w/w zinc, and from about 50 to about 2000 ppm w/w, preferably 100 to 1000 ppm w/w of phosphorus, and more preferably from about 200 to 800 ppm w/w of phosphorus.
Another embodiment of the present invention is directed to an automotive transmission lubricated with the transmission fluids of the present invention.
The transmission fluids of the present invention comprise a major amount of a base oil and a minor amount of an additive composition which comprises (A) at least one zinc detergent and (B) at least one phosphorus-containing additive.
The zinc detergents useful in this invention are exemplified by oil-soluble neutral or overbased salts of zinc with one or more of the following acidic substances (or mixtures thereof): sulfonic acids, carboxylic acids, salicylic acids, alkyl phenols, and sulfurized alkyl phenols.
Oil-soluble neutral zinc-containing detergents are those detergents that contain stoichiometrically equivalent amounts of zinc in relation to the amount of acidic moieties present in the detergent. Thus, in general the neutral zinc detergents will have a low basicity when compared to their overbased counterparts. The neutral zinc detergents most useful in the present invention include zinc sulfonates, zinc carboxylates, zinc salicylates, zinc phenates and sulfurized zinc phenates and mixtures thereof.
Overbased zinc detergents may be formed by reaction between a neutral zinc detergent and a metal hydroxide. This reaction typically takes place using carbon dioxide in the presence of a promoter, which is generally an alcohol-type material. The promoter dissolves a small amount of metal hydroxide, which is subsequently reacted with carbon dioxide to form a metal carbonate. The amount of metal carbonate incorporated into the overbased detergents can vary depending upon the application in which the overbased detergent is used.
The preferred zinc detergents for use in the present invention include zinc sulfonates. The zinc sulfonates suitable for use in the present invention include zinc dihydrocarbyl aromatic sulfonates such as zinc dialkylnaphthalene sulfonate. The zinc dialkylnaphthalene sulfonate has a sulfonate group attached to one ring of the naphthalene nucleus and an alkyl group attached to each ring. Each alkyl group can independently contain from about six to about twenty carbon atoms, but it is preferred that they contain from about eight to twelve carbon atoms. The dialkylnaphthalene sulfonate group is attached to the zinc through the sulfonate group. A particularly preferred zinc dialkylnaphthalene sulfonate is zinc dinonylnaphthylene sulfonate available commercially as NA-SUL(copyright) ZS from King Industries, Inc.
The zinc detergents useful as component (A) in the present invention may also include mixtures of detergents such as blends of zinc sulfonates and zinc carboxylates in a ratio of zinc sulfonate to zinc carboxylate of from about 1:3 to about 3:1 parts by weight. Said blends are available commercially from King Industries, Inc. under the tradename NA-SUL(copyright) ZS-HT.
As is well known, overbased metal detergents are generally regarded as containing overbased quantitities of inorganic bases, probably in the form of micro dispersions or colloidal suspensions. Thus the term xe2x80x9coil solublexe2x80x9d as applied to the zinc detergents is intended to include zinc detergents that are not necessarily completely or truly oil-soluble, in as much as such detergents when mixed into base oils behave in much the same way as if they were fully and totally dissolved in the base oil.
In one embodiment of the present invention, component (A) is present in an amount sufficient to provide at least 10% by weight of the total zinc content of the fluid. In a preferred embodiment of the present invention, component (A) provides substantially all of the zinc to the finished fluid. The term xe2x80x9csubstantially all of the zinc to the finished fluidxe2x80x9d herein means that greater than 50% of the total zinc, preferably greater than 75% of the total zinc, more preferably greater than 90% of the total zinc, and most preferably 100% of the total zinc content in the finished transmission fluid is provided by component (A).
Component (B) comprises at least one oil-soluble phosphorus-containing additive. Preferred phosphorus-containing additives include phosphate esters, acid phosphate esters, phosphite esters, acid phosphite esters, amine salts of the esters and phosphorus-containing ashless dispersants.
Representative phosphate esters include tributyl phosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate, tristearyl phosphate, trioleyl phosphate, and other C3-C30 phosphate esters, tricresyl phosphate, and other C6-C30 aryl phosphate esters, and mixtures thereof.
Examples of phosphite esters include tributyl phosphite, trihexyl phosphite, tri-2-ethylhexyl phosphite, tridecyl phosphite, trilauryl phosphite, trimyristyl phosphite, tripalmityl phosphite, tristearyl phosphite, trioleyl phosphite, and other C3-C30 phosphite esters, tricresyl phosphite, and other C6-C30 aryl phosphite esters, and mixtures thereof.
Representative acid phosphate esters include mono- or dibutyl hydrogen phosphate, mono- or dipentyl hydrogen phosphate, mono- or di-2-ethylhexyl hydrogen phosphate, mono- or dipalmityl hydrogen phosphate, mono- or dilauryl hydrogen phosphate, mono- or distearyl hydrogen phosphate, mono- or dioleyl hydrogen phosphate, and other C3-C30 alkyl or alkenyl acid phosphates, mono- or dicresyl hydrogen phosphate, and other C6-C30 aryl acid phosphates, and mixtures thereof.
Suitable acid phosphite esters inlcude mono- or dibutyl hydrogen phosphite, mono- or dipentyl hydrogen phosphite, mono- or di-2-ethylhexyl hydrogen phosphite, mono- or dipalmityl hydrogen phosphite, mono- or dilauryl hydrogen phosphite, mono- or distearyl hydrogen phosphite, mono- or dioleyl hydrogen phosphite, and other C3-C30 alkyl or alkenyl acid phosphites, mono- or dicresyl hydrogen phosphite, and other C6-C30 aryl acid phosphites, and mixtures thereof.
The above mentioned esters may form amine salts with a mono-, di- or trisubstituted amine. Examples of suitable amines include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine, benzylamine, dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine, benzyl monoethanolamine, phenyl monoethanolamine, tolyl monoethanolamine, tributylamine, triphenylamine, triheyxlamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioelylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl monopropanolamine, dioctyl monoethanolamine, dihexyl monopropanolamine, dibutyl monopropanolamine, oleyl diethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine, triethanolamine, and tripropanolamine, and mixtures thereof.
The phosphorus-containing ashless dispersants may be formed by phosphorylating an ashless dispersant having basic nitrogen and/or at least one hydroxyl group in the molecule, such as a succinimide dispersant, succinic ester dispersant, succinic ester-amide dispersant, Mannich base dispersant, hydrocarbyl polyamine dispersant, or polymeric polyamine dispersant, and mixtures thereof.
The various types of ashless dispersants described above can be phosphorylated by procedures described in U.S. Pat. Nos. 3,184,411; 3,342,735; 3,403,102; 3,502,607; 3,511,780; 3,513,093; 3,513,093; 4,615,826; 4,648,980; 4,857,214 and 5,198,133.
In one embodiment, the phosphorus-containing dispersants of the present invention are also boronated. Methods that can be used for boronating (borating) the various types of ashless dispersants described above are described in U.S. Pat. Nos. 3,087,936; 3,254,025; 3,281,428; 3,282,955; 2,284,409; 2,284,410; 3,338,832; 3,344,069; 3,533,945; 3,658,836; 3,703,536; 3,718,663; 4,455,243; and 4,652,387. Preferred procedures for phosphorylating and boronating ashless dispersants are set forth in U.S. Pat. Nos. 4,857,214 and 5,198,133.
Component (B) is present in an amount sufficient to provide at least about 50 ppm w/w of phosphorus, preferably from about 50 to 2000 ppm w/w of phosphorus to the fluid.
The transmission fluids of the present invention may further include at least one member selected from the group consisting of dispersants, friction modifiers, viscosity index improvers, alkali metal detergents, alkaline-earth metal detergents, seal swell agents, antioxidants, corrosion inhibitors, foam inhibitors, copper corrosion inhibitors, sulfur and/or phosphorus-containing anti-wear/extreme pressure additives, lubricity agents, and dyes.
The transmission fluid compositions of the present invention typically contain at least one ashless dispersant having basic nitrogen and/or at least one hydroxyl group in the molecule, such as a succinimide dispersant, succinic ester dispersant, succinic ester-amide dispersant, Mannich base dispersant, hydrocarbyl polyamine dispersant, or polymeric polyamine dispersant. The dispersants suitable for use in the present invention include non-phosphorus-containing dispersants, the phosphorus-containing dispersants decribed above as well as mixtures of phosphorus and non-phosphorus-containing dispersants.
Polyamine succinimides in which the succinic group contains a hydrocarbyl substituent containing at least 30 carbon atoms are described for example in U.S. Pat. Nos. 3,172,892; 3,202,678; 3,216,936; 3,219,666; 3,254,025; 3,272,746; and 4,234,435. The alkenyl succinimides may be formed by conventional methods such as by heating an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester with a polyamine containing at least one primary amino group. The alkenyl succinic anhydride may be made readily by heating a mixture of olefin and maleic anhydride to, for example, about 180-220xc2x0 C. The olefin is preferably a polymer or copolymer of a lower monoolefin such as ethylene, propylene, 1 -butene, isobutene and the like and mixtures thereof. The more preferred source of alkenyl group is from polyisobutene having a gel permeation chromatography (GPC) number average molecular weight of up to 10,000 or higher, preferably in the range of about 500 to about 2,500, and most preferably in the range of about 800 to about 1,200.
As used herein the term xe2x80x9csuccinimidexe2x80x9d is meant to encompass the completed reaction product from reaction between one or more polyamine reactants and a hydrocarbon-substituted succinic acid or anhydride (or like succinic acylating agent), and is intended to encompass compounds wherein the product may have amide, amidine, and/or salt linkages in addition to the imide linkage of the type that results from the reaction of a primary amino group and an anhydride moiety.
Alkenyl succinic acid esters and diesters of polyhydric alcohols containing 2-20 carbon atoms and 2-6 hydroxyl groups can be used in forming the phosphorus-containing ashless dispersants. Representative examples are described in U.S. Pat. Nos. 3,331,776; 3,381,022; and 3,522,179. The alkenyl succinic portion of these esters corresponds to the alkenyl succinic portion of the succinimides described above.
Suitable alkenyl succinic ester-amides for forming the phosphorylated ashless dispersant are described for example in U.S. Pat. Nos. 3,184,474; 3,576,743; 3,632,511; 3,804,763; 3,836,471; 3,862,981; 3,936,480; 3,948,800; 3,950,341; 3,957,854; 3,957,855; 3,991,098; 4,071,548; and 4,173,540.
Hydrocarbyl polyamine dispersants that can be phosphorylated are generally produced by reacting an aliphatic or alicyclic halide (or mixture thereof) containing an average of at least about 40 carbon atoms with one or more amines, preferably polyalkylene polyamines. Examples of such hydrocarbyl polyamine dispersants are described in U.S. Pat. Nos. 3,275,554; 3,394,576; 3,438,757; 3,454,555; 3,565,804; 3,671,511; and 3,821,302.
In general, the hydrocarbyl-substituted polyamines are high molecular weight hydrocarbyl-N-substituted polyamines containing basic nitrogen in the molecule. The hydrocarbyl group typically has a number average molecular weight in the range of about 750-10,000 as determined by GPC, more usually in the range of about 1,000-5,000, and is derived from a suitable polyolefin. Preferred hydrocarbyl-substituted amines or polyamines are prepared from polyisobutenyl chlorides and polyamines having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms.
Mannich polyamine dispersants which can be utilized in forming the phosphorylated ashless dispersant is a reaction product of an alkyl phenol, typically having a long chain alkyl substituent on the ring, with one or more aliphatic aldehydes containing from 1 to about 7 carbon atoms (especially formaldehyde and derivatives thereof), and polyamines (especially polyalkylene polyamines). Examples of Mannich condensation products, and methods for their production are described in numerous U.S. Patents.
The preferred hydrocarbon sources for preparation of the Mannich polyamine dispersants are those derived from substantially saturated petroleum fractions and olefin polymers, preferably polymers of mono-olefins having from 2 to about 6 carbon atoms. The hydrocarbon source generally contains at least about 40 and preferably at least about 50 carbon atoms to provide substantial oil solubility to the dispersant. The olefin polymers having a GPC number average molecular weight between about 600 and 5,000 are preferred for reasons of easy reactivity and low cost. However, polymers of higher molecular weight can also be used. Especially suitable hydrocarbon sources are isobutylene polymers.
The preferred Mannich base dispersants for this use are Mannich base ashless dispersants formed by condensing about one molar proportion of long chain hydrocarbon-substituted phenol with from about 1 to 2.5 moles of formaldehyde and from about 0.5 to 2 moles of polyalkylene polyamine.
Polymeric polyamine dispersants suitable for preparing phosphorylated ashless dispersants are polymers containing basic amine groups and oil solubilizing groups (for example, pendant alkyl groups having at least about 8 carbon atoms). Such materials are illustrated by interpolymers formed from various monomers such as decyl methacrylate, vinyl decyl ether or relatively high molecular weight olefins, with aminoalkyl acrylates and aminoalkyl acrylamides. Examples of polymeric polyamine dispersants are set forth in U.S. Pat. Nos. 3,329,658; 3,449,250; 3,493,520; 3,519,565; 3,666,730; 3,687,849; and 3,702,300.
The compositions of the present invention may contain one or more friction modifiers. Friction modifiers suitable for use in the present invention include such compounds as aliphatic fatty amines or alkoxylated aliphatic fatty amines, alkoxylated aliphatic ether amines, aliphatic carboxylic acids, polyol esters, aliphatic fatty acid amides, alkoxylated aliphatic fatty acid amides, aliphatic fatty imidazolines, and aliphatic fatty tertiary amines, wherein the aliphatic group usually contains above about eight carbon atoms so as to render the compound suitably oil soluble. Also suitable are aliphatic substituted succinimides formed by reacting one or more aliphatic succinic acids or anhydrides with ammonia or other primary amines such as those taught in EP-A-0389237, as well as mixtures of two or more friction modifiers. Friction modifiers suitable for use in the present invention are described in the following U.S. Patents, incorporated herein by reference for their disclosures relating to friction modifiers: U.S. Pat. Nos. 5,344,579; 5,372,735 and 5,441,656. Polyol esters suitable for use in the present invention include the esters obtained by reacting a polyol, such as glycerol and sorbitan, with a fatty acid. Examples of preferred polyol esters include glycerol monooleate, glycerol dioleate, glycerol monolaurate, sorbitan monooleate and mixtures thereof.
Generally speaking, the compositions of this invention will contain up to about 1.25 wt % on an active ingredient basis, and preferably up to about 1 wt % on an active ingredient basis of one or more friction modifiers.
The compositions of the present invention optionally, but preferably, contain a viscosity index improver (VII). Preferred VIIs include, but are not limited to, olefin copolymer VIIs, polyalkyl (meth) acrylate VIIs, styrene-maleic ester VIIs and mixtures of the foregoing products. Also suitable for use in the present invention are dispersant and dispersant/antioxidant VIIs as well as mixtures of dispersant and non-dispersant VIIs. The viscosity index improver is supplied in the form of a solution in an inert solvent, typically a mineral oil solvent, which usually is a severely refined mineral oil. The viscosity index improver solution as received often will have a boiling point above 200xc2x0 C., and a specific gravity of less than 1 at 25xc2x0 C. On an active ingredient basis (i.e., excluding the weight of inert diluent or solvent associated with the viscosity index improver as supplied), the finished fluid compositions of this invention will normally contain in the range of about 1 to about 20 wt % of the polymeric viscosity index improver. Small departures from this range may be resorted to as necessary or desirable in any given situation.
Specific examples of viscosity index improvers useful in the present invention include, but are not limited to, styrene-maleic ester VIIs such as LUBRIZOL(copyright) 3702, LUBRIZOL(copyright)3706 and LUBRIZOL(copyright)3715 available from The Lubrizol Corporation; polyalkylmethacrylate VIIs such as those available from Rxc3x96HM GmbH (Darmstadt, Germany) under the trade designations: VISCOPLEX(copyright) 5543, VISCOPLEX(copyright) 5548, VISCOPLEX(copyright) 5549, VISCOPLEX(copyright) 5550, VISCOPLEX(copyright) 5551 and VISCOPLEX(copyright) 5151, from Rohm and Haas Company (Philadelphia, Pa.) under the trade designations ACRYLOID(copyright) 1277, ACRYLOID(copyright) 1265 and ACRYLOID(copyright)1269, and from Ethyl Corporation (Richmond, Va.) under the trade designation HiTEC(copyright) 5710 viscosity index improver; and olefin copolymer VIIs such as HiTEC(copyright) 5747 VII, HiTEC(copyright) 5751 VII, HiTEC(copyright) 5770 VII and HiTEC(copyright) 5772 VII available from Ethyl Corporation and SHELLVIS(copyright) 200 available from Shell Chemical Company.
Preferably, the viscosity index improver will be provided as a hydrocarbon solution having a polymer content in the range of from about 25 to about 80 wt % and a nitrogen content in the range of about 0 to about 0.5 wt %.
The transmission fluids of the present invention may contain alkali metal detergents and/or alkaline-earth metal detergents in addition to the zinc detergents described above. The alkali and alkaline-earth metal detergents useful in this invention are exemplified by oil-soluble neutral or overbased salts of alkali and alkaline-earth metals with one or more of the following acidic substances (or mixtures thereof): sulfonic acids, carboxylic acids, salicylic acids, alkyl phenols, and sulfurized alkyl phenols.
Oil-soluble neutral alkali and alkaline-earth metal-containing detergents are those detergents that contain stoichiometrically equivalent amounts of alkali and alkaline-earth metal in relation to the amount of acidic moieties present in the detergent. Thus, in general the neutral alkali and alkaline-earth metal detergents will have a low basicity when compared to their overbased counterparts. Methods of preparation of overbased alkali and alkaline-earth metal-containing detergents are known in the art and there are numerous commercially available overbased detergents on the market.
The alkali and alkaline-earth metal detergents include neutral and overbased sodium sulfonates, sodium carboxylates, sodium salicylates, sodium phenates, sulfurized sodium phenates, calcium sulfonates, calcium carboxylates, calcium salicylates, calcium phenates, sulfurized calcium phenates, lithium sulfonates, lithium carboxylates, lithium salicylates, lithium phenates, sulfurized lithium phenates, magnesium sulfonates, magnesium carboxylates, magnesium salicylates, magnesium phenates, sulfurized magnesium phenates, potassium sulfonates, potassium carboxylates, potassium salicylates, potassium phenates, sulfurized potassium phenates.
The seal swell agents useful in the present invention include esters, alcohols, sulfolanes, or mineral oils that cause swelling of elastomeric materials. The ester based seal swell agents include esters of monobasic and dibasic acids with monoalcohols, or esters of polyols with monobasic esters. Suitable diesters include the adipates, azelates, and sebacates of C8-C13 alkanols (or mixtures thereof), and the phthalates of C4-C13 alkanols (or mixtures thereof). Mixtures of two or more different types of diesters (e.g., dialkyl adipates and dialkyl azelates, etc.) can also be used. Examples of such materials include the n-octyl, 2-ethylhexyl, isodecyl, and tridecyl diesters of adipic acid, azelaic acid, and sebacic acid, and the n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl diesters of phthalic acid. Polyol esters such as Emery(trademark) 2935, 2936, and 2939 esters from the Emery Group of Henkel Corporation and Hatcol(trademark) 2352, 2962, 2925, 2938, 2939, 2970, 3178, and 4322 polyol esters from Hatco Corporation are also suitable.
Alcohol type seal swell agents are typically linear alkyl alcohols of low volatility. Examples of suitable alcohols are decyl alcohol, tridecyl alcohol and tetradecyl alcohol. Examples of substituted sulfolanes are described in U.S. Pat. Nos. 4,029,587 and 4,029,588. Mineral oils useful as seal swellers are typically low viscosity mineral oils with high naphthenic or aromatic content. Examples of suitable mineral oils are Exxon Necton-37 (FN 1380) and Exxon Mineral Seal Oil (FN 3200). Typical fluids produced by this invention will contain from about 1 to about 30 weight percent seal sweller. Preferred ranges of seal sweller are from about 2 to about 20 weight percent and most preferred are from about 5 to about 15 weight percent.
The transmission fluids of the present invention may also contain a metal dihydrocarbyl dithiophosphate characterized by the formula ((R3O)(R4O)PSS)zM wherein R3 and R4 are each independently hydrocarbyl groups containing from 3 to about 13 carbon atoms, preferably from 3 to about 8, M is a metal, and z is an integer equal to the valence of M.
The hydrocarbyl groups R3 and R4 in the dithiophosphate may be alkyl, cycloalkyl, aralkyl or alkaryl groups. Illustrative alkyl groups include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl groups, n-hexyl, methylisobutyl carbinyl, heptyl, 2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, etc. Illustrative lower alkylphenyl groups include butylphenyl, amylphenyl, heptylphenyl, etc. Cycloalkyl groups likewise are useful and these include chiefly cyclohexyl and the lower alkyl-cyclohexyl radicals. Many substituted hydrocarbon groups may also be used, e.g., chloropentyl, dichlorophenyl, and dichlorodecyl.
The phosphorodithioic acids from which the metal salts useful in this invention are prepared are well known. Examples of dihydrocarbyl phosphorodithioic acids and metal salts, and processes for preparing such acids and salts are found in, for example, U.S. Pat. Nos. 4,263,150; 4,289,635; 4,308,154; and 4,417,990. These patents are hereby incorporated by reference for such disclosures.
The phosphorodithioic acids are prepared by the reaction of phosphorus pentasulfide with an alcohol or phenol or mixtures of alcohols. The reaction involves four moles of the alcohol or phenol per mole of phosphorus pentasulfide, and may be carried out within the temperature range from about 50xc2x0 C. to about 200xc2x0 C. Thus the preparation of O,O-di-n-hexyl phosphorodithioic acid involves the reaction of phosphorus pentasulfide with four moles of n-hexyl alcohol at about 100xc2x0 C. for about two hours. Hydrogen sulfide is liberated and the residue is the defined acid. The preparation of the metal salt of this acid may be effected by reaction with metal oxide. Simply mixing and heating these two reactants is sufficient to cause the reaction to take place and the resulting product is sufficiently pure for the purposes of this invention.
The metal salts of dihydrocarbyl dithiophosphates which are useful in this invention include those salts containing Group I metals, Group II metals, aluminum, lead, tin, molybdenum, manganese, cobalt, and nickel. Group I and Group II (including Ia, Ib, IIa and IIb are defined in the Periodic Table of the Elements in the Merck Index, 9th Edition (1976). The Group II metals, aluminum, tin, iron, cobalt, lead, molybdenum, manganese, nickel and copper are among the preferred metals. Zinc is an especially preferred metal.
In one preferred embodiment, the alkyl groups R3 and R4 are derived from secondary alcohols such as isopropyl alcohol, secondary butyl alcohol, 2-pentanol, 2-methyl-4-pentanol, 2-hexanol, and 3-hexanol.
Especially useful metal phosphorodithioates can be prepared from phosphorodithioic acids which in turn are prepared by the reaction of phosphorus pentasulfide with mixtures of alcohols. In addition, the use of such mixtures enables the utilization of cheaper alcohols which in themselves may not yield oil-soluble phosphorodithioic acids or salts thereof. Thus a mixture of isopropyl and hexyl alcohols can be used to produce a very effective, oil-soluble metal phosphorodithioate. For the same reason mixtures of phosphorodithioic acids can be reacted with the metal compounds to form less expensive, oil-soluble salts.
The mixtures of alcohols may be mixtures of different primary alcohols, mixtures of different secondary alcohols or mixtures of primary and secondary alcohols.
When metal dihydrocarbyl dithiophosphates are used, the amount of phosphorus provided to the finished fluid is taken into consideration in calculating the total phosphorus content of the finished fluid. Likewise, when zinc dihydrocarbyl dithiophosphate is used, the amount of zinc and phosphorus must be considered in determining the total zinc and phosphorus contents of the finished fluid. Zinc dihydrocarbyl dithiophosphate, if used, is used in an amount so as to provide less than about 90 weight percent of the total zinc content of the finished fluid, preferably less than about 50 weight percent, more preferably less than about 25 weight percent, and most preferably less than about 10 weight percent, of the total zinc content of the finished fluid.
The lubricant compositions of the present invention typically will contain some inhibitors. The inhibitor components serve different functions including rust inhibition, corrosion inhibition and foam inhibition. The inhibitors may be introduced in a preformed additive package that may contain in addition one or more other components used in the compositions of this invention. Alternatively these inhibitor components can be introduced individually or in various sub-combinations. While amounts can be varied within reasonable limits, the finished fluids of this invention will typically have a total inhibitor content in the range of about 0 to about 4 weight percent and preferably about 0.1 to about 2 weight percent, both on an xe2x80x9cactive ingredient basisxe2x80x9dxe2x80x94i.e., excluding the weight of inert materials such as solvents or diluents normally associated therewith.
Foam inhibitors form one type inhibitor suitable for use as inhibitor components in the compositions of this invention. These include silicones, polyacrylates, surfactants, wetting agents and the like. One suitable acrylic defoamer material is PC-1244 (Monsanto Company).
Copper corrosion inhibitors constitute another class of optional additives suitable for inclusion in the compositions of this invention. Such compounds include thiazoles, triazoles and thiadiazoles. Examples of such compounds include benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole, 2-mercapto benzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles, 2-mercapto-5- hydrocarbyldithio-1,3,4-thiadiazoles, 2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, and 2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles. The preferred compounds are the 1,3,4-thiadiazoles, a number of which are available as articles of commerce, and also combinations of triazoles such as tolyltriazole with a 1,3,5-thiadiazole such as a 2,5-bis(alkyldithio)-1,3,4-thiadiazole. Materials of these types that are available on the open market include Cobratec(trademark) TT-100 and HiTEC(copyright) 4313 additive (Ethyl Petroleum Additives, Inc.). The 1,3,4-thiadiazoles are generally synthesized from hydrazine and carbon disulfide by known procedures. See, for example, U.S. Pat. Nos. 2,765,289; 2,749,311; 2,760,933; 2,850,453; 2,910,439; 3,663,561; 3,862,798; and 3,840,549.
Rust or corrosion inhibitors comprise another type of inhibitor additive for optional use in this invention. Such materials include monocarboxylic acids and polycarboxylic acids. Examples of suitable monocarboxylic acids are octanoic acid, decanoic acid and dodecanoic acid. Suitable polycarboxylic acids include dimer and trimer acids such as are produced from such acids as tall oil fatty acids, oleic acid, linoleic acid, or the like. Products of this type are currently available from various commercial sources, such as, for example, the dimer and trimer acids sold under the HYSTRENE trademark by the Humko Chemical Division of Witco Chemical Corporation and under the EMPOL trademark by Henkel Corporation. Another useful type of rust inhibitor for use in the practice of this invention is comprised of the alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapropenylsuccinic acid, tetrapropenylsuccinic anhydride, tetradecenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenylsuccinic acid, hexadecenylsuccinic anhydride, and the like. Also useful are the half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols. Other suitable rust or corrosion inhibitors include ether amines; acid phosphates; amines; polyalkoxylated compounds such as alkoxylated amines, alkoxylated phenols, and alkoxylated alcohols; imidazolines; aminosuccinic acids or derivatives thereof, and the like. Materials of these types are available as articles of commerce. Mixtures of such rust or corrosion inhibitors can be used.
Antioxidants, although not required, are typically present in the lubricant formulations of the present invention. Suitable antioxidants include phenolic antioxidants, aromatic amine antioxidants and sulfurized phenolic antioxidants, among others. Examples of phenolic antioxidants include 2,6-di-tert-butylphenol, liquid mixtures of tertiary butylated phenols, 2,6-di-tert-butyl-4-methylphenol, 4,4xe2x80x2- methylenebis(2,6-di-tert-butylphenol), 2,2xe2x80x2-methylenebis(4-methyl-6-tert-butylphenol), mixed methylene-bridged polyalkyl phenols, and 4,4xe2x80x2-thiobis(2-methyl-6-tert-butylphenol). N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, 4-isopropylaminodiphenyl amine, phenyl-naphthyl amine, and ring-alkylated diphenylamines serve as examples of aromatic amine antioxidants. Most preferred are the sterically hindered tertiary butylated phenols, the ring-alkylated diphenylamines and combinations thereof.
In selecting any of the foregoing optional additives, it is important to ensure that the selected component(s) is/are soluble or stably dispersible in the additive package and finished composition, are compatible with the other components of the composition, and do not interfere significantly with the performance properties of the composition, such as the friction, viscosity and/or shear stability properties, needed or at least desired in the overall finished composition.
In general, the ancillary additive components are employed in the oils in minor amounts sufficient to improve the performance characteristics and properties of the base fluid. The amounts will thus vary in accordance with such factors as the viscosity characteristics of the base fluid employed, the viscosity characteristics desired in the finished fluid, the service conditions for which the finished fluid is intended, and the performance characteristics desired in the finished fluid. However, generally speaking, the following concentrations (mass percent) of the additional components (active ingredients) in the base fluids are illustrative:
It will be appreciated that the individual components employed can be separately blended into the base fluid or can be blended therein in various sub-combinations, if desired. Moreover, such components can be blended in the form of separate solutions in a diluent. It is preferable, however, to blend the additive components used in the form of a concentrate, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
Additive concentrates can thus be formulated to contain all of the additive components and if desired, some of the base oil component, in amounts proportioned to yield finished fluid blends consistent with the concentrations described above. In most cases, the additive concentrate will contain one or more diluents such as light mineral oils, to facilitate handling and blending of the concentrate. Thus concentrates containing up to about 50% by weight of one or more diluents or solvents can be used, provided the solvents are not present in amounts that interfere with the low and high temperature and flash point characteristics and the performance of the finished power transmission fluid composition. In this connection, the additive components utilized pursuant to this invention should be selected and proportioned such that an additive concentrate or package formulated from such components will have a flash point of 170xc2x0 C. or above, and preferably a flash point of at least 180xc2x0 C., using the ASTM D-92 test procedure.
The base oils used in forming the transmission fluids of this invention can be any suitable natural or synthetic oil having the necessary viscosity properties for this usage. Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil etc.), liquid petroleum oils and hydrorefined, severely hydrotreated, iso-dewaxed, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils. The synthetic lubricating oils suitable for use in this invention include one of any number of commonly used synthetic hydrocarbon oils, which include, but are not limited to, poly-alpha-olefins, synthetic esters, alkylated aromatics, alkylene oxide polymers, interpolymers, copolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification etc., esters of dicarboxylic acids and silicon-based oils. Thus, the base oil may be composed entirely of a natural oil such as mineral oil of suitable viscosity or it may be composed entirely of a synthetic oil such as a poly-alpha-olefin oligomer of suitable viscosity. Likewise, the base oil may be a blend of natural and synthetic base oils provided that the blend has the requisite properties for use in the formation of a transmission fluid. Ordinarily, the base oil should have a kinematic viscosity in the range of 1 to 10, preferably 3 to 8, centistokes (cSt) at 100xc2x0 C. Preferred transmission fluids used in the practice of this invention can be formulated without a viscosity index improver so as to possess a kinematic viscosity of at least 4.0 cSt at 100xc2x0 C. and a Brookfield viscosity of no more than about 50,000 cP, preferably no more than about 30,000 cP, and more preferably no more than about 20,000 cP, at xe2x88x9240xc2x0 C., or formulated using a viscosity index improver so as to possess a kinematic viscosity of at least 5.0, and preferably at least 6.8, cSt at 100xc2x0 C. and a Brookfield viscosity of no more than 20,000 cP at xe2x88x9240xc2x0 C.
Transmission fluids are required by the automotive industry to meet numerous performance criteria. The additive systems of the present invention contribute to not only to a desirable increase in the steel-on-steel coefficient of friction but also to the cleanliness provided by the transmission fluid, increased TBN of the fluid, rust inhibition as determined by ASTM D-130, antioxidancy and demulsibility. The additive systems of the present invention provide flexibility in formulating transmission fluids.

Zinc and phosphorus containing transmission fluids having enhanced performance capabilities


The invention relates to a gas bag module comprising a gas bag including a gas bag wall which has a front and a rear wall section and including at least one chamber. The gas bag further comprises an indentation running from the front wall section in an inflated state in a direction toward the rear wall section. The indentation is formed in that a part of the gas bag wall is prevented from an unimpeded movement towards outside of the module on unfolding of the gas bag. The gas bag, in a region of a mouth of the indentation, has a bubble-like inflatable extension in flow connection with the at least one chamber of the gas bag, which extension closes the indentation.

The invention relates to a gas bag module.
Known gas bag modules comprise a gas bag with a gas bag wall which has a front and a rear wall section, an indentation running from the front wall section in the inflated state in the direction toward the rear wall section, which indentation is formed in that a part of the gas bag wall is prevented from an unimpeded movement towards outside of the module on unfolding of the gas bag. Such gas bags are intended to be incorporated in the steering wheel or the instrument panel and to protect the occupant in a frontal impact. The gas bag has an annular chamber which is to be inflated, and the inner wall, delimiting the indentation, is formed by the indentation. The indentation extends from the front wall centrally towards the rear, and the lowest point of the indentation is formed by a fabric piece which is permanently fastened to the gas bag module and hence on unfolding is not moved freely towards the occupant, to prevent him from being held back. The gas bag usually emerges obliquely outwards from the module owing to the annular shape of the chamber, and only subsequently does the front wall section move towards the occupant.
With an occupant sitting centrally and with a high impact intensity, it is to be prevented that the occupant""s head can plunge into the indentation. This is achieved by constructional approaches that are differingly complicated. The invention provides a simple, cost-effective solution for this.
This is achieved in a gas bag module which comprises a gas bag including at least one chamber as well as including a gas bag wall which has a front and a rear wall section. The gas bag further comprises an indentation running from the front wall section in an inflated state in a direction toward the rear wall section. The indentation is formed in that a part of the gas bag wall is prevented from an unimpeded movement towards outside of the module on unfolding of the gas bag. The gas bag, in a region of a mouth of the indentation, has a bubble-like inflatable extension in flow connection with the at least one chamber of the gas bag, which extension closes the indentation.
According to the preferred embodiment, the gas bag according to the invention has an indentation which at least in sections runs obliquely, which indentation is preferably already closed at its mouth and thus prevents the slightest plunging of the occupant""s head into the indentation. The obliquely running wall section makes it possible that, at least in the case of a heavy occupant plunging in the gas bag, the extension is supported by the gas bag wall defining the indentation. If applicable, such supporting is already provided in the fully inflated state of the gas bag, without an occupant acting. The inflatable extension may impart an asymmetric shape to the gas bag, and may compress the mouth laterally from one side and close it.
Preferably, the extension moves on inflation radially towards the mouth, in order to close it and to give the indentation an oblique orientation. The oblique orientation, however, is not necessarily to be created by the extension. The oblique orientation can be achieved by a middle axis of the indentation running obliquely with respect to the middle axis of the gas bag or by a part of the gas bag wall defining the indentation extending at least partially obliquely so that the indentation has not a fully cylindrical shape.
In the inflated state, the extension preferably projects outwards with respect to the front wall section, which is useful for the stability of the gas bag and also gives the extension, which acts like a closure, a greater stability.
The preferred embodiment of the gas bag makes provision that, in relation to the spread-out, non-inflated state of the gas bag, the latter consists of at least four fabric sections lying one over the other and being connected with each other. An upper and a lower fabric piece are provided to form the front and rear wall sections, respectively. In addition, the gas bag has two inner fabric pieces which delimit the indentation. These inner fabric pieces may have an asymmetrical annular shape and a bulge to form the extension. The inner fabric pieces are usually sewn to each other at their outer edges.
In one embodiment, provision can be made in addition that all the fabric pieces have a central opening, with the possibility of arranging the openings so as to be concentrical to each other, again in relation to the spread-out, non-inflated state of the gas bag.
The inner fabric pieces may have an identical external geometry, which facilitates the sewing of the two fabric pieces on the outer edge.
The bulges of the inner fabric pieces preferably have a shape which is similar to a mushroom cap. A ring segment then adjoins the underside of the cap.

TRW Automotive Safety Systems GmbH and Co. KG


Methods are provided for decreasing aldehyde content in polyolefin materials comprising combining with the polyolefin material an organic additive compound which reacts with aldehydes to form water and a resulting organic compound. The organic additive compound comprises at least two hydrogen-substituted heteroatoms bonded to carbons of the organic additive compound such that the organic additive compound is reactive with aldehydes present in the polyolefin to form water and the resulting organic compound, which comprises an unbridged five- or six-member ring including the at least two heteroatoms. The resulting organic compound advantageously neither imparts an off-taste to food and beverage products in contact with the polyolefin nor discolors the polyolefin. Preferred polyolefins include polypropylene and polyethylene.

The present invention generally relates to polyolefin products such as polyethylene and polypropylene packaging materials for food and beverages. More particularly, this invention relates to reduction of aldehydes in polyolefins by incorporation of additives capable of reacting with these aldehydes.
Polyolefins, particularly polyethylene and polypropylene, are utilized extensively across a wide range of industries in a variety of product forms, including fibers, films, and three-dimensional structures. A particularly important application for polyolefins is containers, especially for food and beverages. Polyolefin materials often are selected for use in food and beverage packages and closures because they are inexpensive, lightweight, easily modified, and impact resistant. Yet despite these advantages, polyolefins can have certain undesirable attributes. For example, they frequently contribute xe2x80x9coff-tastexe2x80x9d to packaged products, particularly sensitive products such as water. This off-taste commonly is referred to as a xe2x80x9cplasticxe2x80x9d off-taste. It would be highly desirable to reduce or eliminate this off-taste from products packaged in polyolefin materials.
One approach that has been taken to mitigate the off-taste problem in the non-polyolefin polymer polyethylene terephthalate (PET) is to incorporate additives that are scavengers for aldehydes that are produced by degradation of the PET itself during heat processing of the polymer. U.S. Pat. No. 4,837,115 to Igarashi discloses incorporating additives of amine-group terminated polyamides and amine-group containing small molecules into PET, wherein the additives selectively react with acetaldehyde (AA) that is generated in the PET. Igarashi teaches that the amine groups are effective because they can react with AA to form imines, where the amine nitrogen forms a double bond with the AA moiety. Igarashi teaches that essentially any amine is effective. Mills (U.S. Pat. Nos. 5,258,233; 5,650,469; and 5,340,884) and Long (U.S. Pat. No. 5,266,416) disclose the use of various polyamides, especially low molecular weight polyamides, while Turner and Nicely (PCT WO 97/28218) disclose the use of polyesteramides. These polyamides and polyesteramides are believed to react with AA in the same manner as described by Igarashi. While these AA scavengers are effective at reducing the AA content of melt-processed PET, they suffer from their own drawbacks. In particular, relatively high loadings of the polyamides are needed to effect significant AA reductions, and a significant yellowing of the PET occurs from incorporation of these amine-containing additives. This coloring is believed to be due to the inherent color of the imine group, which for most applications is undesirable because most polyolefin articles in use today are clear and uncolored.
U.S. Pat. No. 5,663,223 to Teumac discloses using a polymeric liner that includes inorganic sulfites or organic hydrazides as flavor protectant compounds. These compounds are added to scavenge oxygen that otherwise could react with the polymer or additives therein to form off-taste producing aldehydes. Incorporation of these compounds into polyolefins is difficult, however, because these protectant compounds have an extremely low thermal stability. Furthermore, these compounds may themselves contribute to an off-taste in sensitive products, and hydrazides react with aldehydes to form hydrazones, which often are highly colored. Such colors oftentimes are unwanted, as many applications require or desire that the polyolefin packaging be white or clear.
A simple and economical method is therefore needed for reducing aldehyde content in polyolefin products without using aldehyde-scavenging agents that impart an off-taste to products packaged in containers made from polyolefins or that impart a color to such polyolefin containers.
It is therefore an object of the present invention to provide methods for decreasing aldehyde content of products in contact with polyolefin packaging materials.
It is another object of the present invention to provide methods for decreasing aldehyde content in polyolefin materials without coloring the polyolefin materials and without creating another source of product off-taste.
It is a further object of the present invention to provide polyolefin packaging containers which provide a decreased aldehyde content of products contained therein.
Methods are provided for decreasing the aldehyde content in polyolefin materials by combining the polyolefin material with an organic additive compound that reacts with aldehydes to form water and a resulting organic compound. The organic additive compound comprises at least two hydrogen-substituted heteroatoms bonded to carbons of the organic additive compound such that the organic additive compound is reactive with aldehydes present in the polyolefin to form water and the resulting organic compound, which comprises an unbridged five- or six-member ring including the at least two heteroatoms. The resulting organic compound neither imparts an off-taste to food and beverage products in contact with the polyolefin nor discolors the polyolefin.
The organic additive compound can be added at relatively low levels to the polyolefin and still sufficiently decrease the aldehyde content of the polyolefin. The organic additive compound preferably is substantially thermally stable at the melt processing temperature of the polyolefin. Preferred organic additive compounds include anthranilamide, 3,4-diaminobenzoic acid, malonamide, tryptophan, and allantoin.
It has been discovered that the off-taste from beverage and food products packaged in polyolefin materials is in fact largely due to the migration of C8 through C10 aldehydes from the polyolefin into the products, and that these aldehydes typically are the degradation products of various unsaturated additives used as processing aids in the polyolefins. These additives degrade chemically, thermally, or by photo-oxidation to yield these undesirable aldehydes. Examples of processing aid additives are erucic acid derivatives, such as erucamide, which often is used as a processing aid additive due to its efficacy and low cost. Although one might propose eliminating the processing aid additives as a solution to the aldehyde problem, the processing properties provided by the unsaturated additives are important and not readily duplicated. It thus is desirable to continue the use of unsaturated additives while simultaneously minimizing or eliminating the off-taste caused by their degradation. Methods therefore have been developed for substantially decreasing the aldehyde content of processed polyolefins by incorporating low levels of an organic additive compound into the polyolefin, such as during melt processing. The organic additive compound scavenges the aldehyde present in the polyolefin by chemically reacting with the aldehyde.
The Aldehyde-Containing Polyolefin
The present method is useful for removing aldehydes from a variety of polyolefin materials. In preferred embodiments, the polyolefin is polypropylene (PP) or polyethylene (PE). Other useful polymers include polyisoprene, polystyrene, poly(vinyl chloride), and poly(methylmethacrylate). The present method can be used with essentially any polyolefin polymer in which unsaturated additives have been incorporated.
Polyolefins, such as PP and PE, can be processed to form films, sheets, and three-dimensional articles, which can be used as or in packaging containers and closures. As part of the processing of the polyolefin, for example, melt-processing (e.g., extrusion and molding), processing aids typically are added to achieve favorable product properties and/or to improve ease of polymer processing. Representative types of processing aid additives include internal lubricants, external lubricants, and viscosity modifiers. Many of these processing aid additives are unsaturated compounds. Euramide, for example, often is added to polyethylene and polypropylene to act as a lubricant to improve handling and prevent the polymer product from sticking to itself. Other unsaturated additives that may generate the off-taste aldehyde include vegetable oil derivatives and castor oil derivatives. These unsaturated processing aid additives are known to degrade thermally, chemically, or by photo-oxidation to generate aldehydes in the polyolefin material. The aldehydes particularly identified as causing off-taste in products are octanal, nonanal, and decanal (i.e. the C8 through C10 aldehydes).
The Organic Additive Compound
Suitable organic additive compounds effective in the method described herein are characterized as small molecules that include at least two hydrogen-substituted heteroatoms bonded to carbons of the organic additive compound such that the organic additive compound is reactive with aldehyde in the polyolefin to form water and a resulting organic compound comprising an unbridged 5- or 6-member ring including the at least two heteroatoms. Unlike prior art methods that depend on the formation of inherently colored imines, the formation of unbridged 5- or 6-member ring structures do not inherently result in color formation. Moreover, thermodynamics often favor ring formation more than imine formation; therefore, significantly lower amounts of the organic additive compound described herein can effectively decrease the aldehyde content in processed polyolefins.
Heteroatoms capable of reacting with the aldehyde include oxygen (O), nitrogen (N), and sulfur (S). The heteroatoms of the additive compound should have at least one bond to an active hydrogen (H), and in the course of condensing with the aldehyde should split off water. Preferred functional groups containing these heteroatoms include amine (NH2 and NHR), hydroxyl (OH), carboxyl (CO2H), amide (CONH2 and CONHR), and thiol (SH). It is necessary for these functional groups to be sterically arranged so that upon condensation with the aldehyde an unbridged 5- or 6-member ring can be formed. The structural arrangement preferably allows the formation of a six-member ring. Furthermore, it is especially preferred that heteroatoms of the organic additive are attached to a preformed ring or rings. The preformed ring(s) most preferably are aromatic so that the unbridged 5- or 6-member ring of the resulting organic compound is bonded to the aromatic ring.
The organic additive compound preferably is substantially thermally stable at the temperatures required for melt-processing the polyolefin. The organic additive compound also preferably includes functional groups that include the heteroatoms and active hydrogens and that are relatively unreactive toward other additives, if any, present in the polyolefin. High thermal stability and low reactivity to other additives increase the amount of unreacted organic additive compound that is available for condensation with the aldehyde, thus reducing the amount of organic additive compound needed to achieve effective levels of aldehyde scavenging. Compounds with decomposition temperatures greater than 200xc2x0 C. as measured by Thermal Gravimetric Analysis (TGA) are most preferred. Compounds that decompose by intramolecular elimination reactions at temperatures less than about 200xc2x0 C. are less likely to be effective.
Examples of organic additive compounds that satisfy these parameters and that are effective at decreasing the aldehyde content of product in contact with polyolefins include anthranilamide, salicyclamide, salicylanilide, o-phenylenediamine, 3,4-diaminobenzoic acid, 1,8-diaminonaphthalene, o-mercaptobenzamide, N-acetylglycinamide, malonamide, 3-mercapto-1,2-propanediol, histidine, tryptophan, 4-amino-3-hydroxybenzoic acid, 4,5-dihydroxy-2,7-naphthalenedisulfonic acid disodium salt, biuret, 2,3-diaminopyridine, 1,2-diaminoanthraquinone, dianilinoethane, allantoin, 2-amino-2-methyl-1,3-propanediol, pentaerythritol, dipentaerythritol, and poly(vinyl alcohol). Preferred organic additive compounds include anthranilamide, 3,4-diaminobenzoic acid, malonamide, tryptophan, and allantoin. Anthranilamide and 3,4-diaminobenzoic acid are most preferred.
The amount of organic additive compound necessary to achieve the desired decrease in aldehyde content is dependent on which specific additive compound is used and the amount of reduction required. Organic additive compounds that are relatively more effective can achieve greater than 90% reduction in aldehyde content at loadings of between 200 and 500 ppm; additives that are relatively less effective may require addition levels up to 1000 ppm.
Using the Organic Additive Compound
The method of incorporating the organic additive compound into the polyolefin is not critical. For example, the organic additive compound can be dispersed in a liquid carrier which is then mixed with polyolefin pellets immediately before injection molding. The organic additive compound may also be incorporated by spraying a slurry of the additive in water onto the pellets prior to drying. In another embodiment, a melt or suspension of the organic additive compound is injected into pre-melted polyolefin. They also may be incorporated as a masterbatch pellet/pellet blend. The organic additive compound also may be incorporated by making a masterbatch of pellets of the additive compound with polyolefin and then mixing the masterbatch pellets with polyolefin pellets at the desired level before drying and injection.
The following equations illustrate the condensation reaction of suitable organic additive compounds described herein with an aldehyde (octanal) to form water and a resulting compound with an unbridged ring:
In the foregoing equations, X-H and Y-H represent functional groups including at least one active hydrogen represented by H and a heteroatom such as O, N, or S. In equation 3, R1 represents a ring which can be a 5- or 6-member ring and can be aromatic or nonaromatic.
Using the Polyolefin Composition
Containing the Organic Additive Compound
The composition comprising the polyolefin and the organic additive compound is, because of the reduced aldehyde content, particularly suitable for making containers such as a container for use in packaging beverages. With the reduced aldehyde content, the containers impart less of an off-taste to the beverages. This is particularly important for beverages, such as water, which do not have a strong flavor. Particularly preferred polyolefins for use in beverage packaging include polyethylene and polypropylene. Containers can be made with the polyolefin compositions described herein using conventional methods such as injection molding and blow molding. A typical method includes forming a preform with the polyolefin and organic additive compound, and then blow-molding the beverage container. The resulting containers can be used in the manufacture of package beverages according to conventional manufacturing methods.

Method to decrease aldehyde content in polyolefin products


The invention relates to a method of optimising heat exchanges between (i) a thermally-conductive absorbent plate (1) which is exposed to thermal radiation and a heat-transfer fluid (3) circulating in at least one thermally-conductive conduit tube (2) that is in thermal contact with the plate (1) and (ii) within the heat-transfer fluid (3). The invention is characterized in that, in order to promote heat exchanges, the method uses zones of the aforementioned plate (1) in order to form part of the wall of the conduit tube (2), such that the heat-transfer fluid (3) is in direct contact with the plate (1) so as to reduce the thermal resistance between the plate (1) and the heat-transfer fluid (3) circulating inside the conduit tube (2), said conduit tubes (2) being disposed on the two faces of the plate (1) and being interconnected by means of holes (4) that provided on the plate.

1. Field of the Invention
The object of the present invention is a method for providing optimum heat exchange within an assembly consisting of a heat-conducting absorbing plate and a heat transfer fluid flowing in at least one heat-conducting tubular conduit. It is notably, but not exclusively, applied to collectors of solar heat panels.
2. Description of the Prior Art
It is known that collectors of solar heat panels comprise:                a plate, generally in copper or in aluminum, the upper face of which is coated with a selective layer promoting absorption of solar light;        tubing having a circular shaped section which is welded on the lower face of said plate, this tubing generally being in copper or in aluminum;        a heat transfer liquid flowing in the tubing.
In this way, solar light incident on the upper face of said plate is converted into heat, the latter being conducted towards the welding area and then to the walls of the tubing so as to be transmitted to the heat transfer liquid which heats up while it passes in said tubing.
This device nevertheless has the following drawbacks:                transmission of heat from the wall of a tubing towards the heat transfer liquid is optimum when the temperature difference between said wall and the heat transfer liquid is large or, in the vicinity of the wall, the temperature of the heat transfer liquid is close to that of this wall;        as the heat transfer liquid is not as good a heat conductor as copper, transmission of the heat of the liquid located in the vicinity of the wall of a tubing towards the centre of the liquid is not optimum.
Thus, the flow of the heat transfer fluid in the tubing is laminar and the temperature distribution is not uniform, indeed, the temperature of the heat transfer liquid decreases from the upper layers located in proximity to the wall of a tube towards the centre of the liquid, consequently, the heat exchanges within the heat transfer liquid and between the tubing and the heat transfer liquid are not optimum.

Method for providing an optimum heat exchange within an assemby consisting of a heat-conducting absorbing plate and a heat transfer fluid


The present invention is a modular jack assembly which includes an outer insulative housing having top and bottom walls and opposed lateral walls while defining an interior section. This housing also has front and rear open ends. This assembly also includes an insulative insert having a top section, an upper side and a rear section having a base side and a recess. This jack is positioned so that the upper side of its top section is adjacent to top side of the insulative housing such that its terminal end extends into the interior section of the insulative housing and the rear section at least partially covers the rear open end of the insulative housing. This assembly also includes an electronic component mounted in the recess in the rear section of the insulative insert. A conductor is mounted in the electrical insert.

1. Field of the Invention
The present invention relates to electrical connectors and more particularly, to electrical connectors in which noise filter means are incorporated.
2. Brief Description of Prior Developments
In electronic appliances containing modular jacks, various types of filters are used to reduce or eliminate noise. Such filters may include a three terminal capacitor or a common mode choke coil. A disadvantage in the use of such filters is that they may complicate the production of the circuit board. A need, therefore, has been perceived for providing a simple means of filtering noise in modular jacks.
The use of an integral ferrite element for this purpose is proposed in Japanese Patent Publication 64-2273. This reference discloses a modular jack having a modular insert installed in a casing. The body of the insert is formed with ferrite, and on one side of the insert body insert holes are formed for introducing connecting lines to be connected to respective contact springs.
While this reference would appear to simplify the apparatus used for noise filtering in modular jacks, a need for further increasing the compactness of such modular jacks with integral ferrite elements exists.
U.S. Pat. No. 5,456,619 discloses a filtered modular jack assembly having an outer insulative housing with open front and rear sides. A ferrite element with vertical conductive wires is positioned adjacent the rear end, and an elongated insulative insert is superimposed over the ferrite element. The insulative insert is fixed to the housing, and the conductive wire extends vertically from the ferrite element over the upper side of the insert to its terminal end and then bends downwardly and rearwardly to rest on the top surface of an interior medial wall in the housing. While this reference discloses an invention which increases compactness, a need still exists for a jack which can achieve such compactness while using alternate types of filtering elements which are not adapted to be mounted in the same way as the ferrite element.


Disclosed is a method for producing monoethylene glycol, which is a method for producing ethylene glycol that comprises a carbonation step in which ethylene oxide is allowed to react with carbon dioxide in the presence of a carbonation catalyst thereby effecting formation of a reaction solution containing ethylene carbonate, a hydrolysis step in which the reaction solution is converted into an ethylene glycol aqueous solution by hydrolyzing ethylene carbonate in the reaction solution and a distillation step in which purified ethylene glycol and a catalyst solution containing the carbonation catalyst are obtained from the ethylene glycol aqueous solution by distillation, wherein the improvement resides in that the reaction is carried out in the presence of a carbonation catalyst using a bubble column reactor by supplying ethylene oxide, carbon dioxide and water into the reactor.

This invention relates to a method for the production of monoethylene glycol. More particularly, it relates to the improvement of a method in which monoethylene glycol is selectively produced from ethylene oxide via ethylene carbonate.
Monoethylene glycol is broadly used in polyester, polyurethane, non-freezing solution, cellophane, unsaturated polyester and the like.
Production of monoethylene glycol from ethylene oxide is generally carried out by hydrating to ethylene oxide in the absence of catalyst. The thus obtained hydration product is concentrated and then completely dehydrated by rectification while separating byproducts to obtain high purity monoethylene glycol.
In the hydration process of ethylene oxide, successive reaction of unreacted ethylene oxide with formed monoethylene glycol occurs and, as the result, diethylene glycol, triethylene glycol and more higher polyglycols are formed as by-products in addition to monoethylene glycol. In order to obtain monoethylene glycol most in demand with a high yield, it is necessary to supply large excess of water to reduce the successive reaction, generally from 10 to 25 moles of water based on 1 mole of ethylene oxide.
However, the addition of excess water for the purpose of improving the yield causes dilution of product in the formed solution, so that a large quantity of energy is required for removing the excess water in the distillation step.
In addition, the yield of monoethylene glycol obtained in this manner is merely around 90% which is not satisfactory.
In order to avoid such problems, a method has been proposed (JP-A-54-98765 (U.S. Pat. No. 4,314,945); the term "JP-A" as used herein means an "unexamined published Japanese patent application") in which monoethylene glycol is selectively obtained by producing ethylene carbonate from ethylene oxide and carbon dioxide (JP-A-57-31682) and then hydrolyzing ethylene carbonate (JP-A-55-154928 (U.S. Pat. No. 4,283,580)).
An advantage of this method is that the side reaction which generates diethylene glycol from monoethylene glycol and ethylene oxide does not occur and monoethylene glycol therefore is obtained with a markedly high yield, because the reaction for the formation of monoethylene glycol is carried out after ethylene oxide is once converted completely into ethylene carbonate.
However, the reaction for the production of ethylene carbonate from ethylene oxide is slow and requires isolation of ethylene oxide prior to the reaction.
As reactors for use in the production of the intermediate product ethylene carbonate, serial arrangement of a plurality of tube type reactors and condensers (Springmann, Fette Seifen Anstrichmittel, 73, 394-399 (1971)), a loop type reactor (Peppel, Industrial and Engineering, 50, 767-770 (1958)) and a bubble column reactor(JP-A-6-345699 (U.S. Pat. No. 5,508,442)) have been proposed.
Another method for the production of monoethylene glycol has also been proposed in which ethylene carbonate is used as the intermediate and the reaction is carried out by allowing water to coexist in advance in the reaction system [JP-A-54-19905 (U.S. Pat. No. 4,160,116), JP-A-49-86308 (U.S. Pat. No. 3,922,314), JP-B-49-24448 (the term "JP-B" as used herein means an "examined Japanese patent publication"), JP-A-55-145623]. In this method, a mixture of ethylene carbonate and monoethylene glycol is first obtained by allowing ethylene oxide to react with carbon dioxide in water and then the remaining ethylene carbonate is completely hydrolyzed, so that monoethylene glycol as the product of interest can be obtained with a high yield without supplying excess amount of water. When water is present in this manner, the ethylene carbonation can be carried out markedly quickly and thus industrially advantageously, and water-containing ethylene oxide can be used as the material as it is.
Since hydrolysis of ethylene carbonate as the subsequent step is also carried out simultaneously in this method, load of the hydrolysis step can be reduced and the process therefore can be minimized.
In addition, the process can be simplified by directly combining it with an ethylene oxide production process. In general, production of ethylene oxide is carried out by the following method. Firstly, ethylene is converted into ethylene oxide by subjecting it to gas phase catalytic oxidation with oxygen in the presence of a silver catalyst, the thus obtained ethylene oxide-containing gas is allowed to contact with a large volume of water to effect absorption of ethylene oxide contained in the reaction gas by water and then ethylene oxide is recovered in the form of aqueous solution. Next, the thus obtained dilute aqueous solution of ethylene oxide (the ethylene oxide concentration is generally from 1 to 5% by weight) is heated under a reduced pressure to effect stripping and separation of ethylene oxide from the aqueous solution and then ethylene oxide is recovered from the top part of the reaction column. The absorbing water after the removal of ethylene oxide is cooled and again recycled to the absorption treatment. Thereafter, the aqueous mixture containing ethylene oxide as the main component thus obtained by the stripping treatment is subjected to distillation to remove water and thereby isolating and purifying ethylene oxide.
An important point of this method is to carry out the ethylene carbonate formation sufficiently faster than the side reaction which forms diethylene glycol from ethylene oxide and monoethylene glycol. For this purpose, it is essential to supply carbon dioxide to the liquid phase quickly and sufficiently in carrying out this reaction. However, nothing is known about a reactor in which the supply of carbon dioxide can be carried out sufficiently quickly and industrially safely and efficiently.
In addition, this reaction for producing ethylene carbonate from ethylene oxide generates considerably large heat of reaction so that it easily causes run away reaction. As a matter of course, the run away reaction is a problem to be avoided by all means, because it causes decomposition of catalyst and increases formation of aldehyde and the similar by-products, thereby exerting sheer adverse influences upon the quality of the ethylene glycol product.
In the case of the multiple pipe type reactors which are frequently used for this purpose, the reaction is not stable because of the difficulty in supplying each reaction pipe with carbon dioxide uniformly and of the inability to sufficiently cool the gas phase inside the pipes due to separation of carbon dioxide and reaction solution therein, so that the reaction sometimes does not progress smoothly and sometimes progresses too rapidly to cause run away reaction. A vessel type reactor equipped with an agitator requires considerable agitation power which still cannot dissolve carbon dioxide sufficiently in some cases. In addition, this type of reactor is not desirable in treating the toxic and explosive ethylene oxide from the viewpoint of safety, because its bearing part has a rolling friction which possibly causes leakage of gas or combusting and explosive reactions of ethylene oxide due to the frictional heat.
An object of the present invention is to provide a method for carrying out the reaction for obtaining a mixture of ethylene carbonate and monoethylene glycol safely and efficiently, in the process of selectively producing monoethylene glycol by allowing ethylene oxide to react with carbon dioxide in the presence of a carbonation catalyst and water, thereby obtaining said mixture, and then hydrolyzing the remaining ethylene carbonate.
Taking such actual circumstances into consideration, the inventors of the present invention have conducted intensive studies and found as a result of the efforts that stable reactions can be carried out by the use of a bubble column reactor, without accumulation of the heat of reaction or run away reaction. The present invention has been accomplished on the basis of this finding.

Method for producing monoethylene glycol


A hybrid data communications cable includes optical fibers and insulated electrical conductors. The cable includes an elongated filler member having a central portion, walls extending radially from the central portion and a conduit running the length of the filler member. The optical fibers are enclosed within the conduit, and at least one insulated electrical conductor is separated from another insulated electrical conductor by one or more walls of the filler member. The cable further includes a jacket that encloses the filler member and the insulated electrical conductors.

1. Field of Invention
The present invention relates to hybrid cables having both optical and electrical transmission media.
2. Discussion
Fiber optic cables are increasingly used to transmit video, voice, and data. Optical fiber offers advantages of small size, lightweight, large bandwidth and high transmission data rates. Unlike traditional metal wire, optical fiber is immune to electromagnetic interference, which adversely affects transmission quality.
Although optical fiber often performs better than traditional metallic media, the telecommunications industry continues to purchase metal wire for many reasons. For example, existing telecommunications hardware is often incapable of sending and receiving optical transmissions without costly modification. Furthermore, even as the telecommunication industry upgrades to equipment that can send and receive optical signals, it continues to use hardware that depends on metal wire for signal transmission.
Consequently, there is a need for cables that can transmit both electrical and optical signals.
The present invention provides a novel hybrid data communications cable that can be efficiently manufactured without compromising the quality of electrical and optical signals transmitted by the cable.
The hybrid data communications cable includes a filler member having a longitudinal axis, and a conduit embedded in the filler member approximately parallel to the longitudinal axis. The filler member includes a central portion and walls extending radially from the central portion. The filler member, which is typically reinforced with elongated strength members or fillers, includes one or more optical fibers. The cable also includes a first and second group of insulated conductors that are separated from each other by at least one of the walls. Furthermore, the cable includes a jacket for housing the elongated filler member and the insulated electrical conductors.


A fluorooxyalkylene group-containing polymer composition including a liner fluorooxyalkylene group-containing polymer represented by the formula (1) which has a hydrolysable group at a terminal and is hereinafter called “one-terminal modified polymer”, and a liner fluorooxyalkylene group-containing polymer represented by the following formula (2) which has hydrolysable groups at the both terminals and is hereinafter called “both-terminal modified polymer”, wherein an amount of the both-terminal modified polymer is 0.1 mole % or more and less than 10 mole %, relative to a total mole of the one-terminal modified polymer and the both-terminal modified polymer.

Recently, there is an increasing need for technology to attain fingerprint proofness or easy removal of fouling on a surface of a display for better appearance or visibility. Thus, a material which meets these requirements is desired. In particular, a fingerprint smudge adheres easily to a surface of a touch panel display and, therefore, it is desired that a water- and oil-repellent layer is formed on the surface. However, a conventional water- and oil-repellent layer has a problem such that attrition resistance is poor so that the stain resistance deteriorate during use.
Compounds containing a perfluorooxyalkylene moiety generally have a very small surface free energy and, accordingly, have good water- and oil-repellency, chemical resistance, lubricity, releasing property, and antifouling property. Taking advantage of these properties, they are widely used as, for example, water- and oil-repellent agents or antifouling agents for paper or fiber, lubricants for magnetic storage media, oil repellents components for precision apparatuses, releasing agents, cosmetic, and protective coatings. These properties, on the other hand, mean that such compounds do not stick or closely adhere to other materials, either. Even if they can be applied to a material, it is difficult to have a coating closely adhered to the material.
Silane coupling agents are well known as an agent which bonds an organic compound to a surface of a substrate such as glass or a cloth. The silane coupling agents have an organic functional group and a reactive silyl group, usually an alkoxy silyl group, in a molecule. The alkoxy silyl group autocondenses in the presence of moisture in air to become a siloxane and forms a coating. At the same time, the alkoxy silyl group chemically and physically bonds to a surface of glass or metal to form a durable coating.
Japanese Patent Application Laid-Open No. Sho-58-167597 discloses that a fluoroaminosilane compound represented by the following formula is applied on glass to attain high water- and oil-repellency. However, the perfluorooxyalkylene moiety of this compound is relatively short, so that lubricity, a releasing property and an antifouling property are insufficient.

wherein R2 and R3 are alkyl groups having 1 to 4 carbon atoms, R1 is CH2CH2CH2 or CH2CH2NHCH2CH2CH2, h is an integer of from 0 to 8, and "i" is 2 or 3.
Japanese Patent Application Laid-Open No. 2000-143991 discloses perfluoropolyether-modified aminosilane represented by the following formula, as a compound having a branched long perfluorooxyalkylene moiety. The perfluoropolyether-modified aminosilane has a high water- and oil-repellency. However, its stain resistance and lubricity are insufficient due to the branch structure in the main chain.

wherein X is a hydrolyzable group, R4 is a monovalent hydrocarbon group, R6 is a hydrogen atom or a monovalent hydrocarbon group, R5 is an alkylene group optionally interrupted by an NH group, j is an integer of from 14 to 49, and k is 2 or 3.
Japanese Patent Application Laid-Open No. 2003-238577 discloses a perfluoropolyether-modified silane represented by the following formula, which has a liner perfluorooxyalkylene group. Lenses and anti-reflection films treated with the aforesaid perfluoropolyether-modified silane are good in lubricity, a releasing property and abrasion resistance. However, the lubricity intrinsic is not well exhibed due to the both terminals being fixed on a substrate.

wherein Rf is a divalent linear perfluoropolyether group, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, l is an integer of from 0 to 2, m is an integer of from 1 to 5, and a is 2 or 3.
Japanese Patent Application Laid-Open No. 2007-297589 discloses a perfluoropolyether-modified silane represented by the following formula, as a treatment agent which has improved lubricity. However, this compound does not have a terminal fluorinated group, so that its water- and oil-repellency, dynamic friction and releasing property are inferior.(Z2Q)βRf(QZ1Aα)2-β
wherein Rf is a divalent perfluoroether-containing group, Q is a divalent organic group, Z1 and Z2 are organopolysiloxane moieties, A is a monovalent group having a terminal reactive silyl group, α is an integer of from 1 to 8, and β is the number larger than 0 and less than 2.    Patent literature 1: Japanese Patent Application Laid-Open No. Sho-58-167597    Patent literature 2: Japanese Patent Application Laid-Open No. 2000-143991    Patent literature 3: Japanese Patent Application Laid-Open No. 2003-238577    Patent literature 4: Japanese Patent Application Laid-Open No. 2007-297589

Fluorooxyalkylene group-containing polymer composition, a surface treatment agent comprising the same and an article treated with the agent